WO2013133315A1 - 金コロイド溶液及びその製造方法 - Google Patents
金コロイド溶液及びその製造方法 Download PDFInfo
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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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
Definitions
- the present invention relates to a stable colloidal gold solution and a method for producing the same.
- gold nanoparticles have been used in many fields such as catalysts, medicine, sensing, electronics, color materials, paints and the like.
- a gold colloid solution in which gold nanoparticles are stably dispersed in a solvent such as water is often used as a raw material.
- Most colloidal gold solutions are produced using chloroauric acid (HAuCl 4 ) as a raw material, and a large amount of chloride ions remain in the solution when gold nanoparticles are obtained by reducing chloroauric acid. Yes.
- JP 2009-120901 A Japanese Patent Laid-Open No. 11-151436
- the main object of the present invention is to provide a stable colloidal gold solution using water as a solvent.
- Another object of the present invention is to provide a method by which such a colloidal gold solution can be easily prepared.
- the present invention provides a colloidal gold solution and a method for producing the colloidal gold solution according to the following embodiment.
- Item 1. Gold nanoparticles having a particle diameter of 100 nm or less in water and an anion R—COO ⁇ (a) represented by the following general formula (a) (Wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms) A colloidal gold solution.
- Item 2. Item 2.
- Item 3. Item 3.
- Item 4. The colloidal gold solution according to any one of Items 1 to 3, wherein the protective colloid is at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid, sodium polyacrylate, polyvinyl alcohol, and carboxymethylcellulose. .
- Item 6. Item 6.
- Item 7. The colloidal gold solution according to any one of claims 1 to 6, which is substantially free of chloride ions.
- Item 8. A method for producing a colloidal gold solution comprising the following steps: (I) a step of preparing a dispersion by dispersing gold carboxylate in water; and (ii) by reducing the gold carboxylate by acting a reducing agent in the dispersion obtained in step (i). A step of obtaining a colloidal gold solution.
- the reduction uses at least one selected from the group consisting of alcohols having primary hydroxyl groups and / or secondary hydroxyl groups, polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, gelatin, starch, dextrin, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose.
- Item 9. A method for producing a colloidal gold solution according to Item 8.
- Item 10. The method according to Item 8 or 9, wherein the gold carboxylate is gold acetate.
- Item 11. Item 11.
- Item 12. Item 12.
- the protective colloid is at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid, sodium polyacrylate, polyvinyl alcohol, and carboxymethylcellulose.
- a colloidal gold solution that is stable over a long period of time without causing precipitation or the like is provided. More specifically, by using gold carboxylate as a source of gold nanoparticles, the anion represented by the formula (a) is adsorbed on the gold nanoparticle surface without substantially containing chloride ions. This provides a colloidal gold solution that is stably dispersed in water.
- a stable colloidal gold solution containing no chloride ions can be obtained. Therefore, there is no need for post-treatment to remove chloride ions, and a highly concentrated gold colloid solution can be obtained simply and efficiently. Further, according to the method of the present invention, coarse particles are not produced as a by-product in the production process.
- a solution in which a metal salt is completely dissolved is usually used as a starting point, and few examples of preparing a metal colloid using a hardly soluble metal salt have been reported.
- a colloidal gold solution there has been no report of obtaining a highly concentrated colloidal gold solution using a hardly soluble metal salt as a raw material.
- the present invention it is possible to prepare a gold colloid solution having a high concentration with a simple system.
- FIG. 1 is a graph showing the UV-VIS spectrum of colloidal gold prepared from gold acetate in Example 1.
- FIG. 2 is a graph showing a TEM photograph of gold colloid prepared from gold acetate in Example 1 and from which PVP has been removed, and the size distribution of gold particles.
- FIG. 3 is a graph showing the UV-VIS spectrum of colloidal gold prepared from gold acetate in Example 2.
- FIG. 4 is a graph showing a TEM photograph of gold colloid prepared from gold acetate in Example 2 and from which PVP has been removed, and the size distribution of gold particles.
- colloidal gold solution comprises a gold nanoparticle having a particle diameter of 100 nm or less in water and an anion R-COO ⁇ (a) represented by the following general formula (a): (Wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms) It is characterized by including.
- the anion represented by the general formula (a) may be referred to as “carboxylate”, and the gold salt thereof may be referred to as “gold carboxylate”.
- halide ions such as chloride ions
- problems such as corrosion and catalyst poisoning occur when used as a conductive paste or catalyst.
- a gold compound that does not contain halide ions.
- carboxylated gold that is, gold carboxylate
- carboxylated trivalent gold as a source of gold nanoparticles.
- Specific examples of such a gold compound include Au (CH 3 COO) 3 , Au (C 2 H 5 COO) 3 , and Au (HCOO) 3 .
- the gold carboxylate may contain a basic salt such as Au (OH) (CH 3 COO) 2 , Au (OH) 2 (CH 3 COO).
- gold carboxylate one of these may be used alone, or two or more may be used in combination.
- gold acetate Au (CH 3 COO) 3
- Au is preferably used from the viewpoint that it is easily available and has an appropriate solubility in water.
- the average particle diameter of the gold nanoparticles contained in the gold colloid solution of the present invention is 100 nm or less, preferably 50 nm or less, more preferably 2 to 40 nm.
- an average particle diameter refers to the value calculated
- the concentration of the gold nanoparticles in the gold colloid solution of the present invention is usually 0.0001 to 50% by weight, preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight.
- concentration of gold nanoparticles present in the liquid as nanoparticles exhibiting plasmon absorption is the same in the medium (the same concentration when PVP or the like is added to water) and gold.
- the anion represented by the following general formula (a) contained in the colloidal gold solution of the present invention may exist in a state dissolved in the colloidal gold solution, and is adsorbed on the surface of the gold nanoparticle. May be present.
- R represents hydrogen or a linear or branched alkyl group having 1 to 4, preferably 1 to 2, more preferably 1 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl, a butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group, and a methyl group is preferable.
- the anion represented by the general formula (a) is preferably an acetate ion (CH 3 COO ⁇ ).
- the gold colloid solution of the present invention may contain a protective colloid.
- the protective colloid may be appropriately selected from conventionally known colloids.
- PVP polyvinyl pyrrolidone
- polyvinyl alcohol polyethylene glycol
- polyacrylic acid sodium polyacrylate
- gelatin gelatin
- starch dextrin
- carboxymethylcellulose methylcellulose
- examples thereof include ethyl cellulose and glutathione.
- polyvinyl pyrrolidone, polyethylene glycol, polyacrylic acid, sodium polyacrylate, polyvinyl alcohol and carboxymethyl cellulose are preferable, and polyvinyl pyrrolidone and polyethylene glycol are more preferable.
- These protective colloids may be used alone or in combination of two or more.
- protective colloids may be modified or modified within a range not impairing the effects of the present invention.
- a polymer when a polymer is used as the protective colloid, its molecular weight is not particularly limited as long as the effect of the present invention is exhibited.
- polyvinylpyrrolidone is specifically PVP ⁇ ⁇ K-15 (average molecular weight 1) manufactured by Kishida Chemical. 10,000), K-30 (average molecular weight 40,000), K-90 (average molecular weight 360,000), and the like can be used.
- the content thereof is not particularly limited as long as the content is not more than the solubility in water, but usually 0.1 to 1000 mol, preferably 0.
- the amount is 1 to 500 mol, more preferably 0.1 to 100 mol.
- the protective colloid is a polymer, it is handled as a molar amount in the monomer unit.
- Water is used as a solvent for the gold colloid solution of the present invention.
- the water is not particularly limited, but it is desirable to use water that does not contain impurities such as chloride ions, such as distilled water, ion exchange water, purified water, pure water, and ultrapure water.
- the gold colloid solution of the present invention may contain a reducing agent.
- the reducing agent can be appropriately selected from conventionally known reducing agents, and examples thereof include alcohols having a primary hydroxyl group such as methanol, ethanol, 1-propanol, and ethylene glycol; 2-propanol, 2-butanol, and the like.
- Alcohols having secondary hydroxyl groups such as glycerin; aldehydes such as formaldehyde and acetaldehyde; saccharides such as glucose, fructose, glyceraldehyde, lactose, arabinose and maltose; citric acid, citric acid Organic acids such as sodium citrate, potassium citrate, ammonium citrate, tannic acid, ascorbic acid, sodium ascorbate and potassium ascorbate and salts thereof; borohydrides such as sodium borohydride and potassium borohydride and Salt; hydrazine, hydrazine hydrochloride, and hydrazine and its inorganic salts such as hydrazine sulfate.
- aldehydes such as formaldehyde and acetaldehyde
- saccharides such as glucose, fructose, glyceraldehyde, lactose, arabinose and maltose
- citric acid citric acid
- reducing agents may be used alone or in combination of two or more.
- an alcohol having a primary hydroxyl group and / or a secondary hydroxyl group is preferable, and ethanol, methanol and the like are more preferable.
- Some protective colloids can be used as a reducing agent. Specific examples of the protective colloid that can also be used as a reducing agent will be described in the step (i) described later.
- the content thereof is not particularly limited as long as the effects of the present invention are not impaired, but 1 to 100000 mol, preferably 1 to 50000 mol, relative to 1 mol of gold, More preferred is 1 to 20000 mol.
- the gold colloid solution of the present invention preferably contains substantially no halide ion (X) which is any of fluoride ion, chloride ion, bromide ion and iodide ion.
- X halide ion
- the phrase “substantially free of halide ions” means that the amount of halide ions is small relative to the amount of gold in the gold colloid solution.
- the molar ratio (X / Au) of halide ion (X) to gold (Au) in the colloidal gold solution is, for example, 0.4 or less, or 0.04 or less, and further 0.004. It can be.
- a halide ion-containing raw material such as chloroauric acid
- the solution can be made into a gold colloid solution having a predetermined halide ion concentration or less without performing a desalting treatment.
- the colloidal gold solution of the present invention may contain a conventionally known additive depending on the application.
- additives include colorants, stabilizers, surfactants, dispersants, thickeners, and the like.
- the gold colloid solution of the present invention can be applied to uses such as conductive inks, conductive pastes, catalysts, sensors, bonding materials, coloring materials, paints, and biomarkers.
- the present invention provides a method for producing a gold colloid solution, which can easily prepare the gold colloid solution as described above.
- the method for producing the colloidal gold solution includes the following steps (i) and (ii).
- Step (i) In this step (i), gold carboxylate is dispersed in water to obtain a dispersion.
- gold carboxylate and water as a solvent are as described in the above “1. Gold colloid solution”.
- water containing a protective colloid may be used as a solvent.
- the particle size distribution of the gold nanoparticles can be narrowed, and the stability of the resulting gold colloid solution can be improved.
- Specific protective colloids are as described in “1. Colloidal gold solution” above.
- polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, gelatin, starch, dextrin, carboxymethylcellulose, methylcellulose, ethylcellulose and the like can be used as a reducing agent, and among these, preferred May include polyvinyl pyrrolidone, polyethylene glycol, polyacrylic acid, sodium polyacrylate, polyvinyl alcohol, and carboxymethyl cellulose, and more preferable examples of polyvinyl pyrrolidone and polyvinyl alcohol are obtained because a more stable gold colloid solution can be obtained. Therefore, when these are already added to the dispersion as protective colloids in this step (i), a gold colloid solution can be prepared without adding a separate reducing agent in the following step (ii).
- the amount of the protective colloid added is not particularly limited as long as it is not more than the solubility in water, but usually 0.1 to 1000 mol, preferably 0.1 to 500 mol, more preferably 0.1 to 1 mol of gold. Up to 100 moles.
- the method for dispersing the gold carboxylate in water can be appropriately selected from methods usually used for dispersing powder in water.
- a magnetic stirrer, a touch mixer And an ultrasonic cleaner are examples of methods usually used for dispersing powder in water.
- the process (60 second) by an ultrasonic cleaner is illustrated after a touch mixer (240 rpm, 10 second).
- Such treatment may be repeated a plurality of times (for example, 1 to 20 times, preferably 5 to 10 times).
- the dispersion is brown and shows a Tyndall phenomenon, so that it can be confirmed that it is dispersed in a colloidal state.
- the dispersion concentration of the dispersion obtained in this step (i) is not particularly limited as long as it has the dispersion concentration of gold carboxylate necessary to obtain the target colloidal gold solution. From the viewpoint of stability, the amount is usually 0.0001 to 50% by weight, preferably 0.001 to 10% by weight in terms of gold metal.
- Gold carboxylate is known to dissolve slightly in water as ions.
- solubility of gold acetate is described in Non-Patent Document 2 (GC Bond et al., Chapter 4 Preparation of Supported Gold Catalysts, Catalysts by gold (Series editor, G. J. Hutchings, p. 89), p. 89). Press (2006)) is reported to be 10 ⁇ 5 M or less.
- GC Bond et al. Chapter 4 Preparation of Supported Gold Catalysts, Catalysts by gold (Series editor, G. J. Hutchings, p. 89), p. 89). Press (2006)
- gold carboxylate is dispersed in water, some will dissolve in water and the remainder will be dispersed in water as a colloid.
- Step (ii) In this step (ii), a gold colloid solution is obtained by reducing the gold carboxylate by acting a reducing agent in the dispersion obtained in the step (i).
- the reduction of the gold carboxylate can be performed by adding a reducing agent to the dispersion obtained in the step (i).
- the reducing agent is as described in “1. Colloidal gold solution” above, preferably an alcohol having a primary hydroxyl group and / or a secondary hydroxyl group, more preferably ethanol, methanol and the like.
- the amount of the reducing agent that acts on the dispersion is not particularly limited as long as it has a number of moles equal to or greater than the redox equivalent to the number of moles of gold in the dispersion, but for example, 1 to 100,000 per mole of gold.
- Mol preferably 1 to 50000 mol, more preferably 1 to 20000 mol.
- the volume ratio is preferably in a range where it can be uniformly dissolved in water, and such volume ratio can be appropriately set based on the number of moles.
- the conditions for causing the reducing agent to act on the dispersion are not particularly limited as long as the gold carboxylate in the dispersion can react with the reducing agent, and stirring or the like may be performed as necessary.
- the reaction temperature is not particularly limited and can be appropriately set depending on the kind of reducing agent to be used. For example, it is 1 to 100 ° C., preferably 5 to 40 ° C., more preferably 10 to 30 ° C. Can be mentioned.
- the reaction proceeds sufficiently in several minutes at room temperature, but when a weak reducing agent such as 2-propanol or polyvinylpyrrolidone which is also a protective colloid is used. Can take days to months at room temperature. Therefore, when a weak reducing agent is used, the reaction rate can be increased by heating the reaction solution to raise the reaction temperature, and gold colloid can be produced in several minutes to several hours.
- the heating temperature is not particularly limited as long as gold colloid can be produced, and examples thereof include 40 to 100 ° C., preferably 60 to 100 ° C., and more preferably 80 to 100 ° C.
- a high concentration of gold can be obtained by heating at 80 to 100 ° C. for 5 to 60 minutes.
- a colloidal solution can be obtained.
- excess protective colloid may be removed as necessary.
- the removal method is not particularly limited and may be appropriately selected from conventionally known methods. For example, centrifugal filtration, membrane separation, dialysis, electrodialysis and the like can be performed. Depending on the amount of protective colloid to be removed, these treatments may be performed multiple times. Further, the obtained colloidal gold solution may be subjected to treatments such as pH adjustment, concentration and purification according to a conventionally known method, if necessary.
