JP4529160B2 - METAL PARTICLE, PROCESS FOR PRODUCING THE SAME, COMPOSITION CONTAINING THE SAME AND USE THEREOF - Google Patents

Description

The present invention relates to rod-shaped metal fine particles (hereinafter referred to as metal nanorods) having a major axis of 400 nm or less and a minor axis of 15 nm or less and an aspect ratio of greater than 1, a novel production method thereof, and a composition containing the same As well as its use.

When a metal fine particle is irradiated with light, a resonance absorption phenomenon called plasmon absorption occurs. This absorption phenomenon has different absorption wavelengths depending on the type and shape of the metal. For example, a colloidal gold particle in which spherical gold fine particles are dispersed in water has an absorption region around 530 nm. If the shape of the fine particles is made into a rod shape with a short axis of 10 nm, in addition to absorption around 530 nm caused by the short axis of the rod. It is known to have absorption on the long wavelength side due to the long axis of the rod (Non-Patent Document 1).

As methods for synthesizing metal nanorods, an electrochemical method (Non-Patent Document 2), a chemical method (Non-Patent Document 3), and a photochemical method (Non-Patent Document 4) are conventionally known. Further, as a method for producing noble metal fine particles having a spherical shape as a coloring material for paints and resin compositions, a method is known in which a noble metal compound is dissolved in a solvent, a high molecular weight dispersant is added, and then reduced (patent) Reference 1). Furthermore, for the purpose of forming a metal wiring pattern, it is known that plasmon-absorbing inorganic fine particles supported on a solid surface are used as fine rods grown to a diameter of less than 100 nm and an aspect ratio of 1 or more ( Patent Document 2).

The electrochemical method is a method in which metal ions eluted from the anode are reduced at the cathode and grown into rod-shaped fine particles by the action of a surfactant. Electrolytic devices, gold plates, platinum plates, silver plates, etc. This is not suitable for mass production because it requires a working electrode, an ultrasonic irradiator, and the like, and the amount that can be manufactured is limited by the size of the apparatus. In addition, the aspect ratio of the metal nanorods depends on the deterioration of the ultrasonic irradiator and the amount of elution of silver, and the reproducibility tends to be poor.

The chemical method is a method that first adjusts the fine metal species as the growth nucleus, adds the metal species to a separately prepared growth solution, and grows it into a rod shape. The working life of the seed is as short as several hours. There is a problem that a complicated operation for growing metal fine particles in two steps to three steps is required, reproducibility is difficult to obtain, and the concentration of metal nanorods that can be produced is low.

The photochemical method is a method of generating metal nanorods by irradiating metal ions in a surfactant-containing solution with ultraviolet rays for a long period of time, and requires expensive equipment such as an ultraviolet exposure device. Since the production range is limited, the production amount is limited and not suitable for mass production.

In the production method of Patent Document 1, an example of using an amine as a reducing agent is shown, but it is not used in combination with a surfactant and a high molecular weight type dispersant is added. It is used as a protective colloid for the produced noble metal fine particles, and does not control the axial growth when forming the noble metal fine particles. Therefore, the noble metal fine particles produced are spherical fine particles, and rod-shaped metal fine particles cannot be obtained. The plasmon coloration of the spherical gold fine particles obtained by this production method is blue, blue purple, red purple, etc., and the spherical silver fine particles are yellow, and their absorption is around 530 nm for gold and 400 nm for silver. It is limited to the vicinity and the usable colors are limited.

Furthermore, in the conventional manufacturing method, the metal fine particles grown on the solid surface cannot be dispersed in various solvents and binders because the metal fine particles are supported on the solid surface, and can be made into a paint. Can not.
SS.Chang et al, Langmuir, 1999,15, p701-709 Y.-Y. Yu, S.-S. Chang, C.-L. Lee, CRC Wang, J. Phys. Chem. B, 101, 6661 (1997) NRJana, L. Gearheart, CJMurphy, J. Phys. Chem. B, 105, 4065 (2001) F. Kim, JHSong, P. Yang, J. Am. Chem. Soc., 124, 14316 (2002) Japanese Patent Laid-Open No. 11-80647 Japanese Patent Laid-Open No. 2001-064794

The present invention solves the above-mentioned problems in the conventional production method, and can produce metal nanorods easily and in large quantities, and is easy to adjust the particle size, and is obtained by this production method. Provide fine metal particles.

