WO2008032839A1

WO2008032839A1 - Base material covered with metal layer and process for producing the same

Info

Publication number: WO2008032839A1
Application number: PCT/JP2007/068002
Authority: WO
Inventors: Hidekatsu Kuroda
Original assignee: Ube Nitto Kasei Co., Ltd.
Priority date: 2006-09-15
Filing date: 2007-09-07
Publication date: 2008-03-20
Also published as: KR20090073091A; CN101517123B; TW200835809A; JPWO2008032839A1; TWI449804B; CN101517123A

Abstract

A base material covered with metal layer characterized by having a base material, metal nanoparticles in dotted or layered form provided on the base material via a silane coupling agent containing a chelate forming functional group, and a metal layer superimposed on the metal nanoparticles in dotted or layered form. Further, there is provided a process for producing a base material covered with metal layer, characterized by including bringing a base material into contact with a water base solution containing a hydrolysis catalyst, a silane coupling agent containing a chelate forming functional group and a metal nanoparticle forming metal salt and treating the resultant mixture with a reducing agent to thereby obtain metal nanoparticles in dotted or layered form provided on the base material via the silane coupling agent containing a chelate forming functional group, and thereafter forming a metal layer on the metal nanoparticles in dotted or layered form.

Description

Technical Field

The present invention relates to a metal layer coating substrate that can be used for a conductive material, an electromagnetic shielding material, and the like, and a method for producing the same. Background art

As a method for coating a metal on a non-conductive substrate, an electroless plating method is generally used. An example of the electroless plating method is a method of forming a metal layer by immersing the base material in an electroless plating bath containing a metal salt, a metal complexing agent, a pH adjusting agent, a reducing agent, etc. (For example, “Electrical electrolysis mecha-ichi basics and applied one”, 4th edition, edited by the Electroplating Institute, published by Nikkan Egyo Shimbun, published on 1 9 9 9 10th, 1 0 1 ~ 1 2 See page 7.)

Normally, when a metal layer-coated substrate is produced by the electroless plating method, a catalyst for initiating electroless plating, called the activation process, is attached to the substrate before activating the substrate surface. A processing step is required. Generally, this step is performed as follows. Before the substrate is electrolessly attached, it is brought into contact with an aqueous solution of stannous chloride to adsorb tin ions, and then brought into contact with an aqueous solution of palladium chloride. Adsorb palladium colloid. This palladium colloid will act as a catalyst for initiating the electroless union.

After the activation treatment, the substrate is immersed in an electroless plating bath containing components other than a reducing agent such as a metal salt, a metal complexing agent, and a pH adjuster, and then a reducing agent is added, or a metal Immerse the substrate in an electroless plating bath containing components other than metal salts and reducing agents such as complexing agents and pH adjusters, and then add the reducing agent and metal salt to the surface of the substrate. Form a genus layer.

When the metal layer is deposited on the surface of the substrate by the above method, the distribution of tin or palladium becomes non-uniform due to the difference in adsorptivity, etc. Variation in surface potential occurs. Therefore, when electroless plating is performed, a portion where the metal layer is easily deposited and a portion where the metal layer is difficult to deposit are generated, and the metal layer is formed only in a part, resulting in an undeposited portion and exposing the substrate surface. A part arises. Therefore, there is a problem that stable conductivity cannot be secured in the obtained metal layer-coated substrate. In addition, the tin salt used in the active-rich treatment process is corrosive, so it is necessary to wash before the start of electroless plating to remove the remaining tin salt. There is also a problem that the number of palladium colloids is reduced and electroless plating is difficult to proceed. Disclosure of the invention

Under such circumstances, the present invention provides a metal layer-coated base material having stable conductivity, and the metal layer-coated base material is inexpensive without using special equipment or equipment. In addition, the object is to provide a manufacturing method that is simple and has little impact on the environment.

As a result of repeated studies by the inventor of the present invention, the substrate, the interspersed material or layered material of metal nanoparticles formed on the substrate via a chelate-forming functional group-containing silane coupling agent, and the metal A novel metal layer-coated substrate comprising a metal layer formed on a nanoparticle interspersed material or a layered material, the substrate is formed into a hydrolysis catalyst, a chelate-forming functional group-containing silane force pulling agent, and metal nanoparticles. After contact with an aqueous solution containing a functional metal salt, the metal nanoparticles are dispersed or layered via a silane coupling agent containing a biofunctional group containing a chelating agent on the substrate by treating with a reducing agent. And then forming a metal layer on the metal nanoparticle interspersed or layered material, and finding that the obtained metal layer-coated substrate has stable conductivity, Based on such knowledge Thus, the present invention has been completed.