- gold carboxylate can be dispersed in water containing a protective colloid as required, and then a reducing agent can be allowed to act.
- the protective colloid and the reducing agent may be added to water as a solvent to form an aqueous solution, and gold carboxylate may be added thereto to prepare a gold colloid solution.
- the same materials and conditions as described above can be employed.
- preferable combinations of the materials include, for example, gold acetate as the gold carboxylate, polyvinylpyrrolidone and / or polyvinyl alcohol as the protective colloid, and methanol and / or ethanol as the reducing agent.
- the reason why a high concentration of gold colloid can be obtained in the present invention can be considered as follows, for example. Since gold carboxylate such as gold acetate is hardly soluble in water, the gold ion concentration in water is considered to be kept at a dilute concentration suitable for gold colloid formation. And, when gold ions are reduced to metallic gold by a reducing agent, it is considered that gold carboxylate can be dissolved again in a trace amount of water. Thus, it is considered that a gold colloid is formed little by little by repeating a minute dissolution and reduction of gold carboxylate, and as a result, a high concentration of gold colloid can be obtained.
- Example 1 50 mg of polyvinylpyrrolidone (PVP K15, manufactured by Kishida Chemical Co., Ltd.) was dissolved in 10 mL of a 1: 1 solution of ethanol and water. 5 mg of brown powder of gold acetate [Au (CH 3 COO) 3 , manufactured by Alfa Aesar, purity 99.99% described in the manufacturer's analysis certificate] was added, touch mixer (IKA, Vortex Genius 3) and ultrasonic cleaner (Used by ASONE, US-2R).
- the standard condition is that the touch mixer treatment (10 seconds at 2400 rpm) and the ultrasonic cleaner treatment (60 seconds) are alternately repeated 5 to 7 times, but the number of repetitions depends on the remaining state of precipitation.
- the horizontal axis represents the wavelength
- the vertical axis represents the value displayed as absorbance in the spectrophotometer.
- the absorbance includes the influence of scattering and reflection in addition to absorption, and is expressed here as optical density.
- a peak based on surface plasmon absorption was clearly observed in the measured spectrum, and the wavelength ( ⁇ max ) was 527 nm.
- Non-Patent Document 3 Toshikatsu Kobayashi, Chapter 21 Rich Gold Nanoparticle Paste as Coloring Material, Gold Nanotechnology (supervised by Masami Haruta) pp.273-282 CMC Publishing Co., Ltd. (2009)
- the correspondence between the volume average particle diameter (D Au ) and the plasmon absorption wavelength ( ⁇ max ) is shown. If the gold colloid dispersion medium is the same, both the values of D Au and ⁇ max have a linear relationship, and it is possible in principle to determine D Au from the measured value of ⁇ max .
- a dispersion medium for colloidal gold is water
- the dielectric constant of the dispersion medium by mixing the reducing agent and protective colloid PVP such as ethanol or the like is changed, max even ⁇ a D Au is the same fluctuate.
- the relationship between the D Au value obtained from the TEM measurement of Example 1 and Example 2 described later and ⁇ max is added to the data point sequence shown in FIG. 8 of Non-Patent Document 3, and a regression line is obtained by the least square method. It was. As a result, the correlation coefficient is 0.96, which is close to 1, so that it can be said that the state of the gold colloid of the present invention is similar to that of the gold colloid shown in FIG. From the obtained linear equation, the range of D Au corresponding to the range of ⁇ max (524 to 562 nm) measured in Example 1 and Examples 2 to 33 described later is 12 to 37 nm. It was estimated that a gold colloid having an average particle size of about 10 to 40 nm was obtained.
- the optical density at ⁇ max can be used as an index of colloidal gold concentration.
- the optical path length of the quartz cell used for the measurement is L (cm)
- the optical density value at ⁇ max at that time is Y
- the maximum converted optical density value (that is, OD max ) immediately after preparation calculated by the following formula (1) was 6.8 (see Table 1 below).
- OD max Y ⁇ F / L Formula (1)
- Centrifugal filtration was performed to remove PVP from the colloidal gold dispersion (40 days after preparation). Using a centrifugal filter unit (Amicon Ultra-15, manufactured by Millipore) with a molecular weight cut off of 50,000, the colloidal gold dispersion that does not pass through the filter is concentrated to a deep red color after passing through the filter. As a result, a colorless and transparent filtrate was obtained. The operation of adding water to the concentrated dispersion to return to 10 mL and performing centrifugal filtration again was repeated three times.
- Non-Patent Document 4 (Binding of Evans Blue Onto Poly (N-Vinyl-2-Pyrorollone), M. Maruthumuthu and E. Subrariann, Polymer-2, Polymer-2, Polymer-2, 207-2) to determine whether PVP remains in the filtrate. (1985)), Evans Blue (EB) solution was added dropwise to measure UV-VIS absorption.
- the first filtrate showed 639 nm absorption based on the PVP-EB complex, but the third filtrate showed no absorption at 639 nm and only 609 nm absorption based on free EB. It was confirmed that PVP could be removed by three centrifugal filtration operations. Evans blue was added to a part of the obtained colloidal gold dispersion and UV-VIS absorption was measured. As a result, there was no absorption at 639 nm, and it was confirmed that PVP did not remain in the gold colloid dispersion medium. did it. The ⁇ max in UV-VIS absorption of the colloidal gold solution after removing the PVP (portion to which Evans Blue was not added) was 529 nm.
- the gold colloid solution after the PVP removal operation was dropped onto a microgrid and dried, and observed with a transmission electron microscope (TEM).
- TEM transmission electron microscope
- a TEM photograph is shown in FIG. It is a gold nanoparticle mixture of various crystal structures (regular icosahedron structure Ih, pentagonal decahedron structure Dh, face-centered cubic lattice structure Fcc), and its particle diameter is observed from about 5 nm to over 20 nm. It was done.
- the number average particle diameter determined from the size distribution of FIG. 2 was 11.5 nm.
- Table 1 shows that the particle size and concentration fluctuate when PVP is removed, but there is no significant change during the subsequent 7 months, indicating that the colloid is stable.
- Example 1 Chloroauric acid (HAuCl 4) prepared by weighing crystals of chloroauric acid tetrahydrate (Kishida Kagaku) instead of gold acetate in an electronic balance and dissolving it in a predetermined amount of water as the gold carboxylate of the gold colloid material.
- a solution was prepared in the same manner as in Example 1 except that 0.13 mL of 0.1 mol / L aqueous solution of) was used.
- the liquid color at the time of preparation was yellow (liquid color of a normal aqueous solution of chloroauric acid), and the Tyndall phenomenon was not observed, and chloroauric acid was completely dissolved and became a true solution.
- Example 2 6 g of polyvinylpyrrolidone (PVP K15) was dissolved in 20 mL of water, and 2 mL thereof was taken in a glass screw tube bottle. When 20 mg of gold acetate powder was added and dispersed under the same conditions as in Example 1 using a touch mixer and an ultrasonic cleaner, a brown dispersion liquid was obtained. When a stirrer was inserted, the lid with Teflon-coated packing was closed, and the solution was boiled while stirring on a hot plate stirrer, a red colloidal solution (Au 26.7 mmol / L) was obtained in a few minutes.
- FIG. 3 shows the UV-VIS spectrum (absorption peak 530 nm) of the colloidal solution diluted to 1/100. The gold particle diameter determined by (Equation 1) was 18.1 nm.
- Table 2 shows that the particle size and concentration fluctuated when PVP was removed, as in Example 1, but there was no significant change during the subsequent 7 months, indicating that the colloid is stable.
- FIG. 4 shows a TEM photograph of the colloidal gold after the PVP removal operation.
- FIG. 4 shows that, similarly to Example 1, the present Example 2 is also a mixture of gold nanoparticles having various structures.
- the particle size distribution was slightly better than in the case of Example 1.
- the average particle diameter (arithmetic average value usually shown by TEM) obtained from the size distribution of FIG. 4 was 9.8 nm.
- Comparative Example 2 Instead of using 20 mg of gold acetate powder in Example 2, 0.1 mol / L aqueous solution of chloroauric acid (HAuCl 4 ) prepared from chloroauric acid tetrahydrate (Kishida Kagaku) according to the same method as in Comparative Example 1 A solution was prepared in the same manner as in Example 2 except that 0.5 mL was used. Upon boiling to reflux, coarse gold particles precipitated and no gold colloid was produced.
- Examples 3 to 6 25 mg of polyvinylpyrrolidone (PVP K15) was dissolved in 2.5 mL of water in the test tube. 5 mg of gold acetate powder was added, and the mixture was dispersed under the same conditions as in Example 1 using a touch mixer (IKA Corp., Vortex Genius 3) and an ultrasonic washer (Aiwa Medical Industries, AU-25C). Any of 2.5 mL of the reducing agent shown in Table 3 was added and stirred (Example 3: ethanol, Example 4: methanol, Example 5: ethylene glycol, Example 6: 2-propanol). When covered and allowed to stand at room temperature, Examples 3-5 produced red gold colloids.
- PVP K15 polyvinylpyrrolidone
- Example 6 no change was observed after standing at room temperature for 1 day, but when heated to 100 ° C. in boiling water with the lid on, colloidal gold was immediately formed. After the colloid was formed, it was allowed to stand at room temperature for 2 days, and UV-VIS measurement was performed. Based on the measured value of ⁇ max , the OD max value was calculated based on the formula (1). These values are shown in Table 3 below.
- Examples 7 to 16 ⁇ Amount of gold acetate and dispersant>
- the amount of polyvinylpyrrolidone (PVP K15) shown in Table 4 was dissolved in 2.5 mL of water in the test tube.
- the amount of gold acetate powder shown in Table 4 was added to the obtained aqueous solution, and Example 1 was used with a touch mixer (IKA Corp., Vortex Genius 3) and an ultrasonic washer (Aiwa Medical Industries, AU-25C). Dispersion was performed under the same conditions. When 2.5 mL of ethanol was added thereto, the lid was covered and allowed to stand at room temperature, colloidal gold was produced. After standing for 1 day, the UV-VIS spectrum was measured.
- ⁇ max and OD max obtained by the same method as in Example 1 are shown in Table 4 below.
- the Au concentration is the Au concentration by weight in the colloidal solution calculated from the amount of gold acetate used in the preparation.
- PVP / Au is a molar ratio calculated by the monomer unit (molecular weight 111) of PVP.
- Example 13 As a result of changing the amount of gold acetate, an OD max value almost linearly related to the concentration of gold nanoparticles was obtained up to a concentration of gold nanoparticles of 0.55% by weight. In Example 16, the value was about 50% of the OD max value expected from the extrapolation of the straight line.
- ⁇ max of the gold colloid obtained varies depending on the type of protective colloid. More specifically, when PVP K-30 (Example 18) or PVPK-90 (Example 19) having a large molecular weight is used compared to PVP K-15 (Example 17), ⁇ max becomes small and relatively The formation of gold colloid with small particle size was suggested. Further, when sodium polyacrylate or polyacrylic acid (Examples 21 and 22 respectively) was used, ⁇ max was increased, suggesting the formation of a gold colloid with a large particle size.
- Examples 25-33 ⁇ Reduction with various protective colloids> A predetermined amount of the dispersant shown in Table 6 was added to 5 mL or 2 mL of water in the test tube and dissolved. A predetermined amount of gold acetate powder was added, and the mixture was dispersed under the same conditions as in Example 1 using a touch mixer (Vortex Genius 3 manufactured by IKA) and an ultrasonic cleaning machine (AU-25C manufactured by Aiwa Medical Industry). Colloidal gold was formed while capping and heating in boiling water for 2 hours. Thereafter, a UV-VIS spectrum was measured after standing at room temperature for 1 day (however, in Examples 30 to 33, after 3 days, in Example 26, after standing at room temperature for 5 days). Based on the measured value of ⁇ max , the OD max value was calculated based on the formula (1). These values are shown in Table 6 below.
- Table 6 shows that a gold colloid can be produced when PVP, PEG, PVA or CMC is used as a protective colloid without adding ethanol.
- Examples 26 and 27 were compared, a colloid with a large OD max value was obtained in a short time by heating, whereas a long period of time was required for colloid formation at room temperature and the OD max value was small. Further, when the amount of gold acetate was increased, it was possible to produce a colloid having an OD max value exceeding 100 (Examples 29 and 32).
- PVP or PVA was used as the protective colloid, stable colloidal gold was obtained even after standing for 3 days (Examples 25 to 30 and 32).
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Abstract
Description
項1.水中に粒子径100nm以下の金ナノ粒子と、下記一般式(a)で表わされる陰イオン
R-COO- (a)
(式中、Rは炭素数1~4の直鎖状又は分岐鎖状アルキル基を示す)
を含む、金コロイド溶液。
項2.前記陰イオンが酢酸イオンである、項1に記載の金コロイド溶液。
項3.更に、保護コロイドを含む項1又は2に記載の金コロイド溶液。
項4.前記保護コロイドがポリビニルピロリドン、ポリエチレングリコール、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリビニルアルコール及びカルボキシメチルセルロースからなる群より選択される少なくとも1種である、項1~3のいずれかに記載の金コロイド溶液。
項5.更に、1級水酸基及び/又は2級水酸基を有するアルコールからなる還元剤を含む項1~4のいずれかに記載の金コロイド溶液。
項6.前記金ナノ粒子の濃度が0.0001~50重量%である、項1~5のいずれかに記載の金コロイド溶液。
項7.塩化物イオンを実質的に含まない、請求項1~6のいずれかに記載の金コロイド溶液。
項8.下記工程を含む金コロイド溶液の製造方法:
(i)金カルボキシラートを水に分散させて分散液を調製する工程;及び
(ii)前記工程(i)で得られた分散液において、金カルボキシラートに還元剤を作用させて還元することにより金コロイド溶液を得る工程。
項9.前記還元が、1級水酸基及び/又は2級水酸基を有するアルコール、ポリビニルピロリドン、ポリビニルアルコール、ポリエチレングリコール、ゼラチン、デンプン、デキストリン、カルボキシメチルセルロース、メチルセルロース並びにエチルセルロースからなる群より選択される少なくとも1種を用いて行われる、項8に記載の金コロイド溶液の製造方法。
項10.前記金カルボキシラートが酢酸金である、項8又は9に記載の方法。
項11.前記分散液が保護コロイドを含む、項8~10のいずれかに記載の方法。
項12.前記保護コロイドがポリビニルピロリドン、ポリエチレングリコール、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリビニルアルコール及びカルボキシメチルセルロースからなる群より選択される少なくとも1種である、項8~11のいずれかに記載の方法。
本発明の金コロイド溶液は、水中に粒子径100nm以下の金ナノ粒子と下記一般式(a)で表わされる陰イオン
R-COO- (a)
(式中、Rは炭素数1~4の直鎖状又は分岐鎖状アルキル基を示す)
を含むことを特徴とする。
R-COO- (a)
式中、Rは水素又は炭素数1~4、好ましくは1~2、更に好ましくは1の直鎖状又は分岐鎖状アルキル基を示す。具体的なアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル、ブチル基、イソブチル基、sec-ブチル基、t-ブチル基等が挙げられ、好ましくはメチル基が挙げられる。上記一般式(a)で表わされる陰イオンとして好ましくは、酢酸イオン(CH3COO-)が挙げられる。
本発明は、上述のような金コロイド溶液を簡便に調製することが可能な金コロイド溶液の製造方法を提供する。当該金コロイド溶液の製造方法は、下記工程(i)及び(ii)を含む。
本工程(i)においては、金カルボキシラートを水に分散させて分散液を得る。ここで、金カルボキシラート及び溶媒である水については、上記「1.金コロイド溶液」において記載される通りである。
本工程(ii)においては、前記工程(i)で得られた分散液において、金カルボキシラートに還元剤を作用させて還元することにより金コロイド溶液を得る。
エタノールと水の1:1溶液10mLにポリビニルピロリドン(PVP K15,キシダ化学製)を50mg溶かした。酢酸金[Au(CH3COO)3,AlfaAesar製、メーカーの分析証明書に記載の純度99.99%]の茶色粉末5mgを加え、タッチミキサー(IKA社製、Vortex Genius3)及び超音波洗浄機(アズワン製、US-2R)を用いて分散させた。分散処理としては、タッチミキサー処理(2400rpmで10秒)、超音波洗浄機処理(60秒)を交互に各5~7回繰り返すのを標準条件としたが、沈殿の残存状況に応じて繰り返し回数を適宜増減した。このような処理により、溶液中の溶け残りの沈殿はほぼ無くなるが、容器の横からLEDライトの光を当てるとチンダル現象が見られることから真の水溶液ではなく茶色のコロイド分散液となっていることが確認された。
ODmax=Y×F/L 式(1)
金コロイド原料の金カルボキシラートとして、酢酸金の代わりに塩化金酸四水和物(キシダ化学)の結晶を電子天秤で秤量し、所定量の水に溶解して調製した塩化金酸(HAuCl4)の0.1mol/L水溶液0.13mLを用いる他は、実施例1と同様にして溶液を調製した。調製時の液色は黄色(通常の塩化金酸水溶液の液色)でチンダル現象も観察されず塩化金酸は完全に溶けて真の溶液となっていた。実施例1と同様に室温で1晩放置したが、色の変化は全く起こらず黄色の溶液のままであり、金コロイドは生成しなかった。
水20mLに対しポリビニルピロリドン(PVP K15)を6g溶かし、その2mLをガラス製スクリュー管瓶にとった。酢酸金の粉末20mgを加え、タッチミキサと超音波洗浄機を用い実施例1と同様の条件で分散させると、茶色の分散液が得られた。攪拌子を入れて、テフロンコートパッキン付きの蓋を閉めてホットプレートスターラー上で攪拌しながら溶液を沸騰させると、数分で赤色のコロイド液(Au26.7mmol/L)が得られた。1/100に希釈したコロイド液のUV-VISスペクトル(吸収ピーク530nm)を図3に示す。(式1)により求めた金の粒子径は18.1nmであった。
実施例2において酢酸金の粉末20mgを用いる代わりに、比較例1と同様の方法に従って塩化金酸四水和物(キシダ化学)から調製した塩化金酸(HAuCl4)の0.1mol/L水溶液0.5mLを用いる他は、実施例2と同様にして溶液を調製した。沸騰還流すると、粗大金粒子となって沈殿し、金コロイドは生成しなかった。
試験管中の水2.5mLにポリビニルピロリドン(PVP K15)を25mg溶かした。酢酸金の粉末5mgを加え、タッチミキサ(IKA社製、Vortex Genius3)と超音波洗浄機(アイワ医科工業製、AU-25C)を用い実施例1と同様の条件で分散させた。ここに、表3に示した還元剤2.5mLの何れかを加えて攪拌した(実施例3:エタノール、実施例4:メタノール、実施例5:エチレングリコール、実施例6:2-プロパノール)。蓋をして室温で放置すると、実施例3~5は赤色の金コロイドを生成した。実施例6は室温では1日放置しても変化が見られなかったが、蓋をした状態で沸騰水中で100℃に加熱すると直ちに金コロイドを生成した。コロイド生成後、室温で2日間静置し、UV-VIS測定を行った。測定されたλmaxの値より、前記式(1)に基づいてODmax値を算出した。これらの値を下表3に示す。
還元剤としてt-ブタノール2.5mLを用い、他の操作は実施例3~6と同様に行った。室温では1日放置しても変化が見られなかった。更に沸騰水中で2時間加熱したが、茶色の沈殿物が落ち、上澄みは透明となって金コロイドは生成しなかった。結果を下表3に併せて示す。
