CN105017562A - Process for producing metal nanoparticle composite - Google Patents

Process for producing metal nanoparticle composite Download PDF

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Publication number
CN105017562A
CN105017562A CN201510297230.3A CN201510297230A CN105017562A CN 105017562 A CN105017562 A CN 105017562A CN 201510297230 A CN201510297230 A CN 201510297230A CN 105017562 A CN105017562 A CN 105017562A
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China
Prior art keywords
metal
polyimide precursor
particle
precursor resin
gold
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CN201510297230.3A
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Chinese (zh)
Inventor
新田龙三
松村康史
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical Co Ltd
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Publication of CN105017562A publication Critical patent/CN105017562A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/46—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals

Abstract

A process for producing a metal nanoparticle composite wherein metal nanoparticles having a mean particle diameter of 3nm or more are each independently dispersed in a polyimide resin in such a manner that the metal nanoparticles are not in contact with each other and that adjacent nanoparticles are present with a space therebetween, said space being equal to or larger than the larger of the particle diameters of the adjacent metal nanoparticles. The process includes: (a) a step of applying a coating fluid which comprises both a polyimide precursor resin and a metal compound to a substrate so as to give a metal content of 50[mu]g/cm2 or less, and drying the resulting coating to form a coating film which has a dry film thickness of 1.7[mu]m or less; and (b) a step of heat-treating the coating film at a temperature of 160 to 450 DEG C not only to reduce the metal ions (or metal salt) contained in the coating film and make the resulting particulate metal (which acts as the metal nanoparticles) deposited and dispersed in the coating film but also to convert the polyimide precursor resin into a polyimide resin and thus form a polyimide resin layer which has a thickness of 1[mu]m or less and an elastic modulus of 10GPa or less.

Description

The manufacture method of Metal microparticle composite
The Chinese application number that the application is the applying date is on July 22nd, 2011, denomination of invention is " manufacture method of Metal microparticle composite " is the divisional application of 201180038553.0.
Technical field
The present invention relates to the manufacture method being dispersed with the Metal microparticle composite of metal particle in by the matrix that polyimide resin is formed.
Background technology
Local surface plasma resonance (Local Surface Plasmon Resonance; LSPR) be that the light of electronics in the metal particle of several nm ~ 100nm side-to-side dimensions or metal superfine structure and specific wavelength occurs to interact and the phenomenon resonated.Local surface plasma resonance is applied to already by the internal mix metal particle at glass and presents in the tinted shade of bright-colored.In recent years, studying such as make use of the effect strengthening light intensity high-output power emitting laser exploitation or make use of molecular linkage time the resonance state biosensor of character that changes etc. in application.
In order to be applied in sensor by the local surface plasma resonance of this metal particle, to need in the matrix such as synthetic resins stably fixing metal particulate.But metal particle aggegation dispersing characteristic when becoming nano-scale can change, the decentralized stabilization such as caused by electrostatic repulsion effect becomes difficult and easily aggegation occurs.Therefore, for the plasma device utilizing local surface plasma resonance, importantly how the metal particle in matrix can be disperseed with uniform state.
As the technology relevant to the manufacture method being fixed with the Metal microparticle composite of metal particle in the matrix such as resin, such as, propose following patent documentation 1 ~ 4.In patent documentation 1, the good polymer composite that thus Young's modulus is high of cementability of, dispersion of particles little as particle and particle and matrix, disclose a kind of by relative to thermoplasticity or thermosetting polymer substrate with volume fraction be 0.005 ~ 0.01% to disperse equably, fill particle diameter be the metallics of 10 ~ 20 dusts, the polymer-metal cluster complex body of Young's modulus raising.But the manufacture method of patent documentation 1 is difficult to make the complex body that particle diameter is the metal particle of more than tens nanometer level.
Patent Document 2 discloses a kind of manufacture method of microparticle dispersion, it can be used in replacing the formation of novel conductive cell envelope of electroless plating method and the dispersion of the metal particle of granular magnetic thin films to obtain, after resin base material containing ion-exchange group is contacted with the solution containing metal ion, reduce in the gas phase.In the method, because when carrying out hydrogen reduction, metal ion, while to the internal divergence of resin while react, does not therefore exist metal particle in the degree of depth of the surface of resin base material to tens nanometer (being 80nm the embodiment of patent documentation 2).In addition, in manufacture method disclosed in patent documentation 2, contact with the solution containing metal ion by making the resin base material containing ion-exchange group, thus absorption and be combined on the ion-exchange group that contains in matrix resin, therefore the content of metal ion is restricted, and be immobilized because metal ion utilizes ion-exchange group, be thus also difficult to the metal particle making the particle diameter with enough sizes.
Patent Document 3 discloses a kind of following method: the polyimide resin film having been imported carboxyl by alkali aqueous solution process is contacted thus in resin molding after doped metal ion with the solution containing metal ion, more than the reduction temperature of metal ion, the 1st thermal treatment is carried out in reducing gas, be formed in polyimide resin the layer being dispersed with metal nanoparticle, and then at the temperature being different from the 1st thermal treatment temp, carry out the 2nd thermal treatment.Describe following content in patent documentation 3: by the 2nd thermal treatment, the thickness of adjustable metal nanoparticle dispersion layer, thus control the volumetric filling ratio of the metal nanoparticle in composite membrane.But, in the same manner as patent documentation 2, for particle diameter, owing to being the mode by absorption and the reducing metal ions be combined on the ion-exchange group that contains in matrix resin being formed metal particle, therefore the content of metal ion is restricted, and be immobilized because metal ion utilizes ion-exchange group, be thus difficult to make the metal particle of the particle diameter with enough sizes.
Patent documentation 4 discloses following method: in order to solve make metallics be scattered in polymer matrix process in the problem such as consistency, surface imperfection, interparticle compendency of polymer matrix, metal precursor is scattered in after in the matrix of polymer substance with molecular level, and metal precursor is carried out photoreduction by irradiation ultraviolet radiation.But the method for patent documentation 4, owing to making metal particle separate out by ultraviolet reduction, is therefore subject to the impact in uviolizing face, the precipitation density gradient of metal particle can be produced in the skin section of matrix and deep.That is there is following tendency: go deep into along with from the skin section of matrix to deep, particle diameter and the filling proportion of metal particle reduce continuously.In addition, the particle diameter of the metal particle obtained by photoreduction in uviolizing face namely the skin section of matrix reach maximum, but maximum also with regard to tens ran, and be difficult to make that there is metal particle that is equal with this particle diameter or its above particle diameter and be dispersed to deep.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 8-16177 publication
Patent documentation 2: Japanese Patent No. 3846331 publication
Patent documentation 3: Japanese Patent No. 4280221 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-179931 publication
Summary of the invention
The technical problem that invention will solve
When Metal microparticle composite Medium Culture being dispersed with metal particle is applied in the sensor purposes utilizing local surface plasma resonance, importantly at least the intensity of absorption spectrum wants large.In addition, usual absorption spectrum is more sharp-pointed, more can detect in high sensitivity.In order to obtain the large and sharp-pointed absorption spectrum of intensity, Metal microparticle composite needs to possess such as such as the following structural performance:
1) size of metal particle is controlled in the scope of regulation;
2) shape of metal particle is even;
3) metal particle and adjacent metal particle are separated from each other to keep the state at certain above particle interval;
4) metal particle is controlled within a certain range relative to the volume filling proportion of Metal microparticle composite;
5) metal particle is nascent from the skin section of matrix while, also keeps the spacing of particle specified liftoffly to disperse equably in the thickness direction thereof.
The present invention be directed to the unsolved above-mentioned technical problem of prior art to propose, its object is to provide the metal particle of the particle diameter had in specialized range mutually not aggegation and the manufacture method of Metal microparticle composite of disperseing independently.
For the means of technical solution problem
The present inventor conducts in-depth research in view of the above fact, found that: by controlling the thickness of amount of metal and the polyimide resin based matter contained in polyimide resin and the Metal microparticle composite of heat-treating with the temperature in specified range and obtaining meets above-mentioned requirements, thus complete the present invention.
Namely; the manufacture method of Metal microparticle composite of the present invention manufactures following Metal microparticle composite, and described Metal microparticle composite is that the metal particle being more than 3nm by median size is not in contact with each other and is dispersed in independently of each other in polyimide resin with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate.The manufacture method of this Metal microparticle composite possesses following operation a and b:
A) operation: the coating fluid containing polyimide precursor resin and metallic compound is reached 50 μ g/cm with the content of metal ingredient 2following mode is coated on base material, carries out drying, forms the coated film that dried thickness is less than 1.7 μm;
B) operation: by heat-treating at the temperature of above-mentioned coated film more than 160 DEG C and in the scope of less than 450 DEG C, the particle shape metal becoming metal particle is separated out in metal ion (or metal-salt) reduction in above-mentioned coated film, and make it be dispersed in coated film, meanwhile the above-mentioned polyimide precursor resin in above-mentioned coated film is carried out imidization, formation thickness is less than 1 μm and Young's modulus is the polyimide resin layer of below 10GPa.
In the 1st optimal way of the manufacture method of Metal microparticle composite of the present invention, in above-mentioned Metal microparticle composite, the median size of above-mentioned metal particle can be more than 3nm and in the scope of below 25nm, and the volume fraction of above-mentioned metal particle can be more than 0.05% relative to Metal microparticle composite and in the scope of less than 1%.In this case, the content of the metal ingredient in the above-mentioned coating fluid in above-mentioned operation a can be 0.5 μ g/cm 2above and 10 μ g/cm 2in following scope, and the thickness of dried above-mentioned coated film can be more than 500nm and in the scope of less than 1.7 μm.And then the thickness of above-mentioned polyimide resin layer in above-mentioned operation b can be more than 300nm and in the scope of less than 1 μm.
In the 2nd optimal way of the manufacture method of Metal microparticle composite of the present invention, in above-mentioned Metal microparticle composite, the median size of above-mentioned metal particle can be more than 3nm and in the scope of below 30nm, and the volume fraction of above-mentioned metal particle can be more than 0.2% relative to Metal microparticle composite and in the scope of less than 5%.In this case, the content of the metal ingredient in the above-mentioned coating fluid in above-mentioned operation a can be 10 μ g/cm 2above and 50 μ g/cm 2in following scope, and the thickness of dried above-mentioned coated film can be more than 500nm and in the scope of less than 1.7 μm.And then the thickness of the above-mentioned polyimide resin layer in above-mentioned operation b can be more than 300nm and in the scope of less than 1 μm, and the Young's modulus of above-mentioned polyimide resin layer can be more than 3GPa and in the scope of below 10GPa.
In the 3rd optimal way of the manufacture method of Metal microparticle composite of the present invention, in above-mentioned Metal microparticle composite, the median size of above-mentioned metal particle can be more than 3nm and in the scope of below 30nm, and the volume fraction of above-mentioned metal particle can be more than 0.5% relative to Metal microparticle composite and in the scope of less than 5%.In this case, the content of the metal ingredient in the above-mentioned coating fluid in above-mentioned operation a can be 5 μ g/cm 2above and 10 μ g/cm 2in following scope, and the thickness of dried above-mentioned coated film can be more than 150nm and in the scope of below 500nm.And then the thickness of the above-mentioned polyimide resin layer in above-mentioned operation b can be more than 100nm and in the scope of below 300nm, and the Young's modulus of above-mentioned polyimide resin layer can be more than 5MPa and in the scope of below 10GPa.
In the 4th optimal way of the manufacture method of Metal microparticle composite of the present invention, in above-mentioned Metal microparticle composite, the median size of above-mentioned metal particle can be more than 5nm and in the scope of below 35nm, and the volume fraction of above-mentioned metal particle can be more than 1% relative to Metal microparticle composite and in the scope of less than 15%.In this case, the content of the metal ingredient in the above-mentioned coating fluid in above-mentioned operation a can be 10 μ g/cm 2above and 30 μ g/cm 2in following scope, and the thickness of dried above-mentioned coated film can be more than 150nm and in the scope of below 500nm.And then the thickness of the above-mentioned polyimide resin layer in above-mentioned operation b can be more than 100nm and in the scope of below 300nm, and the Young's modulus of above-mentioned polyimide resin layer can be more than 0.5GPa and in the scope of below 10GPa.
In addition, in the manufacture method of Metal microparticle composite of the present invention, above-mentioned operation b can carry out in inertness gas atmosphere.
In addition, in the manufacture method of Metal microparticle composite of the present invention, above-mentioned metallic compound can be the precursor of Au.
Invention effect
The manufacture method of Metal microparticle composite of the present invention due to be in the inside of polyimide precursor resin from the state reduction of metal ion (or metal-salt) precipitating metal particulate, thus easily regulate the content of the metallic compound in polyimide precursor resin, be easy to regulate the content of the metal particle be dispersed in polyimide resin.Therefore, it is possible to manufacturing median size is with comparalive ease that the metal particle of more than 3nm is not in contact with each other and is dispersed in the Metal microparticle composite in polyimide resin with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate independently of each other.And, because its reduction treatment utilizes heating to carry out, therefore, it is possible to utilize the thermodiffusion of metal particle of separating out make metal particle with keep certain above spacing of particle from state be dispersed in matrix resin, and separate loose metal particle with certain above spacing of particle and come into existence from the skin section of matrix resin.
In addition, in the manufacture method of Metal microparticle composite of the present invention, utilize the heat used in reduction treatment can also complete the imidization of polyimide precursor resin, thus can simplify production process.
The Metal microparticle composite manufactured by the inventive method, owing to possessing said structure characteristic, thus can be applied to utilize in that the fields such as the pressure transmitter of local surface plasma effect are representative, the various industrial circle such as such as electromagnetic shielding material, magnetic noise absorbing material, high thermal conductive resin material.
Embodiment
Then, embodiments of the present invention are described in detail.The manufacture method of the Metal microparticle composite of embodiments of the present invention is the manufacture method of the Metal microparticle composite manufacturing following Metal microparticle composite, and described Metal microparticle composite is that the metal particle being more than 3nm by median size is not in contact with each other and is dispersed in independently of each other in polyimide resin with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate.The method possesses following operation a and b.
A) operation: the coating fluid containing polyimide precursor resin and metallic compound is reached 50 μ g/cm with the content of metal ingredient 2following mode is coated on base material, carries out drying, forms the coated film that dried thickness is less than 1.7 μm.
B) operation: by heat-treating above-mentioned coated film at the temperature more than 160 DEG C and in the scope of less than 450 DEG C, the particle shape metal becoming metal particle is separated out in metal ion (or metal-salt) reduction in above-mentioned coated film, and make it be dispersed in coated film, meanwhile the above-mentioned polyimide precursor resin in above-mentioned coated film is carried out imidization, formation thickness is less than 1 μm and Young's modulus is the polyimide resin layer of below 10GPa.
Below, with the median size of metal particle and volume fraction for benchmark, be divided into and preferred embodiment the inventive method be described.In addition, so-called " volume fraction " is the value of the total volume representing metal particle shared in every certain volume of Metal microparticle composite with percentage.
[the 1st embodiment]
The manufacture method of the Metal microparticle composite of the 1st embodiment of the present invention is the method manufacturing following Metal microparticle composite, described Metal microparticle composite be by median size be 3nm ~ 25nm scope in metal particle be not in contact with each other and with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate independently of each other (preferably completely independently) be dispersed in polyimide resin, and the volume fraction of metal particle is more than 0.05% relative to Metal microparticle composite and in the scope of less than 1%, aforesaid method possesses following operation a and operation b.Here, polyimide resin is to heat the polyimide resin making it dewater and cyclization occur and obtains after carrying out imidization to polyimide precursor resin.Compared with the heat-curing resins such as polyimide resin and other synthetic resins such as epoxy resin, resol, acrylic resin, there is the character of thermotolerance and excellent in dimensional stability, thus preferably use.In addition, polyimide resin, owing to heat-treating in the process forming metal particle, is also thus favourable in the thermotolerance at least 160 DEG C of temperature having.
[operation a; Coated film formation process]
In the manufacture method of the Metal microparticle composite of present embodiment, by by the coating solution containing polyimide precursor resin and metallic compound on base material, carry out drying, thus formed coated film.
As the base material used in operation a, be not particularly limited, such as, can be the film (sheet) of polyimide resin, in addition also can enumerate tinsel, sheet glass, resin molding, pottery etc.Utilizing the Metal microparticle composite of the manufacture method manufacture of present embodiment can peel off from base material, also can be the state of the former state with base material.Such as, when utilizing the local surface plasma resonance of Transmission light system under the Metal microparticle composite of present embodiment manufacture is with the state of the former state with base material, base material is preferably transmitance, such as, can use glass substrate, transparent synthetic resins substrate etc.As transparent synthetic resins, such as, can enumerate polyimide resin, PET resin, acrylic resin, MS resin, MBS resin, ABS resin, polycarbonate resin, silicone resin, silicone resin, epoxy resin etc.
As precursor and the polyimide precursor resin of polyimide resin, the known polyimide precursor resin obtained by known acid anhydrides and diamines can be used.Polyimide precursor resin is such as by making tetracarboxylic dianhydride and diamines within 30 minutes ~ 24 hours, carry out polyreaction roughly etc. mole to dissolve in organic solvent and to stir at temperature within the scope of 0 ~ 100 DEG C and obtain.When reacting, should to reach in organic solvent in the scope of 5 ~ 30 % by weight with the polyimide precursor resin of gained, preferably the mode reached in the scope of 10 ~ 20 % by weight carry out solubilizing reaction composition.About the organic solvent used in polyreaction, the organic solvent with polarity should be used, as organic polar solvent, such as N can be enumerated, dinethylformamide, N,N-dimethylacetamide (DMAc), METHYLPYRROLIDONE, 2-butanone, dimethyl sulfoxide (DMSO), methyl-sulfate, pimelinketone, diox, tetrahydrofuran (THF), diglyme, triglyme etc.These solvents can also two or more and be used for using, and then a part can also use the aromatic hydrocarbons of dimethylbenzene, toluene and so on.
The polyimide precursor resin of synthesis uses with the form of solution.Usually, it is favourable for using as reaction solvent solution, but can carry out the organic solvent concentrating, dilute or be replaced as other as required.Namely the solution of preparation like this can be used as coating fluid by interpolation metallic compound and utilize.
Polyimide precursor resin preferably contains the polyimide resin of thermoplasticity or low heat expansion property mode with the polyimide resin after imidization is selected.In addition, as polyimide resin, such as, can enumerate the heat-resistant resin be made up of the polymkeric substance that in the structures such as polyimide, polyamidoimide, polybenzimidazole, polyester-imides, polyetherimide, polysiloxane acid imide, there is imide.
As the diamines preferably used in the preparation of polyimide precursor resin, such as can enumerate 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 4,4 '-diamino-diphenyl ether, 2 '-methoxyl group-4,4 '-diaminobenzene formylaniline, 1, two (4-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene of 3-, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline etc.In addition, as diamines, 2,2-pair-[4-(3-amino-benzene oxygen) phenyl] propane can be shown preference, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen)] biphenyl, two [4-(3-amino-benzene oxygen) biphenyl, two [1-(4-amino-benzene oxygen)] biphenyl, two [1-(3-amino-benzene oxygen)] biphenyl, two [4-(4-amino-benzene oxygen) phenyl] methane, two [4-(3-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(3-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen)] benzophenone, two [4-(3-amino-benzene oxygen)] benzophenone, two [4,4 '-(4-amino-benzene oxygen)] benzanilide, two [4,4 '-(3-amino-benzene oxygen)] benzanilide, two [4-(4-amino-benzene oxygen) phenyl] fluorenes of 9,9-, two [4-(3-amino-benzene oxygen) phenyl] fluorenes of 9,9-etc.
As other diamines, such as, can enumerate 2,2-pair-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-pair-[4-(3-amino-benzene oxygen) phenyl] HFC-236fa, 4,4 '-methylene radical two Ortho Toluidine, 4,4 '-methylene radical two-2,6-xylidine, 4,4 '-methylene radical-2,6-Diethyl Aniline, 4,4 '-diamino-diphenyl propane, 3,3 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl ethane, 3,3 '-diamino-diphenyl ethane, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino diphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl ether, 3,3-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, p-diaminodiphenyl, 3,3 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy benzidine, 4,4 "-diamino-p-terphenyl, 3,3 "-diamino p-terphenyl, mphenylenediamine, Ursol D, DAP, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethylidene)] dianiline, 4,4 '-[1,3-phenylene two (1-methyl ethylidene)] dianiline, bis(p-aminocyclohexyl) methane, two (to beta-amino-tert-butyl-phenyl) ether, two (to Beta-methyl-δ-Aminopentyl) benzene, to two (2-methyl-4-Aminopentyl) benzene, to two (1,1-dimethyl-5-Aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, two (beta-amino-tertiary butyl) toluene of 2,4-, 2,4 di amino toluene, m-xylene-2,5-diamines, p-Xylol-2,5-diamines, MXDP, terephthaldehyde's base diamines, DAP, 2,5-diamino-pyridine, 2,5-diaminostilbene, 3,4-oxadiazole, piperazine etc.
As particularly preferred diamine component, can enumerate and be selected from 2, 2 '-bis-(trifluoromethyl)-4, 4 '-benzidine (TFMB), 2, 2 '-dimethyl-4, 4 '-benzidine (m-TB), 1, two (the 4-amino-benzene oxygen)-2 of 3-, 2-dimethylpropane (DANPG), 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-, 1, two (3-amino-benzene oxygen) benzene (APB) of 3-, Ursol D (p-PDA), 3, 4 '-diamino-diphenyl ether (DAPE34), 4, the diamines of more than a kind in 4 '-diamino-diphenyl ether (DAPE44).
As the acid anhydrides preferably used in the preparation of polyimide precursor resin, such as, can enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 4, the two Tetra hydro Phthalic anhydride of 4 '-oxygen.In addition, as acid anhydrides, also 2 can be illustrated, 2 ' by preference, 3,3 '-, 2,3,3 ', 4 '-or 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3 ', 3,4 '-diphenyl ether tetracarboxylic dianhydride, two (2,3-dicarboxyphenyi) ether dianhydride etc.And then, as acid anhydrides, also can illustrate 3 by preference, 3 "; 4,4 "-, 2,3,3 "; 4 "-or 2,2 ", 3,3 "-p-terphenyl tetracarboxylic dianhydride, 2,2-two (2,3-or 3,4-dicarboxyphenyi) propane dianhydride, two (2,3-or 3,4-dicarboxyphenyi) methane dianhydride, two (2,3-or 3,4-dicarboxyphenyi) sulfone dianhydride, 1, two (2,3-or 3,4-dicarboxyphenyi) ethane dianhydrides of 1-etc.
As particularly preferred acid anhydrides, can enumerate and be selected from pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 4, the two Tetra hydro Phthalic anhydride (ODPA), 3 of 4 '-oxygen, 3 ', 4, the acid anhydrides of more than a kind in 4 '-sulfobenzide tetracarboxylic dianhydride (DSDA).
Diamines, acid anhydrides only can use wherein a kind respectively, and also two or more kinds may be used uses.In addition, can also also with diamines than that described above and acid anhydrides.
In the present embodiment, in order to prepare polyimide precursor resin solution, as the solution containing polyimide precursor resin, also preferably commercially available product can be used.As thermoplastic polyimide precursor resin solution, such as, can enumerate ト レ ニ ー ス #3000 (trade(brand)name) etc. of thermoplastic polyimide precursor resin varnish SPI-200N (trade(brand)name) of Nippon Steel Chemical Co., Ltd, thermoplastic polyimide precursor resin varnish SPI-300N (trade(brand)name), thermoplastic polyimide precursor resin varnish SPI-1000G (trade(brand)name), Dongli Ltd..In addition, as the polyimide precursor resin solution of non-thermal plasticity, such as, can enumerate non-thermal plasticity polyimide precursor resin varnish U-Vanish-A (trade(brand)name) of Ube Industries, Ltd, non-thermal plasticity polyimide precursor resin varnish U-Vanish-S (trade(brand)name) etc.
When the Metal microparticle composite manufactured in present embodiment is such as applied to the purposes of the local surface plasma resonance utilizing Transmission light system, as presenting transparent or colourless polyimide resin, preferred use is difficult to be formed in molecule, the polyimide resin of intermolecular charge transfer (CT) complex compound, the substituent aromatic polyimide resin such as with bulky three-dimensional arrangement, ester ring type polyimide resin, fluorine system polyimide resin, silicon system polyimide resin etc.
As the substituting group of above-mentioned bulky three-dimensional arrangement, such as, fluorene skeleton, adamantane framework etc. can be enumerated.The substituting group of this bulky three-dimensional arrangement can the anhydride residue in substituted aromatic polyimide resin or any one in diamines residue or replace both anhydride residue and diamines residue.As the substituent diamines with bulky three-dimensional arrangement, such as, can enumerate two (4-aminophenyl) fluorenes of 9,9-etc.
Ester ring type polyimide resin refers to and ester ring type acid anhydrides and ester ring type diamines is carried out being polymerized and the resin formed.In addition, ester ring type polyimide resin is also by carrying out hydrogenation to obtain by aromatic polyimide resin.
Fluorine system polyimide resin is the resin that the acid anhydrides that obtains after being replaced by fluorine, perfluoroalkyl, perfiuoroaryl, perfluoro alkoxy, perfluor phenoxy group etc. by the 1 valency element be such as bonded on the carbon such as alkyl, phenyl and/or diamines carry out being polymerized and formed.All or part of fluorine system polyimide resin be substituted of 1 valency element all can use, but the preferred fluorine system polyimide resin that is replaced by fluorine atoms of the 1 valency element of more than 20%.
Silicon system polyimide resin refers to the resin carrying out silicon system diamines and acid anhydrides to be polymerized rear acquisition.
This clear polyimides resin preference is as when the thickness of 10 μm, the optical transmittance at wavelength 400nm place is more than 80%, visible ray average transmittance is more than 90%.
In above-mentioned polyimide resin, the fluorine system polyimide resin that particularly preferably transparency is excellent.As fluorine system polyimide resin, the polyimide resin with the structural unit shown in general formula (1) can be used.Here, in general formula (1), Ar 1expression (2), formula (3) or 4 valency aromatic groups shown in formula (4), Ar 2expression (5), formula (6), formula (7) or the divalent aromatic group shown in formula (8), p represents the repeat number of structural unit.
In addition, R represents fluorine atom or perfluoroalkyl independently, and Y represents the divalent group shown in following structural formula, R 1represent perfluorinated alkylidene, n represents the number of 1 ~ 19.
In above-mentioned general formula (1), Ar 2can be described as the residue of diamines, Ar 1can be described as the residue of acid anhydrides, therefore enumerate diamines and acid anhydrides or the tetracarboxylic acid, acyl chlorides, carboxylate etc. (being designated as below " acid anhydrides etc. ") that can utilize on an equal basis with it illustrate preferred fluorine system polyimide resin.But fluorine system polyimide resin is not limited to the fluorine system polyimide resin obtained by the diamines illustrated and acid anhydrides etc. here.
As becoming Ar 2the diamines of raw material, as long as be bonded to the alkyl except intramolecular amino, all 1 valency elements on the carbon such as phenyl ring are the diamines of fluorine or perfluoroalkyl, it can be arbitrary diamines, such as can enumerate 3, 4, 5, 6,-four fluoro-1, 2-phenylenediamine, 2, 4, 5, 6-tetra-fluoro-1, 3-phenylenediamine, 2, 3, 5, 6-tetra-fluoro-1, 4-phenylenediamine, 4, 4 '-diamino octafluorobiphenyl, two (2, 3, 5, the fluoro-4-aminophenyl of 6-tetra-) ether, two (2, 3, 5, the fluoro-4-aminophenyl of 6-tetra-) sulfone, hexafluoro-2, 2 '-bis trifluoromethyl-4, 4 '-benzidine, 2, two (trifluoromethyl)-4 of 2-, 4 '-benzidine etc.
As becoming Ar 1the acid anhydrides etc. of raw material, such as can enumerate 1, 4-difluoro Pyromellitic Acid, 1-trifluoromethyl-4-fluorine Pyromellitic Acid, 1, 4-bis-(trifluoromethyl) Pyromellitic Acid, 1, 4-bis-(pentafluoroethyl group) Pyromellitic Acid, hexafluoro-3, 3 ', 4, 4 '-biphenyltetracarboxyacid acid, hexafluoro-3, 3 ', 4, 4 '-benzophenone tetracarboxylic acid, 2, 2-two (3, 4-dicarboxyl trifluorophenyl) HFC-236fa, 1, 3-two (3, 4 '-dicarboxyl trifluorophenyl) HFC-236fa, 1, 4-two (3, 4-dicarboxyl trifluoromethoxy phenoxy base) tetra fluoro benzene, hexafluoro-3, 3 ', 4, the two phthalic acid of 4 '-oxygen, 4, 4 '-(hexafluoroisopropylidenyl) two phthalic acid etc.
As the metallic compound contained in coating fluid together with polyimide precursor resin, as long as can by will the metallic compound of metal ion (or metal-salt) heat reduction that contain in polyimide precursor resin and precipitation particles shape metal, its material is not particularly limited, such as, can enumerates the metallic compound of the precursor containing gold (Au), silver (Ag), copper (Cu), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), tin (Sn), rhodium (Rh), iridium (Ir) etc.In addition, these metallic compounds also can a kind or and use with two or more.Such as, can the metal that preferably utilizes can enumerate gold (Au), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), tin (Sn), rhodium (Rh), iridium (Ir) as the metal kind playing local surface plasma resonance effect, be the compound of gold (Au) or silver (Ag) particularly preferably in the metallic compound used in the manufacture method of present embodiment.As metallic compound, the salt or organic carbonylcomplex etc. of above-mentioned metal can be used.As the salt of metal, such as, can enumerate hydrochloride, vitriol, acetate, oxalate, Citrate trianion etc.In addition, as the organic carbonyl compound of organic carbonylcomplex can be formed with above-mentioned metal kind, such as, the β-one carboxylicesterss etc. such as beta-diketon class, the methyl aceto acetates such as methyl ethyl diketone, benzoyl acetone, diphenylpropane-1,3-dione(DPPO) can be enumerated.
As the preferred object lesson of metallic compound, H [AuCl can be enumerated 4], Na [AuCl 4], AuI, AuCl, AuCl 3, AuBr 3, NH 4[AuCl 4] n2H 2o, Ag (CH 3cOO), AgCl, AgClO 4, Ag 2cO 3, AgI, Ag 2sO 4, AgNO 3, Ni (CH 3cOO) 2, Cu (CH 3cOO) 2, CuSO 4, CuCl 2, CuBr 2, Cu (NH 4) 2cl 4, CuI, Cu (NO 3) 2, Cu (CH 3cOCH 2cOCH 3) 2, CoCl 2, CoCO 3, CoSO 4, Co (NO 3) 2, NiSO 4, NiCO 3, NiCl 2, NiBr 2, Ni (NO 3) 2, NiC 2o 4, Ni (H 2pO 2) 2, Ni (CH 3cOCH 2cOCH 3) 2, Pd (CH 3cOO) 2, PdSO 4, PdCO 3, PdCl 2, PdBr 2, Pd (NO 3) 2, Pd (CH 3cOCH 2cOCH 3) 2, SnCl 2, IrCl 3, RhCl 3deng.
According to the difference of metal kind, metallic compound dissociates and to occur between produced metal ion and polyimide precursor resin three-dimensional to be cross-linked to form reaction sometimes.Therefore, As time goes on, coating fluid meeting thickening and gelation, be difficult to use as coating fluid sometimes.In order to prevent this thickening, gelation, in coating fluid, preferably add viscosity modifier as stablizer.By adding viscosity modifier, replace the metal ion in coating fluid and polyimide precursor resin to form chelate complexes, viscosity modifier can form chelate complexes with metal ion.Like this, the three-dimensional cross-linked formation of polyimide precursor resin and metal ion is blocked by viscosity modifier, and thickening and gelation are inhibited.
As viscosity modifier, preferably select the low-molecular-weight organic compound with the reactivity high (that is metal complex can be formed) of metal ion.The molecular weight of low-molecular-weight organic compound is preferably in the scope of 50 ~ 300.As the object lesson of this viscosity modifier, such as, can enumerate methyl ethyl diketone, methyl aceto acetate, pyridine, imidazoles, picoline etc.In addition, the addition of viscosity modifier preferably adds in the scope of 1 ~ 50 mole, preferably relative to the chelate complexes compound that can be formed 1 mole in the scope of 2 ~ 20 moles.
About the use level of the metallic compound in coating fluid, relative in the scope that the weight part 100 of the solids component of polyimide precursor resin and the total of metallic compound is 3 ~ 80 weight parts, be preferably in the scope of 10 ~ 60 weight parts.In this case, when metallic compound is lower than 3 weight part, be difficult to make the median size of metal particle to be more than 3nm.When metallic compound is more than 80 weight part, the metal-salt that sometimes can not be dissolved in coating fluid can precipitate or metal particle is easy to aggegation.Here, median size refers to the mean value (meso-position radius) of the diameter of metal particle, is surface mean diameter when measuring any 100 metal particles.Median size confirms by utilizing transmission electron microscope (TEM) to observe metal particle.
In addition, in coating fluid, as any composition except mentioned component, such as, can coordinate flow agent, defoamer, adaptation imparting agent, linking agent etc.