That is, the present invention

(1) A substrate, a dot or layered product of metal nanoparticles formed on the substrate via a chelate-forming functional group-containing silane coupling agent, and a dot or layer of the metal nanoparticles or A metal layer-coated substrate comprising a metal layer formed on a layered material, (2) The metal layer-coated substrate according to (1) above, wherein the substrate comprises at least one selected from the group consisting of silica, ceramics and glass,

(3) The metal layer-coated substrate according to (1) or (2) above, wherein the shape of the substrate is one selected from the group consisting of a spherical shape, a rod shape, a plate shape, a needle shape, a hollow shape and an unspecified shape ,

(4) The metal layer-coated substrate according to the above (3), wherein the shape of the substrate is a fine particle shape having an average particle size of 0 :! to 100 / im,

(5) The chelate-forming functional group according to any one of the above (1) to (4), wherein the chelate-forming functional group is a functional group having at least one atom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom Metal layer coated substrate,

(6) at least one functional group selected from the group consisting of 1 SH, 1 CN, 1 NH ₂ , -S0 ₂ OH, _S 0 OH, -OPO (OH) ₂ and 1 COOH. The metal layer-coated substrate according to (5) above,

(7) The metal according to any one of (1) to (6), wherein the metal nanoparticle is a nanoparticle composed of at least one metal selected from the group consisting of gold, silver, copper and nickel. Layer coated substrate,

(8) The metal layer-coated substrate according to any one of (1) to (7), wherein the metal layer is a layer made of silver,

(9) The substrate is brought into contact with an aqueous solution containing a hydrolysis catalyst, a chelate-forming functional group-containing silane coupling agent and a metal nanoparticle-forming metal salt, and then treated with a reducing agent to form a base. A metal nanoparticle interspersed or layered material is formed on the material via a chelate-forming functional group-containing silane coupling agent, and then a metal layer is formed on the metal nanoparticle interspersed or layered material. A method for producing a metal-layer-coated substrate, and

(10) The method for producing a metal layer-coated substrate according to (9) above, wherein the metal layer is formed by an electroless plating method

Is to provide.

According to the present invention, a metal nanoparticle interspersed or layered material is formed on a substrate, whereby each metal nanoparticle serves as a starting point and the metal nanoparticle interspersed or layered material is contained. A metal layer can be easily formed, and when a layered product of metal nanoparticles is formed on a substrate, even if an unformed part of the metal layer is formed on the metal nanoparticle layer, Since the metal nanoparticle layer is present between the metal layer and the resulting metal layer-coated substrate, the substrate surface is not exposed, and stable conductivity can be ensured.

In addition, according to the present invention, it is possible to provide a method for producing the metal layer-coated substrate at a low cost and with a simple process, with little influence on the environment, without using special equipment or equipment. Brief Description of Drawings

FIG. 1 is a SEM photograph of the gold nanoparticle layer-forming sili-power particles obtained in Example 1. FIG. 2 is an SEM photograph of the silver layer-coated silica particles obtained in Example 1.

FIG. 3 is a SEM photograph of the silver layer-coated polyimide particles obtained in Example 2.

FIG. 4 is an SEM photograph of the gold nanoparticle layer-forming silli force particles obtained in Example 7. FIG. 5 is an SEM photograph of the silver layer-coated silli force particles obtained in Example 8.

FIG. 6 is an SEM photograph of the silver layer-coated soda-lime glass beads obtained in Example 9.

FIG. 7 is an SEM photograph of the gold nanoparticle layer-forming silica particles obtained in Example 10. FIG. 8 is an SEM photograph of the silver nanoparticle layer-forming silica particles obtained in Example 11-1. FIG. 9 is an SEM photograph of the gold layer-coated sili-force particles obtained in Example 12. BEST MODE FOR CARRYING OUT THE INVENTION

First, the metal layer-coated substrate of the present invention will be described.

The metal layer-coated base material of the present invention includes a base material, interspersed or layered materials of metal nanoparticles formed on the base material via a chelate-forming functional group-containing silane coupling agent, and the metal And a metal layer formed on a nanoparticle interspersed or layered material.

The substrate used in the metal layer-coated substrate of the present invention preferably has an OH group on the substrate surface and interacts with a silane coupling agent described later. In addition, examples of such a substrate include at least one selected from the group consisting of silica, ceramics, and glass.

Examples of the silica include completely crystallized dry silica (cristobalite), water-dispersed silica (colloidal silica), and the like.

Examples of ceramics include aluminum oxide (anoremina), sapphire, mullite, titanium oxide (titania), carbide, nitride, aluminum nitride, and zirconium. Can

Examples of the glass include various shot glasses such as B K 7, SF 11 and La S F N 9, optical crown glass, soda glass, soda lime glass, low expansion borosilicate glass, and the like.

In addition to the materials described above, resins can also be used as a base material on the condition that they interact with a silane coupling agent. Examples of the resins include silicone resins, phenol resins, and naturally-modified phenols. Resin, Epoxy resin, Polybulu alcohol resin, Cellulose / Loose resin, Polyamide resin (Nylon), Polyolefin resin, Styrene resin, Acrylic resin, etc., Modified products thereof, Corona discharge, etc. Can be mentioned.

The shape of the substrate is not particularly limited, and at least 1 selected from the group consisting of spherical, particulate, beaded, rod, plate, needle, powder, hollow, hollow fiber and unspecified shape. It is preferable that it is a seed or more. The shape of the substrate is more preferably a fine particle shape, and the average particle diameter is preferably 0.1 to 100 μππι, more preferably 1 to 20 μππι. In the present specification, the average particle diameter means the volume average particle diameter, and the volume average particle diameter can be measured by, for example, a particle size distribution measuring instrument.

It is preferable that the substrate has an uneven surface because the surface treatment is easy. Examples of such a base material include frosted glass and porous particles. Further, the base material is preferably one whose surface is oxidized.

In the metal layer-coated base material of the present invention, the chelate-forming functional group-containing silane force coupling agent interposed between the base material and the interspersed material or layered material of the metal nanoparticles described later, It consists of a compound having a chelate-forming functional group at one end of the molecule and a silanol group (Si-OH) and / or a hydrolyzable functional group that gives a silanol group by hydrolysis at the other end.

Examples of the chelate-forming functional group include a polar group and a hydrophilic group, and are preferably functional groups having at least one atom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom. , 1 SH, _ CN, 1 NH ₂ , 1 S 0 ₂ 0 H, 1 S 0 OH, 1 OP 0 (OH) ₂ , _C 0 0 H, at least one functional group selected from the group consisting of It is more preferable that

Examples of the hydrolyzable functional group include an alkoxy (1 o R) group directly bonded to a Si atom, and the R constituting the alkoxy group is a straight chain having 1 to 6 carbon atoms. A chain, branched, or cyclic alkyl group is preferable. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec_ptenole ¾, a tert-butylene group. ;, Henotenore, hennore group, cyclopentyl group, cyclohexyl group and the like.

Specific examples of the chelate-forming functional group-containing silane coupling agent used for the metal layer-coated substrate of the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (amino Ethyl) -1-3-aminopropyltrimethyoxysilane, N-2_ (aminoethyl) -1-3-aminomino triethoxysilane, and 3-silaneminopropyl because of the cost and ease of handling of silane coupling agents Trimethysilane is particularly preferred.

In the metal layer-coated base material of the present invention, the chelate-formed synthetic functional group at one end of the silane force coupling agent is coordinated to the metal nanoparticles, and the silanol group at the other end of the silane coupling agent is It interacts with the ○ H group on the surface of the material.

Therefore, it becomes possible to stably fix the interspersed material or layered material of the metal nanoparticle layer to the substrate via the silane coupling agent.

In the metal layer-coated substrate of the present invention, the metal nanoparticles are preferably nanoparticles made of at least one metal selected from the group consisting of gold, silver, copper, and nickel. A metal layer (metal layer made of silver) by silver mirror reaction on metal nanoparticles In the case of forming, it is preferable that the metal nanoparticles are gold nanoparticles in consideration of the familiarity with silver.

The metal nanoparticles only have to be attached to at least a part of the substrate via the silane coupling agent. As the state of existence of the metal nanoparticles, for example, the metal nanoparticles are scattered on the substrate. And a state in which a layered product is uniformly formed on the substrate. Even if the metal nanoparticles are not uniformly deposited on the substrate, the metal layer described later is formed on the metal nanoparticle scattered material starting from each metal nanoparticle. Therefore, the obtained metal layer-coated substrate can ensure stable conductivity.

In addition, when the metal nanoparticles are uniformly deposited on the substrate to form a layered material, it is possible to form a metal layer to be described later on the entire surface of the metal nanoparticle layer. Even if an unformed part of the metal layer occurs, the metal nanoparticle layer is present between the base material and the metal layer, so that the resulting metal layer coated base material is stable without exposing the base material surface. The conductivity can be ensured.

In the present specification, the metal nanoparticles mean very small particles made of a metal having a particle size of 100 nm or less. Comparing the surface area of nanoparticles with the same volume of Balta atoms, the surface area of the nanoparticles is larger and the surface energy is larger (the ratio to the total energy is higher), so it shows different characteristics from the conventional fine particles However, in the metal layer-coated substrate of the present invention, it is considered that metal nanoparticles act as a catalyst when the metal layer is formed by electroless plating.

In the metal layer-coated substrate of the present invention, the metal species constituting the metