JP5493276B2 - Method for producing metal fine particle array film and metal fine particle array film - Google Patents

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 have been many examples of research on organic / inorganic composites, and functional properties of organic polymers can be modified. Therefore, organic / inorganic composite materials in which inorganic materials are combined with organic polymers have been actively developed. Yes. Among them, it is known that a metal-arranged multilayer film in which metal fine particles are arranged in layers in a polymer exhibits electrically and optically useful characteristics (for example, Non-Patent Document 1). In conventional research, for example, when a metal complex is used as a precursor of metal fine particles, sublimated, and brought into contact with a block copolymer composed of two types of monomer units having different metal reducing ability under nitrogen, the metal complex Is selectively reduced only in one phase, and nano-level arrangement of metal fine particles is realized (for example, see Non-Patent Documents 2 to 4).

However, with regard to the arrangement of the metal fine particles in the reported polymer, the distribution (arrangement form) of each polymer in the copolymer is determined in a self-organized manner, and it is difficult to control the structure arbitrarily. There was a problem such as being.
Science 314, 1107 (2006) Langmuir, No. 19, 2963 (2003) Advanced Materials, No. 12, p. 1507 (2000) Nature 414, p.735 (2001) Optical Interference Coatings (OIC) Topical Meeting and Tabletop Exhibit (2007) Proceedings No. MC3 “A Facial, Novel Methodology for Preparation of Multilayer Metal / Polymer Composite Films”

  In view of the above, the inventors of the present invention have provided a method for manufacturing a metal fine particle array film by a general method that is simple and easy to use. Research has been carried out on a method for arranging in a non-patent document (for example, Non-Patent Document 5).

  However, the regularity of the metal fine particle arrangement may not be sufficiently high depending on the polymer type. The present invention has been made to solve this problem, and provides a method for producing a metal fine particle array film by a more versatile and simple method, and further, a wavelength-selective reflective film. The purpose is to provide.

The present inventor has conducted extensive studies and found that a significant effect of promoting alignment can be obtained by adding a small amount of a phosphorus-containing compound as an additive to a conventional polymer solution containing a metal component, thereby completing the present invention. That is, the disclosure items of the present application are summarized as follows.

1. (A) forming a polymer film containing a metal component and a phosphorus-containing compound as an additive on the reflective substrate;
And (B) irradiating the polymer film with light having a specific wavelength.

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

4). The above phosphorus-containing compound is characterized in that, in a spectrum measured by ³¹ P-NMR, a peak is observed in the range of chemical shift δ value of −170 to +150 ppm with 85 wt% phosphoric acid as a standard substance. The manufacturing method in any one of 1-3.

  5. 5. The production method according to any one of the above 1 to 4, wherein the phosphorus-containing compound is selected from the group consisting of phosphines, phosphites, and combinations thereof.

  6). The phosphorus-containing compound is triphenylphosphine, diphenyl (pentafluorophenyl) phosphine, tris (4-chlorophenyl) phosphine, tri (o-tolyl) phosphine and tris (2,4,6-trimethylphenyl) phosphine, triphenylphosphine. 6. The production method according to 5 above, wherein the production method is at least one selected from the group consisting of fights.

  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). 8. The method according to any one of 1 to 7 above, wherein the metal component contains metal fine particles.

  9. 8. The production method according to 7 above, wherein the metal compound is at least one selected from the group consisting of 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. The polymer is at least one selected from the group consisting of polymethacrylate, polyacrylate, polystyrene, polyvinylpyrrolidone, polymethacrylic acid, polyacrylic acid, a copolymer containing a methacrylic acid monomer unit or an acrylic acid monomer unit, and polyvinyl alcohol. 11. The production method according to any one of 1 to 10 above, which is a seed.

  12 A metal fine particle arrangement film produced by the method according to any one of 1 to 11 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.

  13. 13. A wavelength-selective reflective film using the metal fine particle array film described in 12 above.

  ADVANTAGE OF THE INVENTION According to this invention, the metal fine particle arrangement | sequence film which has the structure where the layer of the metal fine particle was periodically laminated | stacked multilayer can be produced with a versatile and 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.

  The method for producing a metal fine particle array film of the present invention includes a step (A) of forming a polymer film containing a metal component and a phosphorus-containing compound as an additive on a reflective substrate, and the polymer film has a specific wavelength. (B) irradiating with light of (λ). Details will be described below.

<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.

<Additives>
In the present invention, a phosphorus-containing compound as an additive is contained in the polymer together with the metal component. The phosphorus-containing compound is not particularly limited as long as it is a compound containing at least one phosphorus in the molecule, and a known compound can be used, but an organic compound is particularly preferable because of its high sequence promoting effect. Among these, in a spectrum measured by ³¹ P-NMR of a phosphorus-containing compound having an appropriate interaction with a metal component, a chemical shift δ value is preferably −200 to +210 ppm with 85 wt% phosphoric acid as a standard substance, More preferably, a compound in which a peak is observed in the range of −180 to +200 ppm, particularly preferably −170 to +150 ppm is preferably used. For compounds that do not meet this range, the interaction with the metal component is too strong, so that it forms a complex with the metal component and precipitates, making it difficult to uniformly dissolve or disperse the metal component and the polymer in the solvent. And there is a problem that the interaction with the metal component becomes weak and a sufficient alignment promoting effect may not be obtained.

  Furthermore, among these compounds, phosphines, phosphites, phosphates, phosphoranes and phosphine oxides are preferably used, although not limited thereto. These may be used as a mixture. In particular, phosphines, phosphites, and mixtures thereof are preferably used because of their high sequence promoting effect.

  Specifically, for example, as phosphines, for example, triphenylphosphine, tri (o-tolyl) phosphine, tri (4-trifluoromethylphenyl) phosphine, tri (4-methoxyphenyl) phosphine, tri (2-furyl) ) Phosphine, diphenylmethylphosphine, diphenylisopropylphosphine, diphenyl (pentafluorophenyl) phosphine, dimethylphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, dimethylphosphinoethane, diphenyl Phosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, diphenylphosphinoferrocene, tris (4-chloro Phenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, BINAP (2,2'-bis (diphenylphosphino) -1,1'-binaphthyl), and their derivatives.

Examples of phosphites include dimethyl phosphite, diethyl phosphite, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, triisodecyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite. 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite, tris (branched C _{3 -6} alkylphenyl) phosphites {e.g., tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di- t-Amylphenyl) phosphite Tris (2-t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) -phenyl] phosphite, tris [2,4- (1,1-dimethylpropyl) -phenyl] phosphite, etc. }, Bis (2-t-butylphenyl) phenyl phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2-t-butyl-4-phenylphenyl) phosphite, bis (C _3-9 alkylaryl) Pentaerythritol diphosphite {eg, bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol Diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (no Butylphenyl) pentaerythritol diphosphite} and derivatives thereof. These compounds may be contained alone or in combination of two or more.

  Of these compounds, triphenylphosphine, diphenyl (pentafluorophenyl) phosphine, tris (4-chlorophenyl) phosphine, tri (o-tolyl) phosphine and tris (2,4,6-trimethylphenyl) phosphine, Phenyl phosphite is preferably used because it is stable and easy to handle.

  The ratio of the additive to be contained in the polymer depends on the molecular weight of the polymer, but is, for example, 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 100 parts by weight of the polymer. Is about 1 to 20 parts by weight.

<Metal component>
The type of the metal element forming the “metal component” 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 the additive and a metal compound and / or metal fine particles to a reflective substrate is preferable, and a method of applying a polymer solution in which the additive and the metal compound are dissolved is particularly preferable. .

  The metal compound used in the present invention is one in which the metal compound is moved by irradiation with a specific wavelength λ to produce metal fine particles. 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, rhodium, 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) 2PPh 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. (CH ₃ C (O) CHC (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 C (} O) CHC (O) CH 3) 2 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) 2,} etc.], an organic salt (or complex) _[e.g., like _{(CH 3 C (O) CHC} (O) CH 3) 2 Pt, (C 6 H 5 CN) 2 PtCl 2] It is done.

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 C (O) CHC (O) CH ₃ ) ₂ Pd, (C ₆ H ₅ CN) ₂ PdCl ₂ , (CH ₃ CN) ₂ PdCl ₂ ], and the like.

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 ] 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 , carboxylates such as {[(CH ₃ ) ₃ CCO ₂ ] ₂ Rh} ₂ , (CH ₃ C (O) CHC (O) CH ₃ ) ₃ Rh] and the like.

  Among these metal compounds, in particular, silver salts and gold compounds are metal compounds that have high photosensitivity and are easily reduced by light, and silver perchlorate, silver nitrate, and chloroauric acid 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 proportion of the metal component contained in the polymer depends on the molecular weight of the polymer, but is, for example, 0.5 parts by weight or more, preferably 1 part by weight or more, and more preferably 5 parts by weight with respect to 100 parts by weight of the polymer. For example, it is about 500 parts by weight or less, preferably about 200 parts by weight or less, more preferably about 100 parts by weight or less, and still more preferably about 50 parts by weight or less.

<Polymer constituting polymer film and film formation of polymer film>
As the polymer constituting the polymer film, a polymer that is transparent at a specific wavelength λ and can contain (is particularly soluble) an additive and a metal component that are uniformly dissolved or dispersed 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, polyacrylate, polymethacrylic acid and polyacrylic acid, methylstyrene resin, acrylonitrile butadiene styrene (ABS ) Resin, styrene resin such as acrylonitrile styrene (AS) resin, polyolefin such as polyethylene, polypropylene and polymethylpentene, polyether such as polyoxetane, transparent polyamide such as nylon 6 and nylon 66, polystyrene , Polyvinyl chloride, polyethersulfone, polysulfone, polyacrylate and cellulose triacetate, polyvinyl alcohol, polyvinyl chloride Various materials including lupyrrolidone, polyacrylonitrile, polyvinyl chloride, cyclic polyolefin, acrylic resin, epoxy resin, cyclohexadiene polymer, amorphous polyester resin, transparent polyimide, transparent polyurethane, transparent fluororesin, thermoplastic elastomer, polylactic acid And transparent polymers. Further, copolymers of monomers that are constituents of these polymers (eg, copolymers containing methacrylic acid monomer units or acrylic acid monomer units) and / or mixtures of these polymers can also be used. Among these, a polymer selected from polymethacrylate, polyacrylate, polystyrene, polyvinylpyrrolidone, polymethacrylic acid, polyacrylic acid, a copolymer containing a methacrylic acid monomer unit or an acrylic acid monomer unit, and polyvinyl alcohol is preferably used. .

  The solvent is usually used to dissolve or disperse (especially dissolve) the polymer, additives and metal components. Such a solvent can be appropriately selected according to the type of polymer, additive and metal component, and includes, for example, water (which may be acidic, neutral or alkaline), alcohols (methanol, ethanol, propanol, isopropanol, butanol, Alkyl alcohols such as isobutanol), 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 (dialkyl ketones such as acetone and ethyl methyl ketone), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, celloso) Butacetate, butoxycarbitol acetate, etc.), cellosolves (methylcellosolve, ethylcellosolve, butylcellosolve, 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.

  Furthermore, the method for forming the polymer solution containing the additive and the metal component on the reflective substrate is not particularly limited as long as film formation is possible, and a conventional coating method such as a spin coating method (rotary coating method), Roll coating method, curtain coating method, dip coating method, casting method, 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 after the polymer solution containing the additive and the metal component is formed on the substrate is not particularly limited, and a conventional solvent distilling method, for example, evaporation by heating or vacuum drying by various evaporators can be used. Can be mentioned.