The method of the coating fluid of coating containing metallic compound is not particularly limited, the coating machine of comma formula, pattern, scraper type, lip pattern etc. such as can be used to be coated with, wherein preferably to use and can be formed uniformly coated film and the spin coater, gravure coater, the bar coater that are easy to the thickness controlling coated film accurately.Since coating fluid, the content of the metal ingredient (below sometimes also referred to as " metal ingredient ") of self-metallization compound reaches 0.5 μ g/cm 2~ 10 μ g/cm 2scope in, preferably reach 3 μ g/cm 2~ 10 μ g/cm 2scope in, preferably reach 6 μ g/cm further 2~ 10 μ g/cm 2scope in mode coat on base material.About the amount of metal being coated with the per unit area of coated film obtained, there is the content of the metal ingredient predetermined in coating fluid and carry out the method that controls and the thickness that predetermines coated film by the thickness of coated film and carried out the method that controls by the content of the metal ingredient in coating fluid.About the thickness of coated film, make dried thickness be more than 500nm and in the scope of less than 1.7 μm, be preferably more than 1 μm and in the scope of less than 1.7 μm, make the thickness of the polyimide resin layer after imidization be in the scope of 300nm ~ 1 μm scope that is interior, preferably 600nm ~ 1 μm.When the thickness of the polyimide resin layer after imidization is lower than 300nm, there is the tendency that metal particle aggegation each other easily occurs, and when more than 1 μm, the tendency that the metal particle that existence is formed in polyimide resin layer diminishes, but also there is the tendency of the median size inequality of the skin section of polyimide resin layer and the metal particle in deep.
In addition, in order to control the median size of metal particle and spacing of particle from, except content range (the 0.5 μ g/cm of the metal ingredient met in above-mentioned coated film 2~ 10 μ g/cm 2) and imidization after polyimide resin layer thickness range (300nm ~ 1 μm) condition beyond, content A [the μ g/cm of the metal ingredient further preferably in coated film 2] meet following formula with the relation of thickness B [nm] of polyimide resin layer after imidization.
0.1≤(A/B)×100≤2.0 (i)
By containing making it dry after the coating solution of metallic compound, form coated film.When drying, preferably carry out control temperature in the mode that the imidization caused by the carrying out of the dehydration closed-loop of polyimide precursor resin can not be made to complete.As the method making its drying, be not particularly limited, such as, should carry out drying with the time within the scope of 1 ~ 60 minute under the temperature condition within the scope of 60 ~ 200 DEG C, under the temperature condition preferably within the scope of 60 ~ 150 DEG C, carry out drying.Even if the part in the structure of dried coated film polyimide precursor resin there occurs imidization, also it doesn't matter, but imide rate is preferably less than 50%, more preferably less than 20%, i.e. the structure of residual more than 50% polyimide precursor resin.In addition, the imide rate of polyimide precursor resin can calculate as follows: use fourier-transform infrared spectrophotometer (as commercially available product, such as Japanese light splitting FT/IR620), utilize transmission method to measure the infrared absorption spectrum of film, thus with 1000cm -1phenyl ring C-H bond be benchmark, by from 1710cm -1the absorbancy of imide calculate.
Coated film can be individual layer, also can be the film of the stepped construction formed by multiple coated film.When for multilayer, the polyimide precursor resin that can be coated with other on the layer of the polyimide precursor resin formed by different constituents is successively formed.When the layer of polyimide precursor resin is formed by more than 3 layers, the polyimide precursor resin of more than 2 times identical formations can be used.Rotating fields simple 2 layers or individual layer, particularly individual layer can industrially advantageously obtain.
In addition, can also on sheet bracing member the layer of the polyimide precursor resin of stacked single or multiple lift, first carry out after imidization makes the polyimide resin layer of single or multiple lift, forming coated film thereon further.In this case, in order to improve the adaptation of the layer of polyimide resin layer and coated film, plasma body is preferably utilized to carry out surface treatment to the surface of polyimide resin layer.Utilize the surface treatment of plasma body by this, the surface roughening of polyimide resin layer can be made or change the chemical structure on surface.Thus, the wettability of the surface of polyimide resin layer improves, and improves, stably can keep coated film on a surface with the affinity of the solution of polyimide precursor resin.
[operation b; Heat treatment step]
In operation b, by the coated film that obtains as above operating in the scope of 160 ~ 450 DEG C, preferably in the scope of 200 ~ 400 DEG C, preferably further to heat-treat in the scope of 300 ~ 400 DEG C, the particle shape metal becoming metal particle is separated out in metal ion (or metal-salt) reduction.When thermal treatment temp is lower than 160 DEG C, being sometimes difficult to make metal ion (or metal-salt) to reduce the median size of the metal particle obtained is more than above-mentioned lower limit.And when thermal treatment temp is more than 450 DEG C, polyimide resin layer can decompose because of heat, be difficult to control metal particle particle interval each other.It is more than 160 DEG C by making thermal treatment temp, the thermodiffusion of metal particle in the inside of polyimide resin layer (or polyimide precursor resin layer) of separating out because of reduction can be carried out fully, and then the imidization of polyimide precursor resin can be carried out, thus utilization can be omitted again heat the operation of carrying out imidization.
About heat-up time, as described later, can according to the spacing of particle of target from and decide according to the content of the metal ion contained in Heating temperature, coated film (or metal-salt), such as, in the scope that can be set as 10 ~ 180 minutes when Heating temperature is 160 DEG C, in the scope that can be set as 1 ~ 60 minute when Heating temperature is 450 DEG C.
In addition, by this thermal treatment, the polyimide precursor resin in coated film is carried out imidization, thus the content forming metal particle is 0.5 μ g/cm 2~ 10 μ g/cm 2scope in, be preferably 3 μ g/cm 2~ 10 μ g/cm 2scope in, more preferably 6 μ g/cm 2~ 10 μ g/cm 2scope in and thickness be 300nm ~ 1 μm scope in, the polyimide resin layer be preferably in the scope of 600nm ~ 1 μm.
As mentioned above, the median size of metal particle and spacing of particle are from thermal treatment temp, the ii that can pass through in i) heat treatment step) content of metal ion (or metal-salt) that contains in coated film and iii) thickness of the final polyimide resin layer formed controls.The present inventor obtains following opinion: and the metal ion (or metal-salt) that in coated film contain constant when thermal treatment temp even if absolute magnitude different time or coated film in the absolute magnitude of metal ion (or metal-salt) that contains constant and the thickness of coated film is different time, the particle diameter of the metal particle of precipitation is different.In addition; have also obtained following opinion: when having carried out thermal treatment when the thickness of the content of the metal ion (or metal-salt) not controlling to contain in thermal treatment temp, coated film and the final polyimide resin layer formed, spacing of particle is to reduce or metal particle can form island in the surperficial aggegation of polyimide resin layer sometimes sometimes.
Use above opinion, found: by control above-mentioned i) ~ iii) condition, can control the median size of metal particle and spacing of particle from.That is, by control i) ~ iii) condition, the median size of metal particle can be controlled within the scope of 3nm ~ 25nm, and be taken respective particle interval (spacing of particle from) L as the particle diameter (D of metal particle larger in adjacent metal particulate by the metal particle that so controls l) more than i.e. L>=D lrelation exist.The Metal microparticle composite of present embodiment, by possessing the prerequisite of operation a and operation b, makes the thermodiffusion of the metal particle of precipitation become easy, thus becomes with particle diameter D larger in adjacent metal particulate labove spacing of particle is dispersed in the state in polyimide resin from L.Even if spacing of particle does not greatly have special problem from L yet, but each spacing of particle formed owing to utilizing thermodiffusion in the metal particle of dispersion state has close relationship from L and the particle diameter D of metal particle and the volume fraction of metal particle, therefore spacing of particle controls from the upper limit of L preferably by the lower value of the volume fraction of metal particle.
In the present embodiment, the volume fraction of metal particle is made to be in the scope of 0.05 ~ 1% relative to Metal microparticle composite, to be preferably in the scope of 0.1 ~ 1%.By making volume fraction be in above-mentioned scope, the spacing of particle of metal particle can be controlled from L.The volume fraction of metal particle can regulate mainly through the content of the metal ingredient in the coating fluid in operation a.
In addition, the hardness of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b can have an impact to the thermal diffusivity of metal particle.That is, the polyimide precursor resin/polyimide resin under thermal treatment temp is softer, be more easy to the thermodiffusion carrying out metal particle, otherwise polyimide precursor resin/polyimide resin is harder, is more difficult to the thermodiffusion carrying out metal particle.From such a viewpoint, L>=D is met in order to be formed lthe Metal microparticle composite that the mode of relation is controlled, preferably regulates the Young's modulus (Young's modulus when heating in the scope that temperature is 160 ~ 450 DEG C) of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b.In addition, the Young's modulus of the polyimide resin after solidification has been shown in aftermentioned embodiment, and this Young's modulus becomes the index of the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of reflection operation b.That is, the Young's modulus of the polyimide resin after solidification is higher, the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of then operation b is higher, the Young's modulus of the polyimide resin after solidification is lower, the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of then operation b is lower, therefore can be controlled the thermodiffusion of metal particle by the Young's modulus of the polyimide resin after controlling solidification.The Young's modulus of the polyimide resin after solidification is preferably adjusted to such as 1 × 10 in advance 5above and 1 × 10 10in the scope of below Pa.
About the speciality of the manufacture method of present embodiment, following industrial advantage can be enumerated: namely may correspond to from laboratory scale to industrial scale with simple equipment without particular limitation; In addition, not only may correspond to batch-type, also may correspond to continous way and without the need to special means etc.In addition, operation b such as can at Ar, N 2carry out Deng in inertness gas atmosphere, in the vacuum of 1 ~ 5KPa or in an atmosphere.As the method (method of reduction treatment) making particle shape metal separate out, the vapour phase reduction of the reducing gas such as hydrogen and light (ultraviolet) is used to reduce and are not suitable for.In vapour phase reduction, can not form metal particle at the near surface of polyimide resin layer, being reduced property of the thermolysis gas of polyimide resin promotes, is difficult to the particle interval controlling metal particle.In addition, in photoreduction, easily produce the density unevenness of the metal particle near surface and deep because of the luminous transparency from polyimide resin layer, be not only difficult to control the particle diameter D of metal particle and spacing of particle from L, and reduction efficiency is also low.In addition, when the particle shape metal of separating out in the process at operation b be the particle shape metal such as Au (gold), Ni (nickel) this can promote that under high-temperature atmosphere polyimide resin (or polyimide precursor resin) decomposes such (having so-called catalyst function) metal kind time, preferably at Ar, N 2deng in inertness gas atmosphere, carry out in the vacuum of 1 ~ 5KPa.
In operation b, the heat used in reduction treatment also can be utilized to complete the imidization of polyimide precursor resin, the operation of precipitation to imidization thus can being undertaken from metal particle by a cooking-pot type, thus can production process be simplified.
In addition, in the reduction utilizing thermal treatment to carry out, metal ion (or metal-salt) reduction that can be present in coated film, and make each metal particle with independently state precipitation by thermodiffusion.The metal particle of formation like this keeps certain above spacing of particle from the state of L and shape is roughly even, and the skin section of metal particle from polyimide resin in polyimide resin layer is disperseed in three dimensions equably.In addition, can also by controlling the structural unit of the resin forming polyimide resin or controlling absolute magnitude and the volume fraction of metal particle of metal ion (or metal-salt), thus control the distribution of the metal particle in the median size of metal particle and polyimide resin layer.
And then, by reaching 6 μ g/cm with the content of the metal particle in polyimide resin layer 2~ 10 μ g/cm 2scope in and the mode that the thickness of polyimide resin layer reaches in the scope of 600nm ~ 870nm forms coated film, can be formed and be dispersed with the metal microparticle layer that median size is the metal particle of more than 13nm.
In addition, in the manufacture method of present embodiment, except above-mentioned operation a and operation b, any operations such as such as etching work procedure can also be carried out.
As mentioned above, according to the manufacture method of Metal microparticle composite of the present invention, owing to metal ion (or metal-salt) being reduced and precipitating metal particulate in the inside of polyimide precursor resin, therefore easily regulate the content of the metallic compound in polyimide precursor resin, easily regulate the content of the metal particle be dispersed in polyimide resin.Therefore, it is possible to manufacture with comparalive ease containing median size be 3nm ~ 25nm scope in metal particle and the volume fraction of metal particle be 0.05 ~ 1% scope in, thickness is Metal microparticle composite in the scope of 300nm ~ 1 μm.And, because this reduction treatment utilizes heating to carry out, therefore, it is possible to utilize the thermodiffusion of metal particle of separating out make metal particle with keep certain above spacing of particle from state be dispersed in matrix resin.In addition, make to separate loose metal particle with certain above spacing of particle to come into existence from the skin section of matrix resin.
In addition, according to the manufacture method of Metal microparticle composite of the present invention, utilize the heat used in reduction treatment can also complete the imidization of polyimide precursor resin, thus can simplify production process.
The Metal microparticle composite manufactured by method of the present invention, owing to possessing said structure characteristic, is utilized in that the field of surface plasmons is representative, the various industrial circle such as such as electromagnetic shielding material, magnetic noise absorbing material, high thermal conductive resin material therefore, it is possible to be applied to pressure transmitter etc.The Metal microparticle composite particularly obtained by method of the present invention has the sufficient thickness of 300nm ~ 1 μm due to polyimide resin layer, and the median size of metal particle is relatively little compared with above-mentioned thickness, for 3nm ~ 25nm, and the volume fraction of metal particle is 0.05 ~ 1% relative to Metal microparticle composite, therefore can preferably be applicable in the purposes of the pressure transmitter utilizing local surface plasma resonance.That is, due to polyimide resin layer thickness relative to the median size of metal particle and spacing of particle from for enough large, the amplitude of recoverable deformation when therefore can increase pressurization, also can increase the miles of relative movement of the metal particle of inside during recoverable deformation.Therefore, it is possible to the detection boundary of pressure transmitter is broadened, and improve accuracy of detection.And because the scope of the median size of metal particle is narrower, be 3nm ~ 25nm, therefore the inequality of particle diameter is little, obtains sharp-pointed absorption when pressurizeing by local surface plasma resonance, thus can carry out highly sensitive detection.Therefore, utilizing pressure range wide and obtaining high detection sensitivity and estimating precision of pressure transmitter can be expected.
[the 2nd embodiment]
Then, the 2nd embodiment of the present invention is described in detail.In addition, below by with the difference of the 1st embodiment centered by be described.The manufacture method of the Metal microparticle composite of the 2nd embodiment of the present invention is the method manufacturing following Metal microparticle composite, described Metal microparticle composite be by median size be 3nm ~ 30nm scope in metal particle be not in contact with each other and with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate independently of each other (preferably completely independently) be dispersed in polyimide resin, and the volume fraction of metal particle is more than 0.2% relative to Metal microparticle composite and in the scope of less than 5%, the manufacture method of described Metal microparticle composite possesses following operation a and operation b.Polyimide resin in the manufacture method of the Metal microparticle composite of present embodiment and polyimide precursor resin can be used in the polyimide resin and polyimide precursor resin that illustrated in the 1st embodiment.
[operation a; Coated film formation process]
In the manufacture method of the Metal microparticle composite of present embodiment, by the coating solution containing polyimide precursor resin and metallic compound on base material, dry formation coated film.Operation a in present embodiment, except for the formation of except content this point different of the metal ingredient in the coating fluid of coated film, can implement in the same manner as the operation a of the 1st embodiment.
Since the coating fluid used in the operation a of present embodiment, the content of the metal ingredient of self-metallization compound reaches 10 μ g/cm 2~ 50 μ g/cm 2scope in, preferably reach 10 μ g/cm 2~ 40 μ g/cm 2scope in, preferably reach 10 μ g/cm further 2~ 30 μ g/cm 2scope in mode be coated on base material.About the amount of metal being coated with the per unit area of coated film obtained, there is the content of the metal ingredient predetermined in coating fluid and carry out the method that controls and the thickness that predetermines coated film by the thickness of coated film and carried out the method that controls by the content of the metal ingredient in coating fluid.About the thickness of coated film, make dried thickness be more than 500nm less than 1.7 μm scope in, be preferably in the scope of more than 1 μm less than 1.7 μm, make the thickness of the polyimide resin layer after imidization be in the scope of 300nm ~ 1 μm scope that is interior, preferably 600nm ~ 1 μm.When the thickness of the polyimide resin layer after imidization is lower than 300nm, there is the tendency that metal particle aggegation each other easily occurs, and when more than 1 μm, the tendency that the metal particle that existence is formed in polyimide resin layer diminishes, but also there is the tendency of the median size inequality of the skin section of polyimide resin layer and the metal particle in deep.
In addition, in order to control the median size of metal particle and spacing of particle from, except meeting content range (the 10 μ g/cm of the metal ingredient in above-mentioned coated film 2~ 50 μ g/cm 2) and imidization after polyimide resin layer thickness range (300nm ~ 1 μm) condition beyond, content A [the μ g/cm of the metal ingredient further preferably in coated film 2] meet following formula with the relation of thickness B [nm] of polyimide resin layer after imidization.