According to the present invention, a method for producing fine metal particles having the following constitution is provided.
[1] A method for producing rod-shaped metal fine particles by chemically reducing metal ions in an aqueous solution, containing amines having a reducing ability and ammonium salts having substantially no reducing ability A method for producing metal fine particles, characterized in that an aqueous solution is used to reduce metal ions with the amines in the presence of the ammonium salt.
[2] A method for producing fine metal particles using the quaternary ammonium salt represented by the following formula (1) as an ammonium salt used in combination with an amine in the method (1).
CH ₃ (CH ₃ ) _n N ⁺ (CH ₃ ) ₃ Br ⁻ (n = 1 to 17 integer) (1)
[3] Metals using one or more alkylamines or alkanolamines represented by the following formulas (2) to (3) as amines used in combination with ammonium salts in the method of (1) or (2) above A method for producing fine particles.
NR ₃ (R: C _n H _{2n + 1} n = 1-8 integer) (2)
_{N (ROH) 3 (R:} C n H 2n n = 1~8 integer) Equation (3)
[4] A method for producing fine metal particles in the method (3) above, wherein triethylamine, tributylamine, tripentylamine, or 2,2 ′, 2 ″ -nitrilotriethanol is used as the amine.
[5] Production of metal fine particles using one or more alkylamines represented by the following formulas (4) to (5) as amines used in combination with ammonium salts in the method (1) or (2) Method.
H ₂ NR (R: C _n H _{2n + 1} n = 1 to 8 integer) (4)
HNR ₂ (R: C _n H _{2n + 1} n = 1 to 8 integer) (5)
[6] The method for producing fine metal particles according to any one of [2] to [5] above, wherein the concentration of the ammonium salt represented by the formula (1) in the aqueous solution is 0.01 to 1.0 mol / L.
[7] The method for producing fine metal particles according to any one of the above [2] to [6], wherein the concentration of the amines represented by the formulas (2) to (5) in the aqueous solution is 0.001 to 10 wt%.
[8] The fine metal particles according to any one of [2] to [7], wherein the amines represented by formulas (2) to (5) have an ionization index (pka value) of 7.0 to 12.5. Production method.
[9] The method for producing metal fine particles according to any one of the above [1] to [6], wherein the particle diameter is controlled by adjusting the concentration of amines and ammonium salt.
[10] The method for producing metal fine particles according to any one of the above [1] to [8], wherein a ketone is added to an aqueous solution containing the amines and ammonium salt to adjust the aspect ratio of the metal fine particles.

Moreover, according to this invention, the metal fine particle which consists of the following structures and its use are provided.
[11] Rod-shaped metal fine particles produced by any one of the above [1] to [10], having a major axis of 400 nm or less, a minor axis of 15 nm or less, and an aspect ratio larger than 1.
[12] Metal fine particles produced by the method of any one of [1] to [10] above and surface-treated with a non-aqueous dispersant having a side chain having affinity for a non-aqueous solvent.
[13] A metal produced by the method of any one of [1] to [10] above, wherein the residual amount of ammonium salt on the surface of the metal fine particles is removed or reduced to 15 parts by weight or less with respect to 100 parts by weight of the metal fine particles. Fine particles.
[14] A composition containing metal fine particles produced by any one of the methods [1] to [10] or metal fine particles described in any one of the above [11] to [13].
[15] The metal fine particle-containing composition according to [14], which contains a binder (resin) and a dispersion medium together with the metal fine particles.
[16] The metal fine particle-containing composition according to [14] or [15] above, which contains one or more of dyes, pigments, phosphors, metal oxides, and metal nanofibers together with metal fine particles.
[17] A light-absorbing material having the form of a coating composition, a coating film, a film, or a plate formed by the metal fine particle-containing composition according to any one of [14] to [16].
[18] Optical filter material and wiring material containing metal fine particles produced by any one of the methods [1] to [10], or metal fine particles described in any one of the above [11] to [13] , Electrode materials, catalysts, colorants, cosmetics, near-infrared absorbers, anti-counterfeit inks, electromagnetic shielding materials, surface-enhanced fluorescent sensors, biomarkers, nanowaveguides, recording materials, recording elements, polarizing materials, drug delivery systems ( DDS) drug holder, biosensor, DNA chip, test drug.

[Specific description]
Hereinafter, the present invention will be specifically described based on embodiments.
The production method of the present invention is a method for producing rod-shaped fine metal particles by chemically reducing metal ions in an aqueous solution, an amine having a reducing ability, and an ammonium salt having substantially no reducing ability. And a metal ion is reduced by the amines in the presence of the ammonium salt.

In general, amines have a weak reducing power, but the present invention provides a suitable reaction field in which metal nanorods are slowly generated by utilizing the weak reducing power of amines in the presence of the surfactant action of an ammonium salt. Thus, metal nanorods finer than conventionally reported particle diameters can be produced.

As the ammonium salt used in combination with amines, for example, a quaternary ammonium salt represented by the following formula (1) is used.
CH ₃ (CH ₃ ) _n N ⁺ (CH ₃ ) ₃ Br ⁻ (n = 1 to 17 integer) (1)
This quaternary ammonium salt is a water-soluble cationic surfactant and is known to form various aggregates (micelles) depending on its concentration when dissolved in water. In general, the concentration changes to spherical micelles, rod-like micelles, and plate-like micelles in proportion to the increase in the concentration of the ammonium salt. In the production method of the present invention, rod-shaped metal fine particles are preferentially produced over spherical metal fine particles by adjusting the ammonium salt concentration and utilizing the regularity of the micelle structure.

Among the ammonium salts represented by the above formula (1), n = 16 hexadecyltrimethylammonium bromide (CT ₁₆ AB) is preferable. Tends to be often the amount of spherical fine particles than with CT ₁₆ AB Using ammonium salt other than CT ₁₆ AB. The concentration of CT ₁₆ AB in aqueous solution is suitably from 0.01 to 1.0 mol / L, and preferably from 0.08 to 0.80 mol / L. If the CT ₁₆ AB concentration is lower than 0.01 mol / L, the amount of spherical fine particles produced increases, and the amount of amines used in combination tends to decrease. On the other hand, if the CT ₁₆ AB concentration is higher than 1.0 mol / L, the solution tends to be high in viscosity, and the reaction tends to take a long time, which is disadvantageous in cost.

As the amine used in combination with the ammonium salt, for example, one or more alkylamines or alkanolamines represented by the following formulas (2) to (5) are used.
NR ₃ (R: C _n H _{2n + 1} n = 1-8 integer) (2)
_{N (ROH) 3 (R:} C n H 2n n = 1~8 integer) Equation (3)
H ₂ NR (R: C _n H _{2n + 1} n = 1 to 8 integer) (4)
HNR ₂ (R: C _n H _{2n + 1} n = 1 to 8 integer) (5)

The alkylamine or alkanolamine has a hydrophobic property that becomes stronger as the alkyl chain length becomes longer, and is difficult to dissolve in water. However, the alkylamine or alkanolamine is used in combination with the ammonium salt and reacts by utilizing the emulsifying action of the ammonium salt. Can be mixed in an aqueous solution. These amines preferably have an ionization index (pka) in the range of 7.0 to 12.5.

Preferred examples of the alkylamine or alkanolamine include a trialkylamine having a pka value of about 10.0 represented by the formula (2), and a 2,2 ′ having a pka value of about 7.8 represented by the formula (3). , 2 ″ -nitrilotriethanol and the like. These amines are suitable for reducing the production of spherical fine particles and preferentially producing rod-shaped fine particles because of their reduction rate.

As specific examples of the trialkylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, and trihexylamine are preferable. Of these, triethylamine is particularly advantageous for obtaining rod-shaped metal fine particles having a short minor axis and a short major axis. Tributylamine and tripentylamine have the effect of suppressing the formation of spherical fine particles and increasing the yield of rod-shaped metal fine particles. When the alkyl chain length is longer than this, the solubility in the reaction aqueous solution tends to decrease. The alkanolamine 2,2 ′, 2 ″ -nitrilotriethanol also has the effect of suppressing the formation of spherical fine particles and increasing the yield of rod-shaped metal fine particles.

In addition, conventionally used reducing agents such as sodium borohydride, hydrazine, and ascorbic acid have a relatively strong reducing power, so that reduction of metal ions is rapid, resulting in spherical metal fine particles having a relatively large particle size. The tendency is strong and it is difficult to obtain metal nanorods.

The concentration of these amines in the reaction aqueous solution is suitably from 0.001 to 10 wt%, preferably from 0.01 to 5.0 wt%. When the concentration is higher than 10 wt%, not only the amines are not completely dissolved in the reaction aqueous solution containing an ammonium salt, but also a reduction reaction of metal ions occurs rapidly and the production of spherical fine particles tends to increase. On the other hand, if this concentration is less than 0.001 wt%, metal ions cannot be completely reduced, and even if metal ions can be reduced, a long time tends to be required.

By adjusting the concentration of amines and ammonium salt, the particle diameter of the metal fine particles can be controlled, and metal nanorods finer than the conventional particle diameter can be obtained. Specifically, amines and ammonium salts are mixed so as to be in the above-mentioned concentration range. Within this concentration range, for example, the reducing power is increased by increasing the concentration of amines, the number of seed fine particles growing on the gold nanorods increases in the initial stage of synthesis, and the metal ions in the synthesis solution as the seed fine particles grow. Therefore, the growth stops at a stage where the particle diameter is fine, and there is a tendency to become a metal nanorod having a fine particle diameter. On the other hand, for example, by increasing the concentration of the ammonium salt, the viscosity of the synthesis solution is increased, and the reduction reaction of metal ions and the growth reaction of metal nanorods are slowed. There is a tendency to become a metal nanorod with a fine diameter.

Various additives may be added as necessary to the reaction aqueous solution containing amines and ammonium salts. In particular, the aspect ratio of the metal fine particles can be adjusted by adding ketones. Among the ketones, acetone is optimal, and the amount added is preferably 0 to 2 wt% in the aqueous solution. When this addition amount is small, the aspect ratio is small and the production of spherical fine particles tends to increase. On the other hand, when this addition amount is large, the aspect ratio increases. If the amount added is more than 2 wt%, the aspect ratio increases, but the major axis length of the metal nanorods tends not to be constant, the particle size distribution of the metal nanorods becomes wider, and sharp absorption is obtained. Not only is it not possible, but the amount of spherical fine particles produced tends to increase. In addition to this, the aspect ratio of the metal nanorods can be adjusted by adding silver.

In the production method of the present invention, metal nanorods are produced in an aqueous solution containing amines and ammonium salts, so that ammonium salts are adsorbed on the surface of the obtained metal nanorods. Since this ammonium salt is hydrophilic, it is difficult to extract the metal nanorod having the ammonium salt adsorbed on the surface thereof into an organic solvent (non-aqueous solvent).