試験管中の水2.5mLにポリビニルピロリドン(PVP K15)の表4に示した量を溶かした。得られた水溶液に酢酸金の粉末を表4に示した量加え、タッチミキサ(IKA社製、Vortex Genius3)と超音波洗浄機(アイワ医科工業製、AU-25C)を用いて実施例1と同様の条件で分散させた。ここに、エタノール2.5mLを加え、蓋をして室温で放置すると金コロイドが生成した。1日放置後、UV-VISスペクトルを測定した。実施例1と同様の方法によって得られたλmax、ODmaxの値を下表4に示す。また、下表4においてAu濃度は調製の際に使用した酢酸金の量から計算したコロイド溶液中のAu重量濃度である。PVP/Auは、PVPのモノマー単位(分子量111)で計算したモル比である。
試験管中の水2.5mLに表5に示す各種の分散剤を25mg溶かした。酢酸金の粉末5mg加え、タッチミキサ(IKA社製、Vortex Genius3)と超音波洗浄機(アイワ医科工業製、AU-25C)を用い実施例1と同様の条件で分散させた。ここに、エタノール2.5mLを加えた。蓋をして室温で放置すると金コロイドが生成した。1日放置後のUV-VISスペクトルを測定した。測定されたλmaxの値より、前記式(1)に基づいてODmax値を算出した。これらの値を表5に示す。
試験管中の水5mLまたは2mLに、表6に示した分散剤を所定量加えて溶かした。酢酸金の粉末を所定量加え、タッチミキサ(IKA社製、Vortex Genius3)と超音波洗浄機(アイワ医科工業製、AU-25C)を用い実施例1と同様の条件で分散させた。蓋をして沸騰水中で2時間加熱する間に金コロイドが生成した。その後、室温で1日静置後(但し、実施例30~33では3日後、実施例26は加熱せず室温で5日静置後)のUV-VISスペクトルを測定した。測定されたλmaxの値より、前記式(1)に基づいてODmax値を算出した。これらの値を下表6に示す。
以上の結果より、本発明によれば安定な金コロイド溶液が得られることが示された。更に、本発明によれば、従来の金コロイド溶液と比べて格段に高濃度のものを調製することも可能であった。また、金ナノ粒子の供給源として金カルボキシラートを使用することにより、塩化物イオン等の残留を懸念することなく、幅広い用途に適用可能な金コロイド溶液を簡便に調製することができることが示された。
Claims (12)
- 水中に粒子径100nm以下の金ナノ粒子と下記一般式(a)で表わされる陰イオン
R-COO- (a)
(式中、Rは炭素数1~4の直鎖状又は分岐鎖状アルキル基を示す)
を含む、金コロイド溶液。 - 前記陰イオンが酢酸イオンである、請求項1に記載の金コロイド溶液。
- 更に、保護コロイドを含む請求項1又は2に記載の金コロイド溶液。
- 前記保護コロイドがポリビニルピロリドン、ポリエチレングリコール、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリビニルアルコール及びカルボキシメチルセルロースからなる群より選択される少なくとも1種である、請求項1~3のいずれかに記載の金コロイド溶液。
- 更に、1級水酸基及び/又は2級水酸基を有するアルコールからなる還元剤を含む請求項1~4のいずれかに記載の金コロイド溶液。
- 前記金ナノ粒子の濃度が0.001~50重量%である、請求項1~5のいずれかに記載の金コロイド溶液。
- 塩化物イオンを実質的に含まない、請求項1~6のいずれかに記載の金コロイド溶液。
- 下記工程を含む金コロイド溶液の製造方法:
(i)金カルボキシラートを水に分散させて分散液を調製する工程;及び
(ii)前記工程(i)で得られた分散液において、金カルボキシラートに還元剤を作用させて還元することにより金コロイド溶液を得る工程。 - 前記還元が、1級水酸基及び/又は2級水酸基を有するアルコール、ポリビニルピロリドン、ポリビニルアルコール、ポリエチレングリコール、ゼラチン、デンプン、デキストリン、カルボキシメチルセルロース、メチルセルロース並びにエチルセルロースからなる群より選択される少なくとも1種を用いて行われる、請求項8に記載の金コロイド溶液の製造方法。
- 前記金カルボキシラートが酢酸金である、請求項8又は9に記載の方法。
- 前記分散液が保護コロイドを含む、請求項8~10のいずれかに記載の方法。
- 前記保護コロイドがポリビニルピロリドン、ポリエチレングリコール、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリビニルアルコール及びカルボキシメチルセルロースからなる群より選択される少なくとも1種である、請求項8~11のいずれかに記載の方法。
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JP2018502982A (ja) * | 2014-10-07 | 2018-02-01 | ビーエーエスエフ コーポレーション | 制御されたサイズおよび形態を有するコロイド状貴金属ナノ粒子の合成 |
US10493433B2 (en) | 2014-10-07 | 2019-12-03 | Basf Corporation | Synthesis of colloidal precious metals nanoparticles with controlled size and morphology |
JP2021073379A (ja) * | 2014-10-07 | 2021-05-13 | ビーエーエスエフ コーポレーション | 制御されたサイズおよび形態を有するコロイド状貴金属ナノ粒子の合成 |
KR102480159B1 (ko) * | 2014-10-07 | 2022-12-22 | 바스프 코포레이션 | 제어된 크기 및 형태학을 갖는 콜로이드성 귀금속 나노입자의 합성 |
JP2018035406A (ja) * | 2016-09-01 | 2018-03-08 | 旭化成株式会社 | 新規なコアシェル型ナノ粒子およびその製造方法 |
JP7089841B2 (ja) | 2016-09-01 | 2022-06-23 | 旭化成株式会社 | 新規なコアシェル型ナノ粒子およびその製造方法 |
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RU2014139968A (ru) | 2016-04-27 |
JP6032622B2 (ja) | 2016-11-30 |
US20150057147A1 (en) | 2015-02-26 |
JPWO2013133315A1 (ja) | 2015-07-30 |
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