2≤(A/B)×100≤12 (ii)
[operation b; Heat treatment step]
In operation b, by by as above operate the coated film of acquisition in the scope of 160 ~ 450 DEG C, preferably in the scope of 200 ~ 400 DEG C, preferably further to heat-treat in the scope of 300 ~ 400 DEG C, the particle shape metal becoming metal particle is separated out in metal ion (or metal-salt) reduction, and makes it be dispersed in coated film.In addition, by this thermal treatment, the polyimide precursor resin in coated film is carried out imidization, to be formed in scope that thickness is 300nm ~ 1 μm and Young's modulus be 3GPa ~ 10GPa scope in polyimide resin layer.Operation b in present embodiment, except the aspect of following explanation, can implement in the same manner as the operation b of the 1st embodiment.
About heat-up time, as described later, can according to the spacing of particle of target from and decide according to the content of the metal ion contained in Heating temperature, coated film (or metal-salt), such as, in the scope that can be set as 10 ~ 180 minutes when Heating temperature is 160 DEG C, in the scope that can be set as 1 ~ 60 minute when Heating temperature is 450 DEG C.
The Young's modulus (Young's modulus when heating in the scope that temperature is 160 ~ 450 DEG C) of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b can have an impact to the thermal diffusivity of metal particle, therefore in order to make the thermodiffusion of metal particle moderately carry out, the Young's modulus of the polyimide precursor resin/polyimide resin in heat treatment process is regulated.In the method for present embodiment, such as reach more than 3GPa with the Young's modulus of the polyimide resin after solidifying and reach more than 4GPa and mode in the scope of below 10GPa regulates the Young's modulus of polyimide precursor resin/polyimide resin in the scope of below 10GPa, preferably.When the Young's modulus of polyimide resin is when cured lower than 3GPa, is difficult to the dispersion controlling metal particle when the thermal treatment of operation b, there is the tendency that metal particle aggegation occurs.And the Young's modulus of polyimide resin when cured more than 10GPa time, the dispersion of metal particle is suppressed significantly, therefore the metal particle generated becomes too small, exist such as utilize local surface plasma resonance sensor purposes in time sensitivity decrease tendency, but also the toughness existed as the polyimide resin of matrix reduces and becomes the tendency of the material be highly brittle.
In addition, in the present embodiment, define the Young's modulus of the polyimide resin after solidification, this is because: this Young's modulus is relevant with the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of operation b, becomes the index of the Young's modulus in reflect heat treating processes.That is, the Young's modulus of the polyimide resin after solidification is higher, the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of then operation b is higher, the Young's modulus of the polyimide resin after solidification is lower, then the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of operation b is lower.Therefore, the Young's modulus by controlling the polyimide resin after solidifying can control the thermodiffusion of metal particle.
In addition, by this thermal treatment, the polyimide precursor resin in coated film is carried out imidization, the content forming metal particle is 10 μ g/cm 2~ 50 μ g/cm 2scope in, be preferably 10 μ g/cm 2~ 40 μ g/cm 2scope in, more preferably 10 μ g/cm 2~ 30 μ g/cm 2scope in and thickness be 300nm ~ 1 μm scope in, the polyimide resin layer be preferably in the scope of 600nm ~ 1 μm.
The median size of metal particle and spacing of particle are from thermal treatment temp, the ii that can pass through in i) heat treatment step) content, the iii of metal ion (or metal-salt) that contain in coated film) thickness of the final polyimide resin layer formed and iv) Young's modulus of polyimide precursor resin/polyimide resin when heat-treating controls.The present inventor obtains following opinion: and the metal ion (or metal-salt) that in coated film contain constant when thermal treatment temp even if absolute magnitude different time or coated film in the absolute magnitude of metal ion (or metal-salt) that contains constant and the thickness of coated film is different time, the particle diameter of the metal particle of precipitation is different.In addition; have also obtained following opinion: when having carried out thermal treatment when the thickness of the content of the metal ion (or metal-salt) not controlling to contain in thermal treatment temp, coated film and the final polyimide resin layer formed, spacing of particle is to reduce or metal particle can form island in the surperficial aggegation of polyimide resin layer sometimes sometimes.In addition, have also obtained following opinion: the Young's modulus of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b can have an impact to the thermal diffusivity of metal particle, under thermal treatment temp, polyimide precursor resin/polyimide resin is softer, more be easy to the thermodiffusion carrying out metal particle, otherwise polyimide precursor resin/polyimide resin is harder, be more difficult to the thermodiffusion carrying out metal particle.
Use above opinion, found: by control above-mentioned i) ~ iv) condition, can control the median size of metal particle and spacing of particle from.That is, by control i) ~ iv) condition, the median size of metal particle can be controlled within the scope of 3nm ~ 30nm, and be taken respective particle interval (spacing of particle from) L as the particle diameter (D of metal particle larger in adjacent metal particulate by the metal particle that so controls l) more than i.e. L>=D lrelation exist.The Metal microparticle composite of present embodiment, by possessing the prerequisite of operation a and operation b, makes the thermodiffusion of the metal particle of precipitation become easy, thus becomes with particle diameter D larger in adjacent metal particulate labove spacing of particle is dispersed in the state in polyimide resin from L.Even if spacing of particle does not greatly have special problem from L yet, but each spacing of particle formed owing to utilizing thermodiffusion in the metal particle of dispersion state has close relationship from L and the particle diameter D of metal particle and the volume fraction of metal particle, therefore spacing of particle controls from the upper limit of L preferably by the lower value of the volume fraction of metal particle.
In the present embodiment, the volume fraction of metal particle is made to be in the scope of 0.2 ~ 5% relative to Metal microparticle composite, to be preferably in the scope of 0.5 ~ 3%.By making volume fraction be in above-mentioned scope, the spacing of particle of metal particle can be controlled from L.The volume fraction of metal particle can regulate mainly through the content of the metal ingredient in the coating fluid in operation a.
In addition, in the manufacture method of present embodiment, except above-mentioned operation a and operation b, any operations such as such as etching work procedure can also be carried out.
As mentioned above, the manufacture method of Metal microparticle composite according to the present embodiment, owing to metal ion (or metal-salt) being reduced and precipitating metal particulate in the inside of polyimide precursor resin, therefore easily regulate the content of the metallic compound in polyimide precursor resin, easily regulate the content of the metal particle be dispersed in polyimide resin.Therefore, it is possible to manufacture with comparalive ease containing median size be 3nm ~ 30nm scope in metal particle and the volume fraction of metal particle be more than 0.2% and in the scope of less than 5%, thickness is Metal microparticle composite in the scope of 300nm ~ 1 μm.And, because this reduction treatment utilizes heating to carry out, therefore, it is possible to utilize the thermodiffusion of metal particle of separating out make metal particle with keep certain above spacing of particle from state be dispersed in matrix resin.In addition, make to separate loose metal particle with certain above spacing of particle to come into existence from the skin section of matrix resin.
In addition, the manufacture method of Metal microparticle composite according to the present embodiment, utilizes the heat used in reduction treatment can also complete the imidization of polyimide precursor resin, thus can simplify production process.
By the Metal microparticle composite of the method manufacture of present embodiment owing to possessing said structure characteristic, utilize in that the field of surface plasmons is representative, the various industrial circle such as such as electromagnetic shielding material, magnetic noise absorbing material, high thermal conductive resin material therefore, it is possible to be applied to pressure transmitter etc.The Metal microparticle composite particularly obtained by the method for present embodiment has the sufficient thickness of 300nm ~ 1 μm due to polyimide resin layer, and the median size of metal particle is relatively little compared with above-mentioned thickness, for 3nm ~ 30nm, and the volume fraction of metal particle is more than 0.2% relative to Metal microparticle composite and less than 5%, therefore can preferably be applicable in the purposes of the pressure transmitter utilizing local surface plasma resonance.That is, due to polyimide resin layer thickness relative to the median size of metal particle and spacing of particle from for enough large, the amplitude of recoverable deformation when therefore can increase pressurization, also can increase the miles of relative movement of the metal particle of inside during recoverable deformation.Therefore, it is possible to the detection boundary of pressure transmitter is broadened, and improve accuracy of detection.And due to the narrow range of the median size of metal particle, be 3nm ~ 30nm, therefore the inequality of particle diameter is little, obtains sharp-pointed absorption when pressurizeing by local surface plasma resonance, thus can carry out highly sensitive detection.Therefore, utilizing pressure range wide and obtaining high detection sensitivity and estimating precision of pressure transmitter can be expected.
Other formation in the manufacture method of the Metal microparticle composite of present embodiment is identical with the 1st embodiment with effect.
[the 3rd embodiment]
Then, embodiments of the present invention are described in detail.In addition, below by with the difference of the 1st embodiment centered by be described.The manufacture method of the Metal microparticle composite of the 3rd embodiment of the present invention is the method manufacturing following Metal microparticle composite, described Metal microparticle composite be by median size be 3nm ~ 30nm scope in metal particle be not in contact with each other and with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate independently of each other (preferably completely independently) be dispersed in polyimide resin, and the volume fraction of metal particle is more than 0.5% relative to Metal microparticle composite and in the scope of less than 5%, the manufacture method of described Metal microparticle composite possesses following operation a and operation b.Polyimide resin in the manufacture method of the Metal microparticle composite of present embodiment and polyimide precursor resin can be used in the polyimide resin and polyimide precursor resin that illustrated in the 1st embodiment.
[operation a; Coated film formation process]
In the manufacture method of the Metal microparticle composite of present embodiment, by the coating solution containing polyimide precursor resin and metallic compound on base material, dry formation coated film.Operation a in present embodiment, except for the formation of except content this point different of the metal ingredient in the coating fluid of coated film, can implement in the same manner as the operation a of the 1st embodiment.
Since the coating fluid used in the operation a of present embodiment, the content of the metal ingredient of self-metallization compound reaches 5 μ g/cm 2~ 10 μ g/cm 2scope in, preferably reach 5 μ g/cm 2~ 9 μ g/cm 2scope in, preferably reach 5 μ g/cm further 2~ 8 μ g/cm 2scope in mode be coated on base material.About the amount of metal being coated with the per unit area of coated film obtained, there is the content of the metal ingredient predetermined in coating fluid and carry out the method that controls and the thickness that predetermines coated film by the thickness of coated film and carried out the method that controls by the content of the metal ingredient in coating fluid.About the thickness of coated film, make dried thickness be in the scope scope that is interior, preferably 200nm ~ 500nm of 150nm ~ 500nm, make the thickness of the polyimide resin layer after imidization be in the scope scope that is interior, preferably 150nm ~ 300nm of 100nm ~ 300nm.When the thickness of the polyimide resin layer after imidization is lower than 100nm, there is the tendency that metal particle aggegation each other easily occurs, and when more than 300nm, the tendency that the metal particle that existence is formed in polyimide resin layer diminishes, but also there is the tendency of the median size inequality of the skin section of polyimide resin layer and the metal particle in deep.
In addition, in order to control the median size of metal particle and spacing of particle from, except meeting content range (the 5 μ g/cm of the metal ingredient in above-mentioned coated film 2~ 10 μ g/cm 2) and imidization after polyimide resin layer thickness range (100nm ~ 300nm) condition beyond, content A [the μ g/cm of the metal ingredient also further preferably in coated film 2] meet following formula with the relation of thickness B [nm] of polyimide resin layer after imidization.
2≤(A/B)×100≤8 (iii)
[operation b; Heat treatment step]
In operation b, by by as above operate the coated film of acquisition in the scope of 160 ~ 450 DEG C, preferably in the scope of 200 ~ 400 DEG C, preferably further to heat-treat in the scope of 300 ~ 400 DEG C, the particle shape metal becoming metal particle is separated out in metal ion (or metal-salt) reduction, and makes it be dispersed in coated film.In addition, by this thermal treatment, the polyimide precursor resin in coated film is carried out imidization, formed thickness be 100nm ~ 300nm scope in and Young's modulus be 5MPa ~ 10GPa scope in polyimide resin layer.Operation b in present embodiment, except the aspect of following explanation, can implement in the same manner as the operation b of the 1st embodiment.
About heat-up time, as described later, can according to the spacing of particle of target from and decide according to the content of the metal ion contained in Heating temperature, coated film (or metal-salt), such as, in the scope that can be set as 10 ~ 180 minutes when Heating temperature is 160 DEG C, in the scope that can be set as 1 ~ 60 minute when Heating temperature is 450 DEG C.
The Young's modulus (Young's modulus when heating in the scope that temperature is 160 ~ 450 DEG C) of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b can have an impact to the thermal diffusivity of metal particle, therefore in order to make the thermodiffusion of metal particle moderately carry out, the Young's modulus of polyimide precursor resin/polyimide resin during thermal treatment is regulated.In the method for present embodiment, such as reach more than 5MPa with the Young's modulus of the polyimide resin after solidifying and reach more than 8MPa and mode in the scope of below 10GPa regulates the Young's modulus of polyimide precursor resin/polyimide resin in the scope of below 10GPa, preferably.When the Young's modulus of polyimide resin is when cured lower than 5MPa, is difficult to the dispersion controlling metal particle when the thermal treatment of operation b, there is the tendency that metal particle aggegation occurs.And the Young's modulus of polyimide resin when cured more than 10GPa time, the dispersion of metal particle is suppressed significantly, therefore the metal particle generated becomes too small, exist such as utilize local surface plasma resonance sensor purposes in time sensitivity decrease tendency, but also the toughness existed as the polyimide resin of matrix reduces and becomes the tendency of the material be highly brittle.
In addition, in the present embodiment, define the Young's modulus of the polyimide resin after solidification, this is because: this Young's modulus is relevant with the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of operation b, becomes the index of the Young's modulus in reflect heat treating processes.That is, the Young's modulus of the polyimide resin after solidification is higher, the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of then operation b is higher, the Young's modulus of the polyimide resin after solidification is lower, then the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of operation b is lower.Therefore, by controlling the Young's modulus of the polyimide resin after solidification, the thermodiffusion of metal particle can be controlled.
In addition, by this thermal treatment, the polyimide precursor resin in coated film is carried out imidization, the content forming metal particle is 5 μ g/cm 2~ 10 μ g/cm 2scope in, be preferably 5 μ g/cm 2~ 9 μ g/cm 2scope in, more preferably 5 μ g/cm 2~ 8 μ g/cm 2scope in and thickness be 100nm ~ 300nm scope in, be preferably 150nm ~ 300nm scope in polyimide resin layer.
The median size of metal particle and spacing of particle are from thermal treatment temp, the ii that can pass through in i) heat treatment step) content, the iii of metal ion (or metal-salt) that contain in coated film) thickness of the final polyimide resin layer formed and iv) Young's modulus of polyimide precursor resin/polyimide resin when heat-treating controls.The present inventor obtains following opinion: and the metal ion (or metal-salt) that in coated film contain constant when thermal treatment temp even if absolute magnitude different time or coated film in the absolute magnitude of metal ion (or metal-salt) that contains constant and the thickness of coated film is different time, the particle diameter of the metal particle of precipitation is different.In addition; have also obtained following opinion: when having carried out thermal treatment when the thickness of the content of the metal ion (or metal-salt) not controlling to contain in thermal treatment temp, coated film and the final polyimide resin layer formed, spacing of particle is to reduce or metal particle can form island in the surperficial aggegation of polyimide resin layer sometimes sometimes.In addition, have also obtained following opinion: the Young's modulus of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b can have an impact to the thermal diffusivity of metal particle, under thermal treatment temp, polyimide precursor resin/polyimide resin is softer, more be easy to the thermodiffusion carrying out metal particle, otherwise polyimide precursor resin/polyimide resin is harder, be more difficult to the thermodiffusion carrying out metal particle.
Use above opinion, found: by control above-mentioned i) ~ iv) condition, can control the median size of metal particle and spacing of particle from.That is, by control i) ~ iv) condition, the median size of metal particle can be controlled within the scope of 3nm ~ 30nm, and be taken respective particle interval (spacing of particle from) L as the particle diameter (D of metal particle larger in adjacent metal particulate by the metal particle that so controls l) more than i.e. L>=D lrelation exist.The Metal microparticle composite of present embodiment, by possessing the prerequisite of operation a and operation b, makes the thermodiffusion of the metal particle of precipitation become easy, thus becomes with particle diameter D larger in adjacent metal particulate labove spacing of particle is dispersed in the state in polyimide resin from L.Even if spacing of particle does not greatly have special problem from L yet, but each spacing of particle formed owing to utilizing thermodiffusion in the metal particle of dispersion state has close relationship from L and the particle diameter D of metal particle and the volume fraction of metal particle, therefore spacing of particle controls from the upper limit of L preferably by the lower value of the volume fraction of metal particle.