The metal nanorods in which the ammonium salt is adsorbed on the surface are stably dispersed in a non-aqueous solvent by surface treatment with a dispersant having a side chain having affinity for the non-aqueous solvent (referred to as a non-aqueous dispersant). Can be made. As such a non-aqueous dispersant, an element having a number average molecular weight of 100 to 10,000, preferably 1000 to 3,000 and having high adsorptivity to metal nanorods, for example, when the metal is gold, silver or copper, nitrogen, A high molecular compound having a plurality of side chains having one of sulfur as an adsorption site in the main chain and having affinity for a non-aqueous solvent is used. When the number average molecular weight is less than 1000, the dispersion stability in the non-aqueous solvent is not sufficient, and when it exceeds 10,000, the solubility in the non-aqueous solvent is lowered and the stability is impaired. The agent itself becomes an impurity, and the performance (for example, electrical characteristics) of the metal nanorod is reduced.

Specific examples of non-aqueous dispersants are Solsperse 134000, Solsperse 24000SC, Solsperse 28000, Solsperse 32000 (above, product names of Avicia products), Floren DOPA-15B, Floren DOPA-17 (above, Kyoeisha Chemical) Product name), Ajisper PB814, Ajisper PB711 (above, Ajinomoto Finetechno product name), Dispersic 160, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 183, Dispersic 184, Dispers Big 185 (above, the trade name of the product of Big Chemie Japan) can be used. For example, Solsperse 24000SC has a large amount of nitrogen, which is an element highly adsorbing to metal nanorods, in the main chain as an adsorption site, and the side chain is against non-aqueous solvents such as aromatics, ketones and esters. It is a so-called [comb structure] dispersant having high solubility, and this dispersant forms a state of being adsorbed on the surface of the metal nanorods at the nitrogen site, whereby the metal fine particles can be stably dispersed in the non-aqueous solvent it can.

Any non-aqueous dispersant containing sulfur may be used as long as it contains sulfur and can be dissolved in a non-aqueous solvent, and butanethiol, hexanethiol, octanethiol, decanethiol, dodecanethiol, and the like are used.

As a method of surface-treating metal fine particles with a non-aqueous dispersant, a solution obtained by dissolving a non-aqueous dispersant in a non-aqueous solvent is used, and this solution is added to the metal nanorod aqueous dispersion and further adsorbed on the surface of the metal nanorods. It is possible to apply a method of adding a solution (desorption liquid) for dissolving or desorbing an ammonium salt such as CT _n AB and replacing the surface ammonium salt with a non-aqueous dispersant. The metal nanorods produced in (1) can be extracted into a non-aqueous solvent.

Note that any desorbing solution for dissolving or desorbing an ammonium salt such as CT _n AB may be used as long as it is hydrophilic and increases the solubility of the ammonium salt. As such a solution, alcohols such as methanol and ethanol, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone can be used.

The amount of the non-aqueous dispersant used is suitably 0.0001 to 20 parts by weight, preferably 0.0001 to 10 parts by weight per 100 parts by weight of the non-aqueous solvent. If the amount added is too large, it is disadvantageous in terms of cost, and the non-aqueous dispersant itself becomes an impurity and the performance of the metal nanorods decreases. On the other hand, when the addition amount is too small, a sufficient surface treatment effect cannot be obtained, and the metal nanorods are not stably dispersed in the non-aqueous solvent and are likely to aggregate.

The volume of the metal nanorod aqueous dispersion (containing 0.3 parts by weight of metal nanorods) with respect to the non-aqueous solvent is suitably 0.01 to 10 times the amount of the non-aqueous solvent, and preferably 0.1 to 1 times. If the volume of the metal nanorod aqueous dispersion is out of the above range, the metal nanorods are not stably extracted into the non-aqueous solvent.

As a method for reducing or removing the ammonium salt on the surface of the metal nanorod, in addition to the above surface treatment, (b) sedimentation method by addition of a poor solvent, (b) centrifugation, etc. can be applied. The precipitation method by adding a poor solvent is a method in which a poor solvent of ammonium salt adsorbed on the surface of the metal nanorods is added to the metal nanorod dispersion, the metal nanorods are precipitated, and the ammonium salt extracted in the supernatant is removed. is there. Centrifugation is a method in which a metal nanorod dispersion is precipitated using a centrifuge and the ammonium salt extracted in the supernatant is removed.

By combining the surface treatment method, the sedimentation method using a poor solvent, and the centrifugal separation method, the ammonium salt on the surface of the metal nanorods can be efficiently removed. For example, the surface treatment of metal nanorods is performed using a non-aqueous dispersant having an affinity for non-aqueous solvent toluene, and the metal nanorods are extracted into a small amount of toluene to form a metal nanorod toluene paste, and at the same time, most of the ammonium salt is removed. Remove. Ethanol, which is a poor solvent, is added to the obtained paste, and metal nanorods coated with a non-aqueous dispersant having an affinity for toluene are aggregated. Centrifugation is performed to accelerate the sedimentation speed of the aggregate, and the metal nanorod aggregate is settled in a short time. Since the ammonium salt is dissolved in ethanol, the ammonium salt is extracted into the supernatant ethanol layer (partially toluene). The supernatant is separated to recover the metal nanorods.

Note that since the metal nanorods coated with a dispersant having affinity for precipitated toluene are redispersed with a small amount of toluene, it is possible to produce a paste with reduced organic content. By repeating the above treatment operation, a metal nanorod from which ammonium salt has been removed or reduced can be obtained. What reduced ammonium salt to 15 weight part or less, Preferably to 5 weight part or less with respect to 100 weight part of metal nanorods is suitable as an electroconductive material.