  Thus, the thickness of the polymer film containing the additive and the metal component formed on the reflective substrate is not particularly limited, and can be appropriately set 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 additive and 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, migration of metal compounds, 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 the light source for irradiation 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 high-pressure mercury lamp (irradiation intensity: 165 W / cm ² or more) is used, the irradiation time is 20 minutes to 20 hours, preferably 40 minutes to 15 hours, particularly preferably 1 hour. -10 hours.

<Metal fine particle alignment film>
By the light irradiation step, metal fine particles are generated from the metal compound in the additive and metal component-containing polymer film, or the metal fine particles move and densely form a layer parallel to the film surface. It becomes a periodic 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.

  It is presumed that the incident light and the reflected light interfere to generate a standing wave having a periodic light intensity distribution, so that the metal compound moves, and as a result, a multilayer structure is formed. Furthermore, it is presumed that by adding a phosphorus-containing compound into the system, the interaction between the polymer and the metal compound is affected, and the arrangement is promoted. 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 arbitrarily. 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. Therefore, at the time of manufacture, light having a wavelength suitable for obtaining a desired repetition distance (pitch). Can be selected. Therefore, it is 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 arbitrary control in this way. 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.

  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 of the present invention may be used in a state of being formed on a reflective substrate, or may be peeled from the reflective substrate. As a peeling method, depending on the adhesive strength with the reflective substrate, it may be mechanically peeled as it is, or a metal fine particle array film is impregnated with a solvent that does not cause dissolution, such as water, so that the adhesive property with the reflective substrate is improved. It is also preferable to peel after weakening. Moreover, it can also peel by the method as demonstrated in the following 2nd Embodiment.

{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, a polymer film containing an additive and a metal component is not directly formed on a reflective substrate, but 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, when the release layer itself is removed in a later step, the metal fine particle array film can be peeled off. 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 and polyacrylate, methyl styrene resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) Styrene resin such as resin, polyolefins such as polyethylene, polypropylene and 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 Olefin, 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, polystyrene 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 a 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, a casting method, or the like 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 way, a polymer film containing an additive and a metal component is formed on the release layer in the same manner as in the first embodiment, and a specific wavelength is formed. Irradiate light of λ. 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, for example, the film produced in Example 1 to be described later has a maximum value of reflection at a wavelength position almost coincident with the wavelength λ when irradiated with light, and the wavelength selective reflection. It became clear that it functions as a membrane.

By calculating the form in which a multilayer is laminated with a period of an optical distance d in a transparent layer, a metal layer (partial reflection / partial transparency) is calculated by simulation.
d = λ / 2
(Where d is the optical distance and λ is the reflected wavelength)
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.

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.

(Reference 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.

Example 1
A solution obtained by sequentially dissolving 15.8 mg of triphenylphosphine and 33.0 mg of silver perchlorate in 3.34 g of a tetrahydrofuran solution of 10 wt% polymethyl methacrylate was spin-coated on the reflective substrate prepared in Reference Example 1 (1500 rpm, 10 seconds) and then dried overnight at room temperature. Thereafter, an ultraviolet light having a wavelength of 365 nm is vertically applied to the thin film on the reflective substrate by using an ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd., “Multilight”) and a narrow band-pass filter. Irradiated for hours. The obtained sample was impregnated with water, and the metal fine particle array film was peeled from the reflective substrate.

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

(Comparative Example 1)
A solution obtained by dissolving 51.2 mg of silver perchlorate in 5.02 g of a 10 wt% polymethyl methacrylate tetrahydrofuran solution on the reflective substrate prepared in Reference Example 1 was spin-coated (1500 rpm, 10 seconds), and then room temperature. For 3.5 hours. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 6 hours to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (manufactured by USHIO INC., “Multi Light”) and a narrow band-pass filter. did.

  A transmission electron microscope (TEM) photograph of the obtained sample cross section is shown in FIG. The silver particles were dispersed in the polymer, and the arrangement regularity of the silver particles in the polymer was low. Furthermore, after irradiating light to the thin film on the produced reflective substrate under the same conditions as above, the obtained sample was impregnated with water, and the reflection spectrum of the metal fine particle array film peeled from the reflective substrate is shown in FIG. Shown in Only a slight maximum value of reflection was observed in the vicinity of the irradiation wavelength of 365 nm.

  As described above, by adding an appropriate phosphorus-containing compound, even in a system in which the regularity of the metal fine particles in the polymer is low in the conventional method, a metal fine particle array film having a high degree of regularity can be obtained.

(Example 2)
A solution obtained by dissolving 36.7 mg of triphenylphosphite and 58.1 mg of silver perchlorate in this order on 5.03 g of a 10 wt% polymethylmethacrylate tetrahydrofuran solution on the reflective substrate prepared in Reference Example 1 was spin-coated ( (1500 rpm for 10 seconds) and then dried overnight at room temperature. Thereafter, an ultraviolet light having a wavelength of 365 nm is vertically applied to the thin film on the reflective substrate by using an ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd., “Multilight”) and a narrow band-pass filter. Irradiated for hours. The obtained sample was impregnated with water, and the metal fine particle array film was peeled from the reflective substrate.

  The reflection spectrum of the obtained thin film is shown in FIG. The maximum value of reflection was shown in the vicinity of the irradiation wavelength of 365 nm.

(Example 3)
A solution obtained by sequentially dissolving 26.6 mg of diphenyl (pentafluorophenyl) phosphine and 59.4 mg of silver perchlorate in 5.00 g of a 10 wt% polymethylmethacrylate tetrahydrofuran solution on the reflective substrate prepared in Reference Example 1 was obtained. After spin coating (1500 rpm, 10 seconds), it was dried overnight at room temperature. Thereafter, an ultraviolet light having a wavelength of 365 nm is vertically applied to the thin film on the reflective substrate by using an ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd., “Multilight”) and a narrow band-pass filter. Irradiated for hours. The obtained sample was impregnated with water, and the metal fine particle array film was peeled from the reflective substrate.

  The reflection spectrum of the obtained thin film is shown in FIG. The maximum value of reflection was shown in the vicinity of the irradiation wavelength of 365 nm.

(Example 4)
A solution obtained by sequentially dissolving 27.6 mg of tris (4-chlorophenyl) phosphine and 57.0 mg of silver perchlorate in 5.00 g of a 10 wt% polymethylmethacrylate tetrahydrofuran solution on the reflective substrate prepared in Reference Example 1 was obtained. After spin coating (1500 rpm, 10 seconds), it was dried overnight at room temperature. Thereafter, an ultraviolet light having a wavelength of 365 nm is vertically applied to the thin film on the reflective substrate by using an ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd., “Multilight”) and a narrow band-pass filter. Irradiated for hours. The obtained sample was impregnated with water, and the metal fine particle array film was peeled from the reflective substrate.

  The reflection spectrum of the obtained thin film is shown in FIG. The maximum value of reflection was shown in the vicinity of the irradiation wavelength of 365 nm.

(Example 5)
A solution obtained by sequentially dissolving 20.5 mg of tri (o-tolyl) phosphine and 59.2 mg of silver perchlorate in 5.02 g of a 10 wt% polymethylmethacrylate tetrahydrofuran solution on the reflective substrate prepared in Reference Example 1 was obtained. After spin coating (1500 rpm, 10 seconds), it was dried overnight at room temperature. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 9 hours to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (manufactured by USHIO INC., “Multi Light”) and a narrow band-pass filter. did. The obtained sample was impregnated with water, and the metal fine particle array film was peeled from the reflective substrate.

  The reflection spectrum of the obtained thin film is shown in FIG. The maximum value of reflection was shown in the vicinity of the irradiation wavelength of 365 nm.

(Example 6)
Obtained by sequentially dissolving 21.2 mg of tris (2,4,6-trimethylphenyl) phosphine and 51.4 mg of silver perchlorate in 5.00 g of a 10 wt% polymethacrylate tetrahydrofuran solution on the reflective substrate prepared in Reference Example 1. The obtained solution was spin-coated (1500 rpm, 10 seconds) and then dried overnight at room temperature. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 9 hours to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (manufactured by USHIO INC., “Multi Light”) and a narrow band-pass filter. did. The obtained sample was impregnated with water, and the metal fine particle array film was peeled from the reflective substrate.

  The reflection spectrum of the obtained thin film is shown in FIG. The maximum value of reflection was shown in the vicinity of the irradiation wavelength of 365 nm.

2 is a TEM photograph of a metal fine particle array film produced in Example 1. FIG. It is a figure which shows the reflective characteristic of the metal microparticle arrangement | sequence film | membrane of Example 1. FIG. 4 is a TEM photograph of a metal fine particle array film produced in Comparative Example 1. It is a figure which shows the reflective characteristic of the thin film of the comparative example 1. It is a figure which shows the reflective characteristic of the metal fine particle arrangement | sequence film | membrane of Example 2. FIG. It is a figure which shows the reflective characteristic of the metal microparticle arrangement | sequence film of Example 3. FIG. It is a figure which shows the reflective characteristic of the metal microparticle arrangement | sequence film | membrane of Example 4. FIG. It is a figure which shows the reflective characteristic of the metal microparticle arrangement | sequence film of Example 5. It is a figure which shows the reflective characteristic of the metal microparticle arrangement | sequence film | membrane of Example 6.

Claims (12)

(A) forming a polymer film containing a metal component and a phosphorus-containing compound as an additive on the reflective substrate;
Wherein in a state where the polymer film is present on a reflective substrate, the polymer film, have a and step (B) for irradiating light of a specific wavelength,
In the step (B), a structure in which a layer in which metal fine particles are densely formed as a multilayer periodically exists in the film thickness direction of the polymer film is formed by light irradiation . The film forming step (A) of the polymer film includes a sub-step of forming a polymer solution containing the additive and a metal component on a reflective substrate, and a sub-step of distilling off the solvent. Item 2. The production method according to Item 1 . The spectrum of the phosphorus-containing compound measured by ³¹ P-NMR is characterized in that a peak is observed in the range of chemical shift δ value of −170 to +150 ppm with 85 wt% phosphoric acid as a standard substance. Item 3. The method according to Item 1 or 2 . The method according to any one of claims 1 to 3 , wherein the phosphorus-containing compound is selected from the group consisting of phosphines, phosphites, and combinations thereof. The phosphorus-containing compound is triphenylphosphine, diphenyl (pentafluorophenyl) phosphine, tris (4-chlorophenyl) phosphine, tri (o-tolyl) phosphine and tris (2,4,6-trimethylphenyl) phosphine, triphenylphosphine. The production method according to claim 4 , wherein the production method is at least one selected from the group consisting of fights. Said metal component, the manufacturing method according to any one of claims 1 to 5, characterized in that it comprises a metal compound which forms a being reduced metal particles by light of said specific wavelength. The process according to any one of claims 1 to 6, wherein said metal component, which comprises metal fine particles. The method according to claim 6 , wherein the metal compound is at least one selected from the group consisting of silver perchlorate, silver nitrate, and chloroauric acid. The production method according to any one of claims 1 to 8 , wherein a polymer constituting the polymer film is transparent at least at the specific wavelength. The polymer is at least one selected from the group consisting of polymethacrylate, polyacrylate, polystyrene, polyvinylpyrrolidone, polymethacrylic acid, polyacrylic acid, a copolymer containing a methacrylic acid monomer unit or an acrylic acid monomer unit, and polyvinyl alcohol. the process according to any one of claims 1 to 9, characterized in that it is a seed. It is a method in any one of Claims 1-10 , Comprising: It manufactures by the method of irradiating the light of the specific wavelength which exists in the range of 200-600 nm in the said process (B) , A metal microparticle is in a polymer film. A metal fine particle array film having a structure in which dense layers are periodically present as multilayers in the film thickness direction. A wavelength-selective reflective film using the metal fine particle array film according to claim 11 .