In the present embodiment, the volume fraction of metal particle is made to be in the scope of 0.5 ~ 5% relative to Metal microparticle composite, to be preferably in the scope of 1 ~ 3%.By making volume fraction be in above-mentioned scope, the spacing of particle of metal particle can be controlled from L.The volume fraction of metal particle can regulate mainly through the content of the metal ingredient in the coating fluid in operation a.
In addition, in the manufacture method of present embodiment, except above-mentioned operation a and operation b, any operations such as such as etching work procedure can also be carried out.
As mentioned above, the manufacture method of Metal microparticle composite according to the present embodiment, owing to metal ion (or metal-salt) being reduced and precipitating metal particulate in the inside of polyimide precursor resin, therefore easily regulate the content of the metallic compound in polyimide precursor resin, easily regulate the content of the metal particle be dispersed in polyimide resin.Therefore, it is possible to manufacture with comparalive ease containing median size be 3nm ~ 30nm scope in metal particle and the volume fraction of metal particle be 0.5 ~ 5% scope in, thickness is Metal microparticle composite in the scope of 100nm ~ 300nm.And, because this reduction treatment utilizes heating to carry out, therefore, it is possible to utilize the thermodiffusion of metal particle of separating out make metal particle with keep certain above spacing of particle from state be dispersed in matrix resin.In addition, make to separate loose metal particle with certain above spacing of particle to come into existence from the skin section of matrix resin.
In addition, the manufacture method of Metal microparticle composite according to the present embodiment, utilizes the heat used in reduction treatment can also complete the imidization of polyimide precursor resin, thus can simplify production process.
By the Metal microparticle composite of the method manufacture of present embodiment owing to possessing said structure characteristic, utilize in that the field of surface plasmons is representative, the various industrial circle such as such as electromagnetic shielding material, magnetic noise absorbing material, high thermal conductive resin material therefore, it is possible to be applied to pressure transmitter etc.The Metal microparticle composite particularly obtained by the method for present embodiment has the sufficient thickness of 100nm ~ 300nm due to polyimide resin layer, and the median size of metal particle is relatively little compared with above-mentioned thickness, for 3nm ~ 30nm, and the volume fraction of metal particle is 0.5 ~ 5% relative to Metal microparticle composite, therefore can preferably be applicable in the purposes of the pressure transmitter utilizing local surface plasma resonance.That is, due to polyimide resin layer thickness relative to the median size of metal particle and spacing of particle from for enough large, the amplitude of recoverable deformation when therefore can increase pressurization, also can increase the miles of relative movement of the metal particle of inside during recoverable deformation.Therefore, it is possible to the detection boundary of pressure transmitter is broadened, and improve accuracy of detection.And due to the narrow range of the median size of metal particle, be 3nm ~ 30nm, therefore the inequality of particle diameter is little, obtains sharp-pointed absorption when pressurizeing by local surface plasma resonance, thus can carry out highly sensitive detection.Therefore, utilizing pressure range wide and obtaining high detection sensitivity and estimating precision of pressure transmitter can be expected.In addition, the Metal microparticle composite obtained by the method for present embodiment, owing to polyimide resin layer film can be turned to 100nm ~ 300nm, is therefore applicable to the purposes of the subtle change of the skin section of Metal microparticle composite being carried out to sensing detection.Utilize such character, such as by carrying out etching and processing to the skin section of Metal microparticle composite, a part for the metal particle of the skin section being present in this complex body is made to expose to surface from matrix, can be advantageously used for the sensor base plate etc. the change of outside atmosphere being carried out to sensing detection, it applies desirable.
Other formation in the manufacture method of the Metal microparticle composite of present embodiment is identical with the 1st embodiment with effect.
[the 4th embodiment]
Then, embodiments of the present invention are described in detail.In addition, below by with the difference of the 1st embodiment centered by be described.The manufacture method of the Metal microparticle composite of an embodiment of the invention is the methods manufacturing following Metal microparticle composite, described Metal microparticle composite be by median size be 5nm ~ 35nm scope in metal particle be not in contact with each other and with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate independently of each other (preferably completely independently) be dispersed in polyimide resin, and the volume fraction of metal particle is more than 1% relative to Metal microparticle composite and in the scope of less than 15%, the manufacture method of described Metal microparticle composite possesses following operation a and operation b.Polyimide resin in the manufacture method of the Metal microparticle composite of present embodiment and polyimide precursor resin can be used in the polyimide resin and polyimide precursor resin that illustrated in the 1st embodiment.
[operation a; Coated film formation process]
In the manufacture method of the Metal microparticle composite of present embodiment, by the coating solution containing polyimide precursor resin and metallic compound on base material, dry formation coated film.Operation a in present embodiment, except for the formation of except content this point different of the metal ingredient in the coating fluid of coated film, can implement in the same manner as the operation a of the 1st embodiment.
Since the coating fluid used in the operation a of present embodiment, the content of the metal ingredient of self-metallization compound reaches 10 μ g/cm 2~ 30 μ g/cm 2scope in, preferably reach 10 μ g/cm 2~ 27 μ g/cm 2scope in, preferably reach 10 μ g/cm further 2~ 25 μ g/cm 2scope in mode be coated on base material.About the amount of metal being coated with the per unit area of coated film obtained, there is the content of the metal ingredient predetermined in coating fluid and carry out the method that controls and the thickness that predetermines coated film by the thickness of coated film and carried out the method that controls by the content of the metal ingredient in coating fluid.About the thickness of coated film, make dried thickness be in the scope scope that is interior, preferably 200nm ~ 500nm of 150nm ~ 500nm, make the thickness of the polyimide resin layer after imidization be in the scope scope that is interior, preferably 150nm ~ 300nm of 100nm ~ 300nm.When the thickness of the polyimide resin layer after imidization is lower than 100nm, there is the tendency that metal particle aggegation each other easily occurs, and when more than 300nm, the tendency that the metal particle that existence is formed in polyimide resin layer diminishes, but also there is the tendency of the median size inequality of the skin section of polyimide resin layer and the metal particle in deep.
In addition, in order to control the median size of metal particle and spacing of particle from, except meeting content range (the 10 μ g/cm of the metal ingredient in above-mentioned coated film 2~ 30 μ g/cm 2) and imidization after polyimide resin layer thickness range (100nm ~ 300nm) condition beyond, content A [the μ g/cm of the metal ingredient also further preferably in coated film 2] meet following formula with the relation of thickness B [nm] of polyimide resin layer after imidization.
5≤(A/B)×100≤25 (iv)
[operation b; Heat treatment step]
In operation b, by by as above operate the coated film of acquisition in the scope of 160 ~ 450 DEG C, preferably in the scope of 200 ~ 400 DEG C, preferably further to heat-treat in the scope of 300 ~ 400 DEG C, the particle shape metal becoming metal particle is separated out in metal ion (or metal-salt) reduction, and makes it be dispersed in coated film.In addition, by this thermal treatment, the polyimide precursor resin in coated film is carried out imidization, formed thickness be 100nm ~ 300nm scope in and Young's modulus be 0.5GPa ~ 10GPa scope in polyimide resin layer.Operation b in present embodiment, except the aspect of following explanation, can implement in the same manner as the operation b of the 1st embodiment.
About heat-up time, as described later, can according to the spacing of particle of target from and decide according to the content of the metal ion contained in Heating temperature, coated film (or metal-salt), such as, in the scope that can be set as 10 ~ 180 minutes when Heating temperature is 160 DEG C, in the scope that can be set as 1 ~ 60 minute when Heating temperature is 450 DEG C.
In addition, the Young's modulus (Young's modulus when heating in the scope that temperature is 160 ~ 450 DEG C) of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b can have an impact to the thermal diffusivity of metal particle, therefore in order to make the thermodiffusion of metal particle moderately carry out, the Young's modulus of polyimide precursor resin/polyimide resin during thermal treatment is regulated.In the method for present embodiment, such as reach more than 0.5GPa with the Young's modulus of the polyimide resin after solidifying and reach more than 0.6GPa and mode in the scope of below 10GPa regulates the Young's modulus of polyimide precursor resin/polyimide resin in the scope of below 10GPa, preferably.When the Young's modulus of polyimide resin is when cured lower than 0.5GPa, is difficult to the dispersion controlling metal particle when the thermal treatment of operation b, there is the tendency that metal particle aggegation occurs.And the Young's modulus of polyimide resin when cured more than 10GPa time, the dispersion of metal particle is suppressed significantly, therefore the metal particle generated becomes too small, exist such as utilize local surface plasma resonance sensor purposes in time sensitivity decrease tendency, but also the toughness existed as the polyimide resin of matrix reduces and becomes the tendency of the material be highly brittle.
In addition, in the present embodiment, define the Young's modulus of the polyimide resin after solidification, this is because: this Young's modulus is relevant with the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of operation b, becomes the index of the Young's modulus in reflect heat treating processes.That is, the Young's modulus of the polyimide resin after solidification is higher, the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of then operation b is higher, the Young's modulus of the polyimide resin after solidification is lower, then the Young's modulus of the polyimide precursor resin/polyimide resin in the heat treatment process of operation b is lower.Therefore, by controlling the Young's modulus of the polyimide resin after solidification, the thermodiffusion of metal particle can be controlled.
In addition, by this thermal treatment, the polyimide precursor resin in coated film is carried out imidization, the content forming metal particle is 10 μ g/cm 2~ 30 μ g/cm 2scope in, be preferably 10 μ g/cm 2~ 27 μ g/cm 2scope in, more preferably 10 μ g/cm 2~ 25 μ g/cm 2scope in and thickness be 100nm ~ 300nm scope in, be preferably 150nm ~ 300nm scope in polyimide resin layer.
As mentioned above, the median size of metal particle and spacing of particle are from thermal treatment temp, the ii that can pass through in i) heat treatment step) content, the iii of metal ion (or metal-salt) that contain in coated film) thickness of the final polyimide resin layer formed and iv) hardness of polyimide precursor resin/polyimide resin when heat-treating controls.The present inventor obtains following opinion: and the metal ion (or metal-salt) that in coated film contain constant when thermal treatment temp even if absolute magnitude different time or coated film in the absolute magnitude of metal ion (or metal-salt) that contains constant and the thickness of coated film is different time, the particle diameter of the metal particle of precipitation is different.In addition; have also obtained following opinion: when having carried out thermal treatment when the thickness of the content of the metal ion (or metal-salt) not controlling to contain in thermal treatment temp, coated film and the final polyimide resin layer formed, spacing of particle is to reduce or metal particle can form island in the surperficial aggegation of polyimide resin layer sometimes sometimes.In addition, have also obtained following opinion: the Young's modulus of polyimide precursor resin/polyimide resin when carrying out the thermal treatment of operation b can have an impact to the thermal diffusivity of metal particle, under thermal treatment temp, polyimide precursor resin/polyimide resin is softer, more be easy to the thermodiffusion carrying out metal particle, otherwise polyimide precursor resin/polyimide resin is harder, be more difficult to the thermodiffusion carrying out metal particle.
Use above opinion, found: by control above-mentioned i) ~ iv) condition, can control the median size of metal particle and spacing of particle from.That is, by control i) ~ iv) condition, the median size of metal particle can be controlled within the scope of 5nm ~ 35nm, and be taken respective particle interval (spacing of particle from) L as the particle diameter (D of metal particle larger in adjacent metal particulate by the metal particle that so controls l) more than i.e. L>=D lrelation exist.The Metal microparticle composite of present embodiment, by possessing the prerequisite of operation a and operation b, makes the thermodiffusion of the metal particle of precipitation become easy, thus becomes with particle diameter D larger in adjacent metal particulate labove spacing of particle is dispersed in the state in polyimide resin from L.Even if spacing of particle does not greatly have special problem from L yet, but each spacing of particle formed owing to utilizing thermodiffusion in the metal particle of dispersion state has close relationship from L and the particle diameter D of metal particle and the volume fraction of metal particle described later, therefore spacing of particle controls from the upper limit of L preferably by the lower value of the volume fraction of metal particle.
In the present embodiment, the volume fraction of metal particle is made to be in the scope of 1 ~ 15% relative to Metal microparticle composite, to be preferably in the scope of 2 ~ 10%.By making volume fraction be in above-mentioned scope, the spacing of particle of metal particle can be controlled from L.The volume fraction of metal particle can regulate mainly through the content of the metal ingredient in the coating fluid in operation a.
In addition, in the manufacture method of present embodiment, except above-mentioned operation a and operation b, any operations such as such as etching work procedure can also be carried out.
As mentioned above, the manufacture method of Metal microparticle composite according to the present embodiment, owing to metal ion (or metal-salt) being reduced and precipitating metal particulate in the inside of polyimide precursor resin, therefore easily regulate the content of the metallic compound in polyimide precursor resin, easily regulate the content of the metal particle be dispersed in polyimide resin.Therefore, it is possible to manufacture with comparalive ease containing median size be 5nm ~ 35nm scope in metal particle and the volume fraction of metal particle be 1 ~ 15% scope in, thickness is Metal microparticle composite in the scope of 100nm ~ 300nm.And, because this reduction treatment utilizes heating to carry out, therefore, it is possible to utilize the thermodiffusion of metal particle of separating out make metal particle with keep certain above spacing of particle from state be dispersed in matrix resin.In addition, make to separate loose metal particle with certain above spacing of particle to come into existence from the skin section of matrix resin.
In addition, the manufacture method of Metal microparticle composite according to the present embodiment, utilizes the heat used in reduction treatment can also complete the imidization of polyimide precursor resin, thus can simplify production process.
By the Metal microparticle composite of the method manufacture of present embodiment owing to possessing said structure characteristic, utilize in that the field of surface plasmons is representative, the various industrial circle such as such as electromagnetic shielding material, magnetic noise absorbing material, high thermal conductive resin material therefore, it is possible to be applied to pressure transmitter etc.The Metal microparticle composite particularly obtained by the method for present embodiment has the sufficient thickness of 100nm ~ 300nm due to polyimide resin layer, and the median size of metal particle is relatively little compared with above-mentioned thickness, for 5nm ~ 35nm, and the volume fraction of metal particle is 1 ~ 15% relative to Metal microparticle composite, therefore can preferably be applicable in the purposes of the pressure transmitter utilizing local surface plasma resonance.That is, due to polyimide resin layer thickness relative to the median size of metal particle and spacing of particle from for enough large, the amplitude of recoverable deformation when therefore can increase pressurization, also can increase the miles of relative movement of the metal particle of inside during recoverable deformation.Therefore, it is possible to the detection boundary of pressure transmitter is broadened, and improve accuracy of detection.And due to the narrow range of the median size of metal particle, be 5nm ~ 35nm, therefore the inequality of particle diameter is little, obtains sharp-pointed absorption when pressurizeing by local surface plasma resonance, thus can carry out highly sensitive detection.Therefore, utilizing pressure range wide and obtaining high detection sensitivity and estimating precision of pressure transmitter can be expected.In addition, the Metal microparticle composite obtained by the method for present embodiment, owing to polyimide resin layer film can be turned to 100nm ~ 300nm, is therefore applicable to the purposes of the subtle change of the skin section of Metal microparticle composite being carried out to sensing detection.Utilize such character, such as by carrying out etching and processing to the skin section of Metal microparticle composite, a part for the metal particle of the skin section being present in this complex body is made to expose to surface from matrix, can be advantageously used for the sensor base plate etc. the change of outside atmosphere being carried out to sensing detection, it applies desirable.
Other formation in the manufacture method of the Metal microparticle composite of present embodiment is identical with the 1st embodiment with effect.
Embodiment
Then, illustrate the present invention by embodiment, but the invention is not restricted to these embodiments.In addition, in an embodiment of the present invention, unless otherwise specified, various mensuration, evaluate based on following content.
[mensuration of the median size of metal particle]
About the mensuration of the median size of metal particle, use slicing machine (Leica Inc., ULTRACUT UTC ultramicrotome) to make ultrathin section(ing) the section of sample, utilize transmission electron microscope (TEM; NEC Inc., JEM-2000EX) observe.In addition, owing to being difficult to observe by aforesaid method the sample made on the glass substrate, being therefore used in the sample that polyimide film makes with the same terms and observing.In addition, the median size of metal particle is surface mean diameter.
[absorption spectrometry of sample]
The absorption spectrum of obtained sample is observed by ultraviolet-visible-near-infrared spectroscopy (Japanese light splitting Inc., UV-vis U-4000).
[mensuration of optical transmittance]
Optical transmittance uses UV-vis spectroscopy analysis (Japanese light splitting Inc., UV-vis V-550) to measure.
[mensuration of Young's modulus]
Use the RSA II of Rheometrics Inc., heat-up rate be 10 DEG C/min, under temperature range is 40 DEG C to 450 DEG C, frequency is 1Hz, shape becomes the condition of 0.001, dynamic visco-elastic property is measured to the polyimide film being cut into 5 × 33mm size, obtains the Young's modulus of polyimide at each temperature.