By the above production method of the present invention, for example, metal nanorods having a minor axis of 15 nm or less, preferably 5 nm or less can be produced easily and efficiently. Metal nanorods change the absorption wavelength range by adjusting the aspect ratio, and when the metal species is gold, they exhibit a wide range of specific absorption wavelengths from visible light (around 530 nm) to the near infrared range.

The major axis of the metal nanorod of the present invention is 400 nm or less, preferably 200 nm or less. When the long axis of the metal nanorod is 400 nm or less, it is difficult to recognize as a particle with the naked eye, and a highly transparent coating film can be obtained when applied for filter applications or the like. Furthermore, the metal nanorod of the present invention is in the form of a rod having an aspect ratio (major axis length / minor axis length) greater than 1. The metal fine particles having an aspect ratio of 1 are spherical particles, and the light absorption region is limited to around 530 nm when gold is used, and is limited to around 400 nm when silver is used, and is selective to any wavelength of visible light and near infrared light. A good absorption effect cannot be obtained.

A metal nanorod-containing composition can be obtained by mixing the metal fine particles (metal nanorods) of the present invention with a binder (resin) together with a dispersion medium, for example. As the binder (resin), various resins that are transmissive to light in the visible to near-infrared region, which are usually used for paints and moldings, can be used without particular limitation. For example, various organic resins such as acrylic resin, polyester resin, alkyd resin, urethane resin, silicone resin, fluorine resin, epoxy resin, polycarbonate resin, polyvinyl chloride resin, polyvinyl alcohol, radical polymerizable oligomers and monomers (depending on the case Typical examples thereof include a sol-gel solution using an alkoxysilane as a resin skeleton, and the like in combination with a curing agent and a radical polymerization initiator.

In the metal nanorod-containing composition of the present invention, as a solvent to be blended as necessary, a solvent in which a binder (resin) is dissolved or stably dispersed may be appropriately selected. Specifically, water, methanol, Alcohols such as ethanol, propanol, hexanol and ethylene glycol, alcohols such as ethylene glycol, aromatic hydrocarbons such as xylene and toluene, alicyclic hydrocarbons such as cyclohexane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate Typical examples thereof include, but are not limited to, esters such as butyl acetate, ethers such as ethylene glycol monobutyl ether, and mixtures thereof.

The addition amount of the metal nanorods is suitably from 0.01 to 1900 parts by weight with respect to 100 parts by weight of the binder, and preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the binder for optical applications. In use, 566 to 1900 parts by weight is preferable with respect to 100 parts by weight of the binder. In the case of optical use, if the addition amount is less than that, there is little absorption, and the desired coloring (reduction of transmittance in the case of the near infrared region) cannot be obtained. If the amount added is larger than that, the metal nanorods aggregate and sharp absorption cannot be obtained. In the case of conductive use, if the amount of metal nanorods added is less than that, the influence of the insulating effect of the binder is increased, so that it is difficult to obtain high conductive properties. Moreover, when there is much addition amount, aggregation of metal nanorods will occur easily and the storage stability as a coating composition will worsen.

Metal nanorods blended in the binder (resin) have a reduced amount of residual ammonium salt by surface treatment with a non-aqueous dispersant having a side chain that has affinity for the non-aqueous solvent, or by poor solvent precipitation or centrifugation. preferable. In the case of an optical application, the surface treated with a non-aqueous dispersant is 5 to 50 wt%, preferably 8 to 30 wt% with respect to the metal nanorods. Outside this range, metal nanorods tend to aggregate. Moreover, in the case of the use of a conductive material, the amount of the non-aqueous dispersant is preferably 8 to 15 wt% with respect to the metal nanorods. If the amount added is more than that, the conductivity will deteriorate.

Depending on the purpose, the metal nanorod-containing composition may contain one or more of dyes, pigments, phosphors, metal oxides, and metal nanofibers. Furthermore, you may add a leveling agent, an antifoamer, and other various additives as needed. In addition, metal nanorods can be used in combination of the same type or two or more different types.

The metal nanorod-containing composition of the present invention can be used in various forms such as a coating composition, a coating film, a film, or a plate material, and has a filter layer formed by the composition for forming a light absorbing material. Can be obtained. Specifically, for example, (i) a cured coating film is formed as a visible light / near-infrared light absorbing filter by directly applying or printing on a substrate that wants to absorb visible light / near-infrared light. (B) The composition of the present invention is formed into a film shape, a plate shape or the like, and the composition is laminated or surrounded as a visible light / near infrared light absorption filter on a base material to absorb visible light / near infrared light. . (C) The formed film or film formed by the composition of the present invention is laminated on a transparent glass or plastic substrate, and the laminate is visible as a visible light / near infrared light absorbing filter. It is used by laminating or surrounding a base material that wants to absorb light and near infrared light. In each of the above usage forms, the thickness of the light absorption filter is suitably about 0.01 μm to 1 mm, and preferably 0.1 μm to 100 μm in view of cost, light transmittance, and the like.

What has a coating film, a film, a board | plate material, etc. which were formed with the said composition of this invention as a filter layer is, for example, visible light / near infrared light cut film, visible light / near infrared light cut filter, or visible light / It can be used as a light absorbing material excellent in heat resistance such as near infrared light cut glass.

The metal nanorods of the present invention have wavelength absorption characteristics corresponding to the metal species, particle shape, and aspect ratio. For example, when the metal species is gold, it has plasmon absorption characteristics at a wavelength higher than around 530 nm depending on the aspect ratio, and has high heat resistance, weather resistance, and chemical resistance based on gold. It is suitable as a material such as a near infrared absorber, an anti-counterfeit ink absorber, a biosensor, a DNA chip, and a sensitizer for a surface-enhanced fluorescent sensor. In addition, since gold is a material that is safe for the living body, it can be used as a material for food additives, cosmetics, biomarkers, drug carriers for drug delivery systems (DDS), testing agents, and the like. . Further, since gold exhibits high conductivity, it can be used as a wiring material, an electrode material, and an electromagnetic shielding material. In addition, it can be used as a polarizing material, a recording material, a recording element, and a nano waveguide based on the shape anisotropy of the nanorod. Furthermore, since it is a fine particle and has a large surface area, it is suitable as a material for providing a field for catalytic reaction.

As described above, the production method of the present invention uses a weak reducing power of amines in the presence of a surface-active action of an ammonium salt to form a reaction field in which metal nanorods are slowly generated. It is possible to manufacture metal nanorods that are finer than those of the present invention, and to significantly suppress plasmon absorption due to the short axis. In addition, since the production method of the present invention can control the aspect ratio of the metal nanorods by adjusting the mixing ratio of the amines and ammonium salts used together, the metal nanorods having the desired light absorption characteristics can be easily obtained. be able to. Furthermore, according to the production method of the present invention, metal nanorods can be produced easily and in large quantities, which is suitable for practical use.

The present invention is specifically shown below by examples and comparative examples. Each example relates to a gold nanorod and mainly shows a light absorption function in a wavelength range of 530 nm to 1150 nm, but it can be further increased by changing conditions such as the type, length, and composition of the metal nanorod. The same light absorption function can be provided for the high wavelength region. Spectral characteristics were measured with V-570 manufactured by JASCO Corporation. The specific resistance value was measured by Loresta GP, a product of Mitsubishi Chemical Corporation. The production conditions and results of each example are shown in Tables 1 to 3. Moreover, the optical characteristic of the metal nanorod obtained in each example was shown in FIGS.

To 10 ml of 0.08 mol / L hexadecyltrimethylammonium bromide (CT ₁₆ AB) aqueous solution, 0.05 ml of triethylamine (pka = 10.7) was added and dissolved. To this, 0.6 ml of 0.01 mol / L silver nitrate aqueous solution was added as an aspect ratio adjuster. To this aqueous solution was added 0.8 ml of 0.024 mol / L chloroauric acid aqueous solution, immediately after that 0.2 ml of acetone was added and kept at 30 ° C. for 4 hours. As a result, a gold nanorod having a minor axis of about 4 nm, a major axis of about 20 nm, an aspect ratio of about 5, and an absorption wavelength peak of about 810 nm was obtained.

To 10 ml of 0.56 mol / L hexadecyltrimethylammonium bromide (CT ₁₆ AB) aqueous solution, 0.10 ml of 2,2 ′, 2 ″ -nitrilotriethanol (pka = 7.8) was added and dissolved. 0.42 ml of an aqueous solution of silver nitrate / L was added, 0.8 ml of 0.024 mol / L aqueous solution of chloroauric acid was added to this aqueous solution, and 0.2 ml of acetone was added immediately thereafter, and the mixture was kept at 30 ° C. for 48 hours. A gold nanorod having a short axis of about 8 nm, a long axis of about 88 nm, an aspect ratio of about 11, and an absorption wavelength peak of about 1150 nm was obtained.

To 10 ml of 0.08 mol / L hexadecyltrimethylammonium bromide (CT ₁₆ AB) aqueous solution, 0.05 ml of triethylamine (pka = 10.7) was added and dissolved. To this was added 0.6 ml of a 0.01 mol / L silver nitrate aqueous solution. To this aqueous solution, 0.8 ml of 0.024 mol / L chloroauric acid aqueous solution was added, and acetone was not added. Hold at 30 ° C. for 4 hours. As a result, a gold nanorod having a minor axis of about 3.4 nm, a major axis of about 6.8 nm, an aspect ratio of about 2, and an absorption wavelength peak of about 658 nm was obtained.

To 10 ml of a 0.56 mol / L hexadecyltrimethylammonium bromide (CT ₁₆ AB) aqueous solution, 0.09 ml of tri-n-butylamine was added and dissolved. To this, 0.6 ml of 0.01 mol / L silver nitrate aqueous solution was added as an aspect ratio adjuster. To this aqueous solution, 0.8 ml of 0.024 mol / L chloroauric acid aqueous solution was added, and immediately after that, 0.2 ml of acetone was added and kept at 30 ° C. for 24 hours. As a result, a gold nanorod having a short axis of about 8 nm, a long axis of about 49 nm, an aspect ratio of about 6, and an absorption wavelength peak of about 980 nm was obtained.

To 10 ml of a 0.56 mol / L hexadecyltrimethylammonium bromide (CT ₁₆ AB) aqueous solution, 0.1 ml of tri-n-pentylamine was added and dissolved. To this, 0.6 ml of 0.01 mol / L silver nitrate aqueous solution was added as an aspect ratio adjuster. To this aqueous solution, 0.8 ml of 0.024 mol / L chloroauric acid aqueous solution was added, and immediately after that, 0.2 ml of acetone was added and kept at 30 ° C. for 48 hours. As a result, a gold nanorod having a minor axis of about 8 nm, a major axis of about 88 nm, an aspect ratio of about 11, and an absorption wavelength peak of about 1200 nm was obtained.

To 250 parts by weight of the gold nanorod aqueous dispersion produced in Example 1, 100 parts by weight of toluene in which 1 wt% of the nitrogen-containing dispersant Solsperse 24000SC was dissolved was added and stirred for 3 minutes. 500 parts by weight of ethanol was added to the mixture, and the mixture was further stirred for 5 minutes. After the stirring was completed, the mixture was allowed to stand for 24 hours. The mixed solution was clearly separated into two layers from a transparent aqueous layer in the lower layer and a toluene layer in which the gold nanorods were dispersed in the upper layer. When the upper layer was collected and the gold content was measured by ICP, the metal nanorods surface-treated with the dispersant were almost extracted into the non-aqueous solvent. Further, when the storage stability was confirmed, the dispersion was stable for 90 days or more.

To 250 parts by weight of the gold nanorod aqueous dispersion produced in Example 1, 100 parts by weight of n-hexane in which 1 wt% of dodecanethiol as a sulfur-containing dispersant was dissolved was added and stirred for 3 minutes. 500 parts by weight of acetone was added to the mixture, and the mixture was further stirred for 5 minutes. After the stirring was completed, the mixture was allowed to stand for 24 hours. The mixed solution was clearly separated into two layers from an aqueous layer having a transparent lower layer and an n-hexane layer having gold nanorods dispersed in an upper layer. When the upper layer was collected and the gold content was measured by ICP, the metal nanorods surface-treated with the dispersant were almost extracted into the non-aqueous solvent. Further, when the storage stability was confirmed, the dispersion was stable for 90 days or more.

Toluene was removed from the gold nanorod toluene dispersion extracted in Example 4 with an evaporator to prepare a toluene paste containing 5 wt% of gold nanorods. When this residue was measured with Tg-DTA, this paste contained 25 wt% of organic components (CT ₁₆ AB, Solsperse 24000SC, triethylamine). When 100 parts by weight of ethanol, which is a poor solvent for Solsperse 24000SC, was added to 100 parts by weight of the paste, aggregates of Solsperse 24000SC and gold nanorods were generated. This solution was centrifuged at 40,000 G for 30 minutes to precipitate the aggregates, and the supernatant ethanol solution containing CT ₁₆ AB and triethylamine was removed. This sediment was redispersed with toluene to obtain a toluene dispersion containing 5 wt% of gold nanorods. When the heating residue was measured with Tg-DTA, the organic content of this paste was reduced to 0.5 wt%. This gold nanorod toluene paste was applied with a bar coater # 40, heated at 300 ° C. for 30 minutes, and the specific resistance of the coated film after heating was measured. The specific resistance was 1 × 10 ⁻⁵ Ω · cm.

The gold nanorods produced in Example 3 were subjected to the same surface treatment as in Example 4, and were further made into a paste in the same manner as in Example 6 to remove the organic content so that the residual organic content was 0.5 wt%. A gold nanorod toluene dispersion containing 5 wt% of gold nanorods was obtained. This gold nanorod toluene paste was applied with a bar coater # 40, heated at 300 ° C. for 30 minutes, and the specific resistance of the coating film after heating was measured. The specific resistance was 1 × 10 ⁻⁴ Ω · cm.

Gold nanorods having a minor axis of 5 nm and a major axis of 35 nm (aspect ratio: 7.0, absorption wavelength peak: 950 nm), a binder, and a solvent were mixed at a ratio shown in Table 4 to prepare a coating composition. This paint was applied to a glass substrate with a spin coater, allowed to stand for 5 minutes, and then cured by irradiating with ultraviolet rays with a high-pressure mercury lamp to form a light absorbing material filter. The transmittance of this filter was measured. The results are shown in Table 4. The spectral characteristics are shown in FIG. The transmittance in the visible light region was as high as 60%, and the transmittance in the vicinity of 950 nm, which is the plasmon absorption peak of the gold nanorods, was as excellent as 11%.

Comparative example

[Comparative Example 1]
To 10 ml of 0.08 mol / L aqueous sodium dodecyl sulfate solution, 0.05 ml of triethylamine (pka = 10.7) was added and dissolved. To this was added 0.6 ml of a 0.01 mol / L silver nitrate aqueous solution. To this aqueous solution, 0.8 ml of 0.024 mol / L chloroauric acid aqueous solution was added, and immediately after that, 0.2 ml of acetone was added and stored at 30 ° C. for 4 hours. As a result, the obtained gold fine particles were spherical gold fine particles having an aspect ratio of about 1, and rod-shaped fine particles were not obtained.

[Comparative Example 2]
To 250 parts by weight of the gold nanorod aqueous dispersion prepared in Example 1, 100 parts by weight of toluene was added and stirred for 3 minutes. To this mixed solution, 500 parts by weight of ethanol was added, stirred for 5 minutes, and allowed to stand for 24 hours after completion of stirring. The produced metal nanorods were hardly extracted into the non-aqueous solvent, and the CT ₁₆ AB adsorbed on the gold nanorods was desorbed from the gold nanorod surface and dissolved by ethanol. It settled and did not redisperse in water or a non-aqueous solvent.

[Comparative Example 3]
Toluene was removed from the gold nanorod toluene dispersion extracted in Example 4 with an evaporator to prepare a toluene paste containing 5 wt% of gold nanorods. When this residue was measured with Tg-DTA, this paste contained 25 wt% of organic components (CT ₁₆ AB, Solsperse 24000SC, triethylamine). When this gold nanorod toluene paste was applied with a bar coater # 40, heated at 300 ° C. for 30 minutes, and the specific resistance of the coating film after heating was measured, conductivity was not confirmed.

Wavelength absorption graph of gold fine particles of Examples 1 to 3 and Comparative Example 1 Wavelength absorption graph of gold fine particles of Example 8

Claims (18)

In a method for producing rod-shaped fine metal particles by chemically reducing metal ions in an aqueous solution, an aqueous solution containing an amine having a reducing ability and an ammonium salt having substantially no reducing ability is used. A method for producing fine metal particles, wherein metal ions are reduced by the amines in the presence of the ammonium salt.
The method of claim 1, wherein the quaternary ammonium salt represented by the following formula (1) is used as an ammonium salt used in combination with an amine.
CH ₃ (CH ₃ ) _n N ⁺ (CH ₃ ) ₃ Br ⁻ (n = 1 to 17 integer) (1)
3. The method for producing fine metal particles according to claim 1, wherein one or more alkylamines or alkanolamines represented by the following formulas (2) to (3) are used as amines used in combination with ammonium salts.
NR ₃ (R: C _n H _{2n + 1} n = 1-8 integer) (2)
_{N (ROH) 3 (R:} C n H 2n n = 1~8 integer) Equation (3)
4. The method of producing fine metal particles according to claim 3, wherein triamineamine, tributylamine, tripentylamine, or 2,2 ′, 2 ″ -nitrilotriethanol is used as the amine.
3. The method for producing fine metal particles according to claim 1 or 2, wherein one or more alkylamines represented by the following formulas (4) to (5) are used as amines used in combination with an ammonium salt.
H ₂ NR (R: C _n H _{2n + 1} n = 1 to 8 integer) (4)
HNR ₂ (R: C _n H _{2n + 1} n = 1 to 8 integer) (5)
The method for producing metal fine particles according to any one of claims 2 to 5, wherein the concentration of the ammonium salt represented by the formula (1) in the aqueous solution is 0.01 to 1.0 mol / L.
The method for producing fine metal particles according to any one of claims 2 to 6, wherein the concentration of the amines represented by the formulas (2) to (5) in the aqueous solution is 0.001 to 10 wt%.
The method for producing metal fine particles according to any one of claims 2 to 7, wherein the ionization index (pka value) of the amines represented by the formulas (2) to (5) is 7.0 to 12.5.
The method for producing fine metal particles according to any one of claims 1 to 8, wherein the particle diameter is controlled by adjusting the concentrations of amines and ammonium salt.
The method for producing metal fine particles according to any one of claims 1 to 9, wherein a ketone is added to the aqueous solution containing the amines and ammonium salt to adjust the aspect ratio of the metal fine particles.
A rod-shaped metal fine particle produced by the method according to any one of claims 1 to 10, wherein the major axis is 400 nm or less, the minor axis is 15 nm or less, and the aspect ratio is greater than 1.
Metal fine particles produced by the method according to any one of claims 1 to 10 and surface-treated with a non-aqueous dispersant having a side chain having an affinity for a non-aqueous solvent.
Metal fine particles produced by the method according to any one of claims 1 to 10, wherein the residual amount of ammonium salt on the surface of the metal fine particles is removed or reduced to 15 parts by weight or less with respect to 100 parts by weight of the metal fine particles.
The composition containing the metal microparticle manufactured by the method in any one of Claims 1-10, or the metal microparticle in any one of Claims 11-13.
The metal fine particle-containing composition according to claim 14, comprising a binder (resin) and a dispersion medium together with the metal fine particles.
The metal fine particle-containing composition according to claim 14 or 15, which contains one or more of dyes, pigments, phosphors, metal oxides, and metal nanofibers together with the metal fine particles.
The light absorption material which has the form of the coating composition formed by the metal microparticle containing composition in any one of Claims 14-16, a coating film, a film, or a board | plate material.
An optical filter material, a wiring material, an electrode material, a catalyst, a colorant containing the metal fine particles produced by the method according to any one of claims 1 to 10, or the metal fine particles according to any one of claims 11 to 13, Cosmetics, near-infrared absorber, anti-counterfeiting ink, electromagnetic shielding material, surface-enhanced fluorescent sensor, biomarker, nanowaveguide, recording material, recording element, polarizing material, drug delivery system (DDS) drug holder, biosensor, DNA chip, test drug.

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