Synthesis example 1
In the removable flask of 1000ml, at the N of 425g, 2 of 31.8g is added in N-N,N-DIMETHYLACETAMIDE (DMAc), 2 '-dimethyl-4,1,3-two (4-amino-benzene oxygen) benzene (APB) of 4 '-benzidine (m-TB) and 4.9g also at room temperature stirs 30 minutes.Then, the pyromellitic acid anhydride (PMDA) of 28.6g and 3,4 of 9.6g are added, 3 ', 4 '-biphenyl tetracarboxylic dianhydride (BPDA), stirs in room temperature with constant under nitrogen atmosphere and carries out polyreaction in 3 hours, obtains the polyimide precursor resin solution S of thickness 1.The polyimide precursor resin solution S of gained 1the viscosity result that utilizes E type viscometer (BROOKFIELD Inc., DV-II+Pro CP type) to record be 28000 centipoises (25 DEG C).
By the polyimide precursor resin solution S of gained 1be coated on stainless steel substrate, at 130 DEG C, drying 3 minutes, made it be warmed up to 360 DEG C with 15 minutes and completes imidization, thus obtained the polyimide film be layered on stainless steel substrate.This polyimide film is peeled off from stainless steel substrate, obtains the polyimide film P that thickness is 25 μm 1.The optical transmittance that this film is 400nm, 500nm and 600nm place at wavelength is respectively 0%, 70.5% and 82%.In addition, to this film measure temperature be 200 DEG C, 300 DEG C and 400 DEG C time the result of Young's modulus be respectively 3GPa, 2GPa and 0.6GPa.
Synthesis example 2
In the removable flask of 500ml, stir and 2,2 ' of 15.24g-bis-(trifluoromethyl)-4,4 '-benzidine (TFMB) 47.6mmol is dissolved in the DMAc of 170g.Then, in this solution, add 4 of 14.76g under nitrogen gas stream, two Tetra hydro Phthalic anhydride (ODPA) 47.6mmol of 4 '-oxygen, at room temperature Keep agitation carries out polyreaction in 4 hours, obtains the polyimide precursor resin solution S of colorless viscous 2.The polyimide precursor resin solution S of gained 2the viscosity result that utilizes E type viscometer (BROOKFIELD Inc., DV-II+Pro CP type) to record be 3251 centipoises (25 DEG C).Weight-average molecular weight (Mw) is by gel permeation chromatography (GPC; TOSOH Co., Ltd's system, HLC-8220GPC) measure, be Mw=163900.
By the polyimide precursor resin solution S of gained 2be coated on stainless steel substrate, at 130 DEG C, drying 3 minutes, made it be warmed up to 360 DEG C with 15 minutes and completes imidization, thus obtained the polyimide film be layered on stainless steel substrate.This polyimide film is peeled off from stainless steel substrate, obtains the polyimide film P that thickness is 10 μm 2.This film the optical transmittance that wavelength is 400nm place be 95%, visible ray average transmittance is 96%.In addition, to this film measure temperature be 200 DEG C, 300 DEG C and 400 DEG C time the result of Young's modulus be respectively 0.2GPa, 0.01GPa and 0.001GPa.
Synthesis example 3
In the removable flask of 1000ml, in the N,N-dimethylacetamide (DMAc) of 425g, add 1,3-two (4-amino-benzene oxygen) benzene (APB) of 36.4g and at room temperature stir 30 minutes.Then, the pyromellitic acid anhydride (PMDA) of 11.1g and 3,3 ' of 27.4g is added, 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA), stirs in room temperature with constant under nitrogen atmosphere and carries out polyreaction in 3 hours, obtains the polyimide precursor resin solution S of thickness 3.The polyimide precursor resin solution S of gained 3the viscosity result that utilizes E type viscometer (BROOKFIELD Inc., DV-II+Pro CP type) to record be 2500 centipoises (25 DEG C).
By the polyimide precursor resin solution S of gained 3be coated on stainless steel substrate, at 130 DEG C, drying 3 minutes, made it be warmed up to 360 DEG C with 15 minutes and completes imidization, thus obtained the polyimide film be layered on stainless steel substrate.This polyimide film is peeled off from stainless steel substrate, obtains the polyimide film P that thickness is 25 μm 3.The optical transmittance that this film is 400nm, 500nm and 600nm place at wavelength is respectively 0%, 60% and 72%.In addition, to this film measure temperature be 200 DEG C, 300 DEG C and 400 DEG C time the result of Young's modulus be respectively 1GPa, 0.08GPa and 0.008GPa.
Production example 1
By the 5N aqueous sodium hydroxide solution process 5 minute of the test film 10cm × 10cm (thickness is 0.7mm) of non-alkali glass (Asahi Glass Co., Ltd's system, AN-100) with 50 DEG C.Then, after the glass substrate pure water of test film, drying, it is made to be impregnated in 3-aminopropyl trimethyoxysilane (hereinafter referred to as " γ-the APS ") aqueous solution of 1 % by weight.Carry out drying after being taken out from the γ-APS aqueous solution by this glass substrate, heat 5 minutes at 110 DEG C, obtained glass substrate G1.
[embodiment 1-1]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.191g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-1 containing gold complex forming that on glass substrate G1 thickness is about 1380nm.The gold content of the per unit area of the polyimide precursor resin film 1-1 containing gold complex is 8.19 μ g/cm 2.The polyimide precursor resin film 1-1 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-1 (thickness is 828nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-1 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 10.6nm; Maximum particle diameter: 18.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-1: 0.5%; Spacing of particle from mean value: 39.4nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-1 observes that summit is 560nm, peak width at half height is the absorption peak of 72nm.
[embodiment 1-2]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.191g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-2 containing gold complex forming that on glass substrate G1 thickness is about 1473nm.The gold content of the per unit area of the polyimide precursor resin film 1-2 containing gold complex is 8.74 μ g/cm 2.The polyimide precursor resin film 1-2 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-2 (thickness is 884nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-2 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 12.2nm; Maximum particle diameter: 29.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-2: 0.5%; Spacing of particle from mean value: 45.3nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-2 observes that summit is 564nm, peak width at half height is the absorption peak of 92nm.
[embodiment 1-3]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.191g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-3 containing gold complex forming that on glass substrate G1 thickness is about 1440nm.The gold content of the per unit area of the polyimide precursor resin film 1-3 containing gold complex is 8.55 μ g/cm 2.The polyimide precursor resin film 1-3 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-3 (thickness is 865nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-3 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 15.0nm; Maximum particle diameter: 29.0nm; Minimum grain size: 6.0nm; The volume fraction of the gold in nano composite membrane 1-3: 0.5%; Spacing of particle from mean value: 55.7nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-3 observes that summit is 570nm, peak width at half height is the absorption peak of 76nm.
[embodiment 1-4]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.191g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-4 containing gold complex forming that on glass substrate G1 thickness is about 1370nm.The gold content of the per unit area of the polyimide precursor resin film 1-4 containing gold complex is 7.98 μ g/cm 2.The polyimide precursor resin film 1-4 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-4 (thickness is 827nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-4 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 13.3nm; Maximum particle diameter: 22.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-4: 0.5%; Spacing of particle from mean value: 49.4nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-4 observes that summit is 560nm, peak width at half height is the absorption peak of 80nm.
[embodiment 1-5]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.191g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-5 containing gold complex forming that on glass substrate G1 thickness is about 1260nm.The gold content of the per unit area of the polyimide precursor resin film 1-5 containing gold complex is 7.29 μ g/cm 2.The polyimide precursor resin film 1-5 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-5 (thickness is 755nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-5 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 17.4nm; Maximum particle diameter: 26.0nm; Minimum grain size: 7.0nm; The volume fraction of the gold in nano composite membrane 1-5: 0.5%; Spacing of particle from mean value: 64.6nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-5 observes that summit is 574nm, peak width at half height is the absorption peak of 69nm.
[embodiment 1-6]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.191g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-6 containing gold complex forming that on glass substrate G1 thickness is about 1220nm.The gold content of the per unit area of the polyimide precursor resin film 1-6 containing gold complex is 7.06 μ g/cm 2.The polyimide precursor resin film 1-6 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-6 (thickness is 730nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-6 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 19.8nm; Maximum particle diameter: 35.0nm; Minimum grain size: 10.0nm; The volume fraction of the gold in nano composite membrane 1-6: 0.5%; Spacing of particle from mean value: 73.5nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-6 observes that summit is 576nm, peak width at half height is the absorption peak of 72nm.
[embodiment 1-7]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.127g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-7 containing gold complex forming that on glass substrate G1 thickness is about 750nm.The gold content of the per unit area of the polyimide precursor resin film 1-7 containing gold complex is 4.45 μ g/cm 2.The polyimide precursor resin film 1-7 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-7 (thickness is 450nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-7 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 8.5nm; Maximum particle diameter: 11.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-7: 0.5%; Spacing of particle from mean value: 31.6nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-7 observes that summit is 546nm, peak width at half height is the absorption peak of 83nm.
[embodiment 1-8]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.127g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-8 containing gold complex forming that on glass substrate G1 thickness is about 770nm.The gold content of the per unit area of the polyimide precursor resin film 1-8 containing gold complex is 4.55 μ g/cm 2.The polyimide precursor resin film 1-8 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-8 (thickness is 460nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-8 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 9.6nm; Maximum particle diameter: 17.0nm; Minimum grain size: 5.0nm; The volume fraction of the gold in nano composite membrane 1-8: 0.5%; Spacing of particle from mean value: 35.6nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-8 observes that summit is 560nm, peak width at half height is the absorption peak of 77nm.
[embodiment 1-9]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.127g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-9 containing gold complex forming that on glass substrate G1 thickness is about 760nm.The gold content of the per unit area of the polyimide precursor resin film 1-9 containing gold complex is 4.53 μ g/cm 2.The polyimide precursor resin film 1-9 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-9 (thickness is 458nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-9 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 9.8nm; Maximum particle diameter: 19.0nm; Minimum grain size: 5.0nm; The volume fraction of the gold in nano composite membrane 1-9: 0.5%; Spacing of particle from mean value: 36.4nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-9 observes that summit is 560nm, peak width at half height is the absorption peak of 69nm.
[embodiment 1-10]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.127g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-10 containing gold complex forming that on glass substrate G1 thickness is about 732nm.The gold content of the per unit area of the polyimide precursor resin film 1-10 containing gold complex is 4.24 μ g/cm 2.The polyimide precursor resin film 1-10 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-10 (thickness is 439nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-10 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 9.1nm; Maximum particle diameter: 14.0nm; Minimum grain size: 7.0nm; The volume fraction of the gold in nano composite membrane 1-10: 0.5%; Spacing of particle from mean value: 33.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-10 observes that summit is 542nm, peak width at half height is the absorption peak of 71nm.
[embodiment 1-11]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.127g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-11 containing gold complex forming that on glass substrate G1 thickness is about 730nm.The gold content of the per unit area of the polyimide precursor resin film 1-11 containing gold complex is 4.23 μ g/cm 2.The polyimide precursor resin film 1-11 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-11 (thickness is 438nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-11 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 12.3nm; Maximum particle diameter: 22.0nm; Minimum grain size: 6.0nm; The volume fraction of the gold in nano composite membrane 1-11: 0.5%; Spacing of particle from mean value: 45.7nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-11 observes that summit is 550nm, peak width at half height is the absorption peak of 65nm.
[embodiment 1-12]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.127g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-12 containing gold complex forming that on glass substrate G1 thickness is about 592nm.The gold content of the per unit area of the polyimide precursor resin film 1-12 containing gold complex is 3.43 μ g/cm 2.The polyimide precursor resin film 1-12 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-12 (thickness is 355nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-12 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 12.4nm; Maximum particle diameter: 22.0nm; Minimum grain size: 8.0nm; The volume fraction of the gold in nano composite membrane 1-12: 0.5%; Spacing of particle from mean value: 46.0nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-12 observes that summit is 552nm, peak width at half height is the absorption peak of 69nm.
[embodiment 1-13]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.038g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-13 containing gold complex forming that on glass substrate G1 thickness is about 1430nm.The gold content of the per unit area of the polyimide precursor resin film 1-13 containing gold complex is 1.69 μ g/cm 2.The polyimide precursor resin film 1-13 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-13 (thickness is 857nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-13 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 4.9nm; Maximum particle diameter: 8.0nm; Minimum grain size: 3.0nm; The volume fraction of the gold in nano composite membrane 1-13: 0.1%; Spacing of particle from mean value: 34.6nm.
[embodiment 1-14]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.038g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-14 containing gold complex forming that on glass substrate G1 thickness is about 1455nm.The gold content of the per unit area of the polyimide precursor resin film 1-14 containing gold complex is 1.73 μ g/cm 2.The polyimide precursor resin film 1-14 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-14 (thickness is 873nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-14 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 6.1nm; Maximum particle diameter: 9.0nm; Minimum grain size: 3.0nm; The volume fraction of the gold in nano composite membrane 1-14: 0.1%; Spacing of particle from mean value: 43.1nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-14 observes that summit is 558nm, peak width at half height is the absorption peak of 60nm.
[embodiment 1-15]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.038g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-15 containing gold complex forming that on glass substrate G1 thickness is about 1430nm.The gold content of the per unit area of the polyimide precursor resin film 1-15 containing gold complex is 1.69 μ g/cm 2.The polyimide precursor resin film 1-15 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-15 (thickness is 857nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-15 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 6.9nm; Maximum particle diameter: 9.0nm; Minimum grain size: 5.0nm; The volume fraction of the gold in nano composite membrane 1-15: 0.1%; Spacing of particle from mean value: 48.7nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-15 observes that summit is 552nm, peak width at half height is the absorption peak of 68nm.
[embodiment 1-16]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.025g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-16 containing gold complex forming that on glass substrate G1 thickness is about 780nm.The gold content of the per unit area of the polyimide precursor resin film 1-16 containing gold complex is 0.93 μ g/cm 2.The polyimide precursor resin film 1-16 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-16 (thickness is 470nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-16 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 4.8nm; Maximum particle diameter: 6.0nm; Minimum grain size: 3.0nm; The volume fraction of the gold in nano composite membrane 1-16: 0.1%; Spacing of particle from mean value: 33.9nm.
[embodiment 1-17]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.025g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-17 containing gold complex forming that on glass substrate G1 thickness is about 705nm.The gold content of the per unit area of the polyimide precursor resin film 1-17 containing gold complex is 0.84 μ g/cm 2.The polyimide precursor resin film 1-17 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-17 (thickness is 423nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-17 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 5.5nm; Maximum particle diameter: 7.0nm; Minimum grain size: 3.0nm; The volume fraction of the gold in nano composite membrane 1-17: 0.1%; Spacing of particle from mean value: 38.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-17 observes that summit is 544nm, peak width at half height is the absorption peak of 57nm.
[embodiment 1-18]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.025g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-18 containing gold complex forming that on glass substrate G1 thickness is about 690nm.The gold content of the per unit area of the polyimide precursor resin film 1-18 containing gold complex is 0.82 μ g/cm 2.The polyimide precursor resin film 1-18 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-18 (thickness is 414nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-18 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 6.6nm; Maximum particle diameter: 8.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-18: 0.1%; Spacing of particle from mean value: 46.6nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-18 observes that summit is 546nm, peak width at half height is the absorption peak of 63nm.
[embodiment 1-19]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.038g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-19 containing gold complex forming that on glass substrate G1 thickness is about 1510nm.The gold content of the per unit area of the polyimide precursor resin film 1-19 containing gold complex is 1.75 μ g/cm 2.The polyimide precursor resin film 1-19 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-19 (thickness is 905nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-19 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 5.6nm; Maximum particle diameter: 7.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-19: 0.1%; Spacing of particle from mean value: 39.5nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-19 observes that summit is 544nm, peak width at half height is the absorption peak of 56nm.
[embodiment 1-20]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.038g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-20 containing gold complex forming that on glass substrate G1 thickness is about 1180nm.The gold content of the per unit area of the polyimide precursor resin film 1-20 containing gold complex is 1.37 μ g/cm 2.The polyimide precursor resin film 1-20 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-20 (thickness is 708nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-20 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 6.2nm; Maximum particle diameter: 8.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-20: 0.1%; Spacing of particle from mean value: 43.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-20 observes that summit is 530nm, peak width at half height is the absorption peak of 72nm.
[embodiment 1-21]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.038g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-21 containing gold complex forming that on glass substrate G1 thickness is about 1310nm.The gold content of the per unit area of the polyimide precursor resin film 1-21 containing gold complex is 1.52 μ g/cm 2.The polyimide precursor resin film 1-21 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-21 (thickness is 788nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-21 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 7.2nm; Maximum particle diameter: 10.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-21: 0.1%; Spacing of particle from mean value: 50.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-21 observes that summit is 538nm, peak width at half height is the absorption peak of 72nm.
[embodiment 1-22]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.025g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-22 containing gold complex forming that on glass substrate G1 thickness is about 680nm.The gold content of the per unit area of the polyimide precursor resin film 1-22 containing gold complex is 0.79 μ g/cm 2.The polyimide precursor resin film 1-22 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-22 (thickness is 410nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-22 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 5.2nm; Maximum particle diameter: 7.0nm; Minimum grain size: 3.0nm; The volume fraction of the gold in nano composite membrane 1-22: 0.1%; Spacing of particle from mean value: 36.7nm.
[embodiment 1-23]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.025g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-23 containing gold complex forming that on glass substrate G1 thickness is about 680nm.The gold content of the per unit area of the polyimide precursor resin film 1-23 containing gold complex is 0.78 μ g/cm 2.The polyimide precursor resin film 1-23 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-23 (thickness is 406nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-23 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 5.8nm; Maximum particle diameter: 8.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-23: 0.1%; Spacing of particle from mean value: 40.9nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-23 observes that summit is 542nm, peak width at half height is the absorption peak of 77nm.
[embodiment 1-24]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.025g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-24 containing gold complex forming that on glass substrate G1 thickness is about 580nm.The gold content of the per unit area of the polyimide precursor resin film 1-24 containing gold complex is 0.68 μ g/cm 2.The polyimide precursor resin film 1-24 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-24 (thickness is 350nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 1-24 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: roughly spherical; Median size: 6.6nm; Maximum particle diameter: 9.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 1-24: 0.1%; Spacing of particle from mean value: 46.6nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-24 observes that summit is 538nm, peak width at half height is the absorption peak of 84nm.
[embodiment 1-25]
The polyimide precursor resin solution S obtained in 6.67g synthesis example 2 2middle interpolation is dissolved in the 0.118g Silver Nitrate in the DMAc of 13.33g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing silver complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of silver complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-25 containing silver complex forming that on glass substrate G1 thickness is about 667nm.The silver content of the per unit area of the polyimide precursor resin film 1-25 containing silver complex is 3.78 μ g/cm 2.The polyimide precursor resin film 1-25 this being contained silver complex is heat treated 10 minutes at 300 DEG C under vacuo, obtained in yellow argent microparticulate nano composite membrane 1-25 (thickness is 402nm).The argent particulate be formed in nano composite membrane 1-25 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal silver particulate.In addition, argent particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the argent particulate in this film is as described below.
Shape: roughly spherical; Median size: 7.9nm; Maximum particle diameter: 10.5nm; Minimum grain size: 5.2nm; The volume fraction of the silver in nano composite membrane 1-25: 0.9%; Spacing of particle from mean value: 18.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the argent particulate of nano composite membrane 1-25 observes that summit is 442nm, peak width at half height is the absorption peak of 76nm.
[comparative example 1-1]
The polyimide precursor resin solution S obtained in 7.50g synthesis example 1 1middle interpolation is dissolved in the 0.489g hydrochloro-auric acid tetrahydrate in the DMAc of 7.50g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-25 containing gold complex forming that on glass substrate G1 thickness is about 1275nm.The gold content of the per unit area of the polyimide precursor resin film 1-25 containing gold complex is 20.48 μ g/cm 2.The polyimide precursor resin film 1-25 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-25 (thickness is 765nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-25.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-25 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 11.5nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 28.0nm.
2) face of distance nano composite membrane 1-25 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 23.0nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 84.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-25 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-25 observes that summit is 576nm and 690nm, peak width at half height is the absorption peak of 133nm.
[comparative example 1-2]
The polyimide precursor resin solution S obtained in 7.50g synthesis example 1 1middle interpolation is dissolved in the 0.489g hydrochloro-auric acid tetrahydrate in the DMAc of 7.50g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-26 containing gold complex forming that on glass substrate G1 thickness is about 1260nm.The gold content of the per unit area of the polyimide precursor resin film 1-26 containing gold complex is 20.29 μ g/cm 2.The polyimide precursor resin film 1-26 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-26 (thickness is 758nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-26.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-26 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 12.6nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 28.0nm.
2) face of distance nano composite membrane 1-26 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 25.5nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 85.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-26 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-26 observes that summit is 580nm and 682nm, peak width at half height is the absorption peak of 147nm.
[comparative example 1-3]
The polyimide precursor resin solution S obtained in 7.50g synthesis example 2 2middle interpolation is dissolved in the 0.489g hydrochloro-auric acid tetrahydrate in the DMAc of 7.50g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-27 containing gold complex forming that on glass substrate G1 thickness is about 1137nm.The gold content of the per unit area of the polyimide precursor resin film 1-27 containing gold complex is 17.83 μ g/cm 2.The polyimide precursor resin film 1-27 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-27 (thickness is 682nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-27.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-27 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 17.0nm; Minimum grain size: about 12.0nm; Maximum particle diameter: about 27.0nm.
2) face of distance nano composite membrane 1-27 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 66.8nm; Minimum grain size: about 49.0nm; Maximum particle diameter: about 83.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-27 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-27 observes that summit is 572nm and 688nm, peak width at half height is the absorption peak of 189nm.
[comparative example 1-4]
The polyimide precursor resin solution S obtained in 7.50g synthesis example 2 2middle interpolation is dissolved in the 0.489g hydrochloro-auric acid tetrahydrate in the DMAc of 7.50g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-28 containing gold complex forming that on glass substrate G1 thickness is about 1150nm.The gold content of the per unit area of the polyimide precursor resin film 1-28 containing gold complex is 18.04 μ g/cm 2.The polyimide precursor resin film 1-28 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-28 (thickness is 690nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-28.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-28 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 20.2nm; Minimum grain size: about 13.0nm; Maximum particle diameter: about 29.0nm.
2) face of distance nano composite membrane 1-28 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 65.1nm; Minimum grain size: about 50.0nm; Maximum particle diameter: about 87.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-28 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-28 observes that summit is 620nm and 698nm, peak width at half height is the absorption peak of 216nm.
[comparative example 1-5]
The polyimide precursor resin solution S obtained in 7.50g synthesis example 2 2middle interpolation is dissolved in the 0.489g hydrochloro-auric acid tetrahydrate in the DMAc of 7.50g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-29 containing gold complex forming that on glass substrate G1 thickness is about 1117nm.The gold content of the per unit area of the polyimide precursor resin film 1-29 containing gold complex is 17.52 μ g/cm 2.The polyimide precursor resin film 1-29 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-29 (thickness is 670nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-29.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-29 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 23.0nm; Minimum grain size: about 15.0nm; Maximum particle diameter: about 30.0nm.
2) face of distance nano composite membrane 1-29 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 70.0nm; Minimum grain size: about 52.0nm; Maximum particle diameter: about 90.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-29 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-29 observes that summit is 630nm and 698nm, peak width at half height is the absorption peak of 200nm.
[comparative example 1-6]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-30 containing gold complex forming that on glass substrate G1 thickness is about 750nm.The gold content of the per unit area of the polyimide precursor resin film 1-30 containing gold complex is 12.05 μ g/cm 2.The polyimide precursor resin film 1-30 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-30 (thickness is 450nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-30.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-30 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 7.1nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 13.0nm.
2) face of distance nano composite membrane 1-30 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 17.6nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 36.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-30 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-30 observes that summit is 592nm and 650nm, peak width at half height is the absorption peak of 120nm.
[comparative example 1-7]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-31 containing gold complex forming that on glass substrate G1 thickness is about 640nm.The gold content of the per unit area of the polyimide precursor resin film 1-31 containing gold complex is 10.28 μ g/cm 2.The polyimide precursor resin film 1-31 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-31 (thickness is 384nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-31.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-31 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 10.0nm; Minimum grain size: about 5.0nm; Maximum particle diameter: about 16.0nm.
2) face of distance nano composite membrane 1-31 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 20.8nm; Minimum grain size: about 5.0nm; Maximum particle diameter: about 48.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-31 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-31 observes that summit is 590nm and 650nm, peak width at half height is the absorption peak of 102nm.
[comparative example 1-8]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-32 containing gold complex forming that on glass substrate G1 thickness is about 798nm.The gold content of the per unit area of the polyimide precursor resin film 1-32 containing gold complex is 12.52 μ g/cm 2.The polyimide precursor resin film 1-32 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-32 (thickness is 479nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-32.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-32 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 9.0nm; Minimum grain size: about 7.0nm; Maximum particle diameter: about 12.0nm.
2) face of distance nano composite membrane 1-32 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 26.0nm; Minimum grain size: about 12.0nm; Maximum particle diameter: about 39.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-32 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-32 observes that summit is 574nm and 642nm, peak width at half height is the absorption peak of 102nm.
[comparative example 1-9]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-33 containing gold complex forming that on glass substrate G1 thickness is about 675nm.The gold content of the per unit area of the polyimide precursor resin film 1-33 containing gold complex is 10.59 μ g/cm 2.The polyimide precursor resin film 1-33 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-33 (thickness is 405nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-33.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-33 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 13.6nm; Minimum grain size: about 10.0nm; Maximum particle diameter: about 21.0nm.
2) face of distance nano composite membrane 1-33 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 34.6nm; Minimum grain size: about 25.0nm; Maximum particle diameter: about 50.0nm.
In addition, the volume fraction of the gold in nano composite membrane 1-33 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-33 observes that summit is 588nm and 652nm, peak width at half height is the absorption peak of 107nm.
[comparative example 1-10]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 1-34 containing gold complex forming that on glass substrate G1 thickness is about 650nm.The gold content of the per unit area of the polyimide precursor resin film 1-34 containing gold complex is 10.20 μ g/cm 2.The polyimide precursor resin film 1-34 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 1-34 (thickness is 390nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 1-34.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 1-34 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 16.4nm; Minimum grain size: about 14.0nm; Maximum particle diameter: about 26.0nm.
2) face of distance nano composite membrane 1-34 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 41.1nm; Minimum grain size: about 35.0nm; Maximum particle diameter: about 47.6nm.
In addition, the volume fraction of the gold in nano composite membrane 1-34 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 1-34 observes that summit is 592nm and 654nm, peak width at half height is the absorption peak of 134nm.
[embodiment 2-1]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 2-1 containing gold complex forming that on glass substrate G1 thickness is about 1270nm.The gold content of the per unit area of the polyimide precursor resin film 2-1 containing gold complex is 20.40 μ g/cm 2.The polyimide precursor resin film 2-1 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 2-1 (thickness is 762nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 2-1 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 2-1 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 10.2nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 38.0nm.
2) face of distance nano composite membrane 2-1 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 20.7nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 51.0nm.
In addition, the volume fraction of the gold in nano composite membrane 2-1 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 2-1 observes that summit is 570nm, peak width at half height is the absorption peak of 115nm.
[embodiment 2-2]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 8.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 2-2 containing gold complex forming that on glass substrate G1 thickness is about 725nm.The gold content of the per unit area of the polyimide precursor resin film 2-2 containing gold complex is 11.64 μ g/cm 2.The polyimide precursor resin film 2-2 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 2-2 (thickness is 435nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 2-2 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 2-2 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 6.5nm; Minimum grain size: about 3.0nm; Maximum particle diameter: about 12.0nm.
2) face of distance nano composite membrane 2-2 face side is the region (wherein, when thickness is lower than 600nm, taking thickness as the upper limit) in the thickness range of 100nm ~ 600nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 11.6nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 25.0nm.
In addition, the volume fraction of the gold in nano composite membrane 2-2 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 2-2 observes that summit is 568nm, peak width at half height is the absorption peak of 89nm.
[comparative example 2-1]
The polyimide precursor resin solution S obtained in 7.50g synthesis example 1 1middle interpolation is dissolved in the 0.489g hydrochloro-auric acid tetrahydrate in the DMAc of 7.50g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 2-3 containing gold complex forming that on glass substrate G1 thickness is about 1275nm.The gold content of the per unit area of the polyimide precursor resin film 2-3 containing gold complex is 20.48 μ g/cm 2.The polyimide precursor resin film 2-3 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 2-3 (thickness is 765nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 2-3.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 2-3 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 11.5nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 28.0nm.
2) face of distance nano composite membrane 2-3 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 23.0nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 84.0nm.
In addition, the volume fraction of the gold in nano composite membrane 2-3 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 2-3 observes that summit is 576nm and 690nm, peak width at half height is the absorption peak of 133nm.
[comparative example 2-2]
The polyimide precursor resin solution S obtained in 7.50g synthesis example 1 1middle interpolation is dissolved in the 0.489g hydrochloro-auric acid tetrahydrate in the DMAc of 7.50g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 2-4 containing gold complex forming that on glass substrate G1 thickness is about 1260nm.The gold content of the per unit area of the polyimide precursor resin film 2-4 containing gold complex is 20.29 μ g/cm 2.The polyimide precursor resin film 2-4 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 2-4 (thickness is 758nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 2-4.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 2-4 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 12.6nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 28.0nm.
2) face of distance nano composite membrane 2-4 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 25.5nm; Minimum grain size: about 8.0nm; Maximum particle diameter: about 85.0nm.
In addition, the volume fraction of the gold in nano composite membrane 2-4 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 2-4 observes that summit is 580nm and 682nm, peak width at half height is the absorption peak of 147nm.
[comparative example 2-3]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 2-5 containing gold complex forming that on glass substrate G1 thickness is about 750nm.The gold content of the per unit area of the polyimide precursor resin film 2-5 containing gold complex is 12.05 μ g/cm 2.The polyimide precursor resin film 2-5 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 2-5 (thickness is 450nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 2-5.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 2-5 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 7.1nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 13.0nm.
2) face of distance nano composite membrane 2-5 face side is the region (wherein, when thickness is lower than 600nm, taking thickness as the upper limit) in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 17.6nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 36.0nm.
In addition, the volume fraction of the gold in nano composite membrane 2-5 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 2-5 observes that summit is 592nm and 650nm, peak width at half height is the absorption peak of 120nm.
[comparative example 2-4]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 2-6 containing gold complex forming that on glass substrate G1 thickness is about 640nm.The gold content of the per unit area of the polyimide precursor resin film 2-6 containing gold complex is 10.28 μ g/cm 2.The polyimide precursor resin film 2-6 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 2-6 (thickness is 384nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 2-6.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 2-6 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 10.0nm; Minimum grain size: about 5.0nm; Maximum particle diameter: about 16.0nm.
2) face of distance nano composite membrane 2-6 face side is the region (wherein, when thickness is lower than 600nm, taking thickness as the upper limit) in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 20.8nm; Minimum grain size: about 5.0nm; Maximum particle diameter: about 48.0nm.
In addition, the volume fraction of the gold in nano composite membrane 2-6 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 2-6 observes that summit is 590nm and 650nm, peak width at half height is the absorption peak of 102nm.
[embodiment 3-1]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-1 containing gold complex forming that on glass substrate G1 thickness is about 377nm.The gold content of the per unit area of the polyimide precursor resin film 3-1 containing gold complex is 6.05 μ g/cm 2.The polyimide precursor resin film 3-1 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-1 (thickness is 226nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-1 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 8.7nm; Maximum particle diameter: 20.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 3-1: 1.35%; Spacing of particle from mean value: 20.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-1 observes that summit is 550nm, peak width at half height is the absorption peak of 80nm.
[embodiment 3-2]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-2 containing gold complex forming that on glass substrate G1 thickness is about 315nm.The gold content of the per unit area of the polyimide precursor resin film 3-2 containing gold complex is 5.06 μ g/cm 2.The polyimide precursor resin film 3-2 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-2 (thickness is 189nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-2 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 10.2nm; Maximum particle diameter: 21.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 3-2: 1.35%; Spacing of particle from mean value: 24.3nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-2 observes that summit is 564nm, peak width at half height is the absorption peak of 76nm.
[embodiment 3-3]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 1 1middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-3 containing gold complex forming that on glass substrate G1 thickness is about 367nm.The gold content of the per unit area of the polyimide precursor resin film 3-3 containing gold complex is 5.89 μ g/cm 2.The polyimide precursor resin film 3-3 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-3 (thickness is 220nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-3 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 13.8nm; Maximum particle diameter: 21.0nm; Minimum grain size: 4.0nm; The volume fraction of the gold in nano composite membrane 3-3: 1.35%; Spacing of particle from mean value: 32.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-3 observes that summit is 564nm, peak width at half height is the absorption peak of 87nm.
[embodiment 3-4]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 3 3middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-4 containing gold complex forming that on glass substrate G1 thickness is about 338nm.The gold content of the per unit area of the polyimide precursor resin film 3-4 containing gold complex is 5.33 μ g/cm 2.The polyimide precursor resin film 3-4 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-4 (thickness is 203nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-4 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 12.4nm; Maximum particle diameter: 30.0nm; Minimum grain size: 5.0nm; The volume fraction of the gold in nano composite membrane 3-4: 1.35%; Spacing of particle from mean value: 29.6nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-4 observes that summit is 556nm, peak width at half height is the absorption peak of 112nm.
[embodiment 3-5]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 3 3middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-5 containing gold complex forming that on glass substrate G1 thickness is about 332nm.The gold content of the per unit area of the polyimide precursor resin film 3-5 containing gold complex is 5.22 μ g/cm 2.The polyimide precursor resin film 3-5 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-5 (thickness is 199nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-5 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 14.2nm; Maximum particle diameter: 30.0nm; Minimum grain size: 6.0nm; The volume fraction of the gold in nano composite membrane 3-5: 1.35%; Spacing of particle from mean value: 33.8nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-5 observes that summit is 564nm, peak width at half height is the absorption peak of 111nm.
[embodiment 3-6]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 3 3middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-6 containing gold complex forming that on glass substrate G1 thickness is about 413nm.The gold content of the per unit area of the polyimide precursor resin film 3-6 containing gold complex is 6.51 μ g/cm 2.The polyimide precursor resin film 3-6 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-6 (thickness is 248nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-6 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 19.4nm; Maximum particle diameter: 49.0nm; Minimum grain size: 6.0nm; The volume fraction of the gold in nano composite membrane 3-6: 1.35%; Spacing of particle from mean value: 46.2nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-6 observes that summit is 570nm, peak width at half height is the absorption peak of 94nm.
[embodiment 3-7]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-7 containing gold complex forming that on glass substrate G1 thickness is about 337nm.The gold content of the per unit area of the polyimide precursor resin film 3-7 containing gold complex is 5.28 μ g/cm 2.The polyimide precursor resin film 3-7 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-7 (thickness is 202nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-7 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 12.3nm; Maximum particle diameter: 16.0nm; Minimum grain size: 7.0nm; The volume fraction of the gold in nano composite membrane 3-7: 1.35%; Spacing of particle from mean value: 29.2nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-7 observes that summit is 548nm, peak width at half height is the absorption peak of 78nm.
[embodiment 3-8]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-8 containing gold complex forming that on glass substrate G1 thickness is about 348nm.The gold content of the per unit area of the polyimide precursor resin film 3-8 containing gold complex is 5.46 μ g/cm 2.The polyimide precursor resin film 3-8 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-8 (thickness is 209nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 3-8 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 16.5nm; Maximum particle diameter: 23.0nm; Minimum grain size: 11.0nm; The volume fraction of the gold in nano composite membrane 3-8: 1.35%; Spacing of particle from mean value: 39.4nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-8 observes that summit is 562nm, peak width at half height is the absorption peak of 76nm.
[comparative example 3-1]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-9 containing gold complex forming that on glass substrate G1 thickness is about 750nm.The gold content of the per unit area of the polyimide precursor resin film 3-9 containing gold complex is 12.05 μ g/cm 2.The polyimide precursor resin film 3-9 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-9 (thickness is 450nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 3-9.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 3-9 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 7.1nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 13.0nm.
2) face of distance nano composite membrane 3-9 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 17.6nm; Minimum grain size: about 4.0nm; Maximum particle diameter: about 36.0nm.
In addition, the volume fraction of the gold in nano composite membrane 3-9 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-9 observes that summit is 592nm and 650nm, peak width at half height is the absorption peak of 120nm.
[comparative example 3-2]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 1 1middle interpolation is dissolved in the 0.348g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-10 containing gold complex forming that on glass substrate G1 thickness is about 640nm.The gold content of the per unit area of the polyimide precursor resin film 3-10 containing gold complex is 10.28 μ g/cm 2.The polyimide precursor resin film 3-10 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-10 (thickness is 384nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 3-10.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
1) face of distance nano composite membrane 3-10 face side is the region in the thickness range of 0nm ~ 100nm:
Shape: polyhedral and spherical particle mixing exist; Median size: about 10.0nm; Minimum grain size: about 5.0nm; Maximum particle diameter: about 16.0nm.
2) face of distance nano composite membrane 3-10 face side is the region in the thickness range of 100nm ~ 600nm:
Shape: polyhedral; Median size: about 20.8nm; Minimum grain size: about 5.0nm; Maximum particle diameter: about 48.0nm.
In addition, the volume fraction of the gold in nano composite membrane 3-10 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-10 observes that summit is 590nm and 650nm, peak width at half height is the absorption peak of 102nm.
[comparative example 3-3]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 1.566g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-11 containing gold complex forming that on glass substrate G1 thickness is about 362nm.The gold content of the per unit area of the polyimide precursor resin film 3-11 containing gold complex is 16.58 μ g/cm 2.The polyimide precursor resin film 3-11 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-11 (thickness is 217nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 3-11.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 41.7nm; Maximum particle diameter: 68.0nm; Minimum grain size: 22.0nm.In addition, the volume fraction of the gold in nano composite membrane 3-11 is 3.96%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-11 observes that summit is 570nm and 640nm, peak width at half height is the absorption peak of 171nm.
[comparative example 3-4]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 0.522g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-12 containing gold complex forming that on glass substrate G1 thickness is about 328nm.The gold content of the per unit area of the polyimide precursor resin film 3-12 containing gold complex is 5.15 μ g/cm 2.The polyimide precursor resin film 3-12 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-12 (thickness is 197nm) taken on a red color.For the metallic gold particulate be formed in nano composite membrane 3-12, confirm the position having aggegation in few part.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 23.5nm; Maximum particle diameter: 34.0nm; Minimum grain size: 16.0nm.In addition, the volume fraction of the gold in nano composite membrane 3-12 is 1.35%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-12 observes that summit is 574nm and 620nm, peak width at half height is the absorption peak of 92nm.
[comparative example 3-5]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 1.566g hydrochloro-auric acid tetrahydrate in the DMAc of 52.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 3-13 containing gold complex forming that on glass substrate G1 thickness is about 118nm.The gold content of the per unit area of the polyimide precursor resin film 3-13 containing gold complex is 5.42 μ g/cm 2.The polyimide precursor resin film 3-13 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 3-13 (thickness is 71nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 3-13.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 32.0nm; Maximum particle diameter: 56.0nm; Minimum grain size: 12.0nm.In addition, the volume fraction of the gold in nano composite membrane 3-13 is 3.96%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 3-13 observes that summit is 554nm and 640nm, peak width at half height is the absorption peak of 158nm.
[embodiment 4-1]
The polyimide precursor resin solution S obtained in 2.67g synthesis example 1 1middle interpolation is dissolved in the 0.726g hydrochloro-auric acid tetrahydrate in the DMAc of 7.33g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 4-1 containing gold complex forming that on glass substrate G1 thickness is about 298nm.The gold content of the per unit area of the polyimide precursor resin film 4-1 containing gold complex is 19.15 μ g/cm 2.The polyimide precursor resin film 4-1 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 4-1 (thickness is 179nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 4-1 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 17.0nm; Maximum particle diameter: 54.0nm; Minimum grain size: 5.0nm; The volume fraction of the gold in nano composite membrane 4-1: 5.54%; Spacing of particle from mean value: 18.9nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 4-1 observes that summit is 572nm, peak width at half height is the absorption peak of 103nm.
[embodiment 4-2]
The polyimide precursor resin solution S obtained in 2.67g synthesis example 1 1middle interpolation is dissolved in the 0.726g hydrochloro-auric acid tetrahydrate in the DMAc of 7.33g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 4-2 containing gold complex forming that on glass substrate G1 thickness is about 337nm.The gold content of the per unit area of the polyimide precursor resin film 4-2 containing gold complex is 21.61 μ g/cm 2.The polyimide precursor resin film 4-2 this being contained gold complex under air at 300 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 4-2 (thickness is 202nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 4-2 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 22.4nm; Maximum particle diameter: 68.0nm; Minimum grain size: 5.0nm; The volume fraction of the gold in nano composite membrane 4-2: 5.54%; Spacing of particle from mean value; 24.9nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 4-2 observes that summit is 570nm, peak width at half height is the absorption peak of 103nm.
[embodiment 4-3]
The polyimide precursor resin solution S obtained in 2.67g synthesis example 1 1middle interpolation is dissolved in the 0.726g hydrochloro-auric acid tetrahydrate in the DMAc of 7.33g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 4-3 containing gold complex forming that on glass substrate G1 thickness is about 282nm.The gold content of the per unit area of the polyimide precursor resin film 4-3 containing gold complex is 18.01 μ g/cm 2.The polyimide precursor resin film 4-3 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 4-3 (thickness is 169nm) taken on a red color.The metallic gold particulate be formed in nano composite membrane 4-3 is fully independent separately, with interval dispersion more than particle diameter larger in adjacent metal gold particulate.In addition, metallic gold particulate comes into existence from the skin section of matrix resin.
In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 24.5nm; Maximum particle diameter: 71.0nm; Minimum grain size: 5.0nm; The volume fraction of the gold in nano composite membrane 4-3: 5.54%; Spacing of particle from mean value: 27.3nm.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 4-3 observes that summit is 576nm, peak width at half height is the absorption peak of 101nm.
[comparative example 4-1]
The polyimide precursor resin solution S obtained in 5.33g synthesis example 2 2middle interpolation is dissolved in the 0.696g hydrochloro-auric acid tetrahydrate in the DMAc of 10.67g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 4-4 containing gold complex forming that on glass substrate G1 thickness is about 325nm.The gold content of the per unit area of the polyimide precursor resin film 4-4 containing gold complex is 10.07 μ g/cm 2.The polyimide precursor resin film 4-4 this being contained gold complex under air at 200 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 4-4 (thickness is 195nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 4-4.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 19.8nm; Maximum particle diameter: 30.0nm; Minimum grain size: 11.0nm.In addition, the volume fraction of the gold in nano composite membrane 4-4 is 2.67%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 4-4 observes that summit is 554nm and 622nm, peak width at half height is the absorption peak of 109nm.
[comparative example 4-2]
The polyimide precursor resin solution S obtained in 8.00g synthesis example 2 2middle interpolation is dissolved in the 1.566g hydrochloro-auric acid tetrahydrate in the DMAc of 16.00g, under nitrogen atmosphere in stirred at ambient temperature 15 minutes, thus the polyimide precursor resin solution of preparation containing gold complex.Use spin coater (Mikasa Co., Ltd. system, SPINCOATER 1H-DX2) by after being coated with on the glass substrate G1 of production example 1 containing the polyimide precursor resin solution of gold complex of gained, at 70 DEG C dry 3 minutes and at 130 DEG C dry 10 minutes, thus the polyimide precursor resin film 4-5 containing gold complex forming that on glass substrate G1 thickness is about 362nm.The gold content of the per unit area of the polyimide precursor resin film 4-5 containing gold complex is 16.58 μ g/cm 2.The polyimide precursor resin film 4-5 this being contained gold complex under air at 400 DEG C heat treated 10 minutes, the obtained metallic gold microparticulate nano composite membrane 4-5 (thickness is 217nm) in purple.Confirm the metallic gold particle fraction aggegation be formed in nano composite membrane 4-5.In addition, the feature being formed at the metallic gold particulate in this film is as described below.
Shape: polyhedral and spherical particle mixing exist; Median size: 41.7nm; Maximum particle diameter: 68.0nm; Minimum grain size: 22.0nm.In addition, the volume fraction of the gold in nano composite membrane 4-5 is 3.96%.
In addition, the absorption spectrum of the local surface plasma resonance produced by the metallic gold particulate of nano composite membrane 4-5 observes that summit is 570nm and 640nm, peak width at half height is the absorption peak of 171nm.
Above, understand embodiments of the present invention in detail to be illustrated as object, but the present invention does not limit by above-mentioned embodiment, can carry out various distortion.In addition, No. 2010-217173, Japanese patent application, No. 2010-217174, Japanese patent application and Japanese patent application 2010-217175 CLAIM OF PRIORITY that this international application is applied for based on No. 2010-178634, the Japanese patent application applied on August 9th, 2010 and on September 28th, 2010, and its full content is incorporated herein.

Claims (5)

1. the manufacture method of a Metal microparticle composite; it is characterized in that; manufacture following Metal microparticle composite; described Metal microparticle composite is that the metal particle being more than 3nm by median size is not in contact with each other and is dispersed in independently of each other in polyimide resin with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate; described metal particle has been the particulate of local surface plasma resonance effect
The manufacture method of described Metal microparticle composite possesses following operation a and b:
A) operation: the coating fluid containing polyimide precursor resin and metallic compound is reached 50 μ g/cm with the content of metal ingredient 2following mode is coated on base material, carries out drying, forms the coated film that dried thickness is less than 1.7 μm;
B) operation: by heat-treating at the temperature of described coated film more than 160 DEG C and in the scope of less than 450 DEG C, metal ion in described coated film or metal salt back are separated out the particle shape metal becoming metal particle, and make it be dispersed in coated film, meanwhile the described polyimide precursor resin in described coated film is carried out imidization, formation thickness is less than 1 μm and Young's modulus is the polyimide resin layer of below 10GPa
In described Metal microparticle composite, the median size of described metal particle is more than 3nm and in the scope of below 25nm, and the volume fraction of described metal particle is more than 0.05% relative to Metal microparticle composite and in the scope of less than 1%,
The content of the metal ingredient in the described coating fluid in described operation a is 0.5 μ g/cm 2above and 10 μ g/cm 2in following scope, and the thickness of dried described coated film is more than 500nm and in the scope of less than 1.7 μm,
The thickness of the described polyimide resin layer in described operation b is more than 300nm and in the scope of less than 1 μm.
2. the manufacture method of a Metal microparticle composite; it is characterized in that; manufacture following Metal microparticle composite; described Metal microparticle composite is that the metal particle being more than 3nm by median size is not in contact with each other and is dispersed in independently of each other in polyimide resin with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate; described metal particle has been the particulate of local surface plasma resonance effect
The manufacture method of described Metal microparticle composite possesses following operation a and b:
A) operation: the coating fluid containing polyimide precursor resin and metallic compound is reached 50 μ g/cm with the content of metal ingredient 2following mode is coated on base material, carries out drying, forms the coated film that dried thickness is less than 1.7 μm;
B) operation: by heat-treating at the temperature of described coated film more than 160 DEG C and in the scope of less than 450 DEG C, metal ion in described coated film or metal salt back are separated out the particle shape metal becoming metal particle, and make it be dispersed in coated film, meanwhile the described polyimide precursor resin in described coated film is carried out imidization, formation thickness is less than 1 μm and Young's modulus is the polyimide resin layer of below 10GPa
In described Metal microparticle composite, the median size of described metal particle is more than 3nm and in the scope of below 30nm, and the volume fraction of described metal particle is more than 0.2% relative to Metal microparticle composite and in the scope of less than 5%,
The content of the metal ingredient in the described coating fluid in described operation a is 10 μ g/cm 2above and 50 μ g/cm 2in following scope, and the thickness of dried described coated film is more than 500nm and in the scope of less than 1.7 μm,
The thickness of the described polyimide resin layer in described operation b is more than 300nm and in the scope of less than 1 μm, and the Young's modulus of described polyimide resin layer is more than 3GPa and in the scope of below 10GPa.
3. the manufacture method of a Metal microparticle composite; it is characterized in that; manufacture following Metal microparticle composite; described Metal microparticle composite is that the metal particle being more than 3nm by median size is not in contact with each other and is dispersed in independently of each other in polyimide resin with the interval more than particle diameter of the larger metal particle of particle diameter in adjacent metal particulate; described metal particle has been the particulate of local surface plasma resonance effect
The manufacture method of described Metal microparticle composite possesses following operation a and b:
A) operation: the coating fluid containing polyimide precursor resin and metallic compound is reached 50 μ g/cm with the content of metal ingredient 2following mode is coated on base material, carries out drying, forms the coated film that dried thickness is less than 1.7 μm;
B) operation: by heat-treating at the temperature of described coated film more than 160 DEG C and in the scope of less than 450 DEG C, metal ion in described coated film or metal salt back are separated out the particle shape metal becoming metal particle, and make it be dispersed in coated film, meanwhile the described polyimide precursor resin in described coated film is carried out imidization, formation thickness is less than 1 μm and Young's modulus is the polyimide resin layer of below 10GPa
In described Metal microparticle composite, the median size of described metal particle is more than 5nm and in the scope of below 35nm, and the volume fraction of described metal particle is more than 1% relative to Metal microparticle composite and in the scope of less than 15%,
The content of the metal ingredient in the described coating fluid in described operation a is 10 μ g/cm 2above and 30 μ g/cm 2in following scope, and the thickness of dried described coated film is more than 150nm and in the scope of below 500nm,
The thickness of the described polyimide resin layer in described operation b is more than 100nm and in the scope of below 300nm, and the Young's modulus of described polyimide resin layer is more than 0.5GPa and in the scope of below 10GPa.
4. the manufacture method of the Metal microparticle composite according to any one of claims 1 to 3, is characterized in that, described operation b carries out in inertness gas atmosphere.
5. the manufacture method of the Metal microparticle composite according to any one of claims 1 to 3, is characterized in that, described metallic compound is the precursor of Au.
CN201510297230.3A 2010-08-09 2011-07-22 Process for producing metal nanoparticle composite Pending CN105017562A (en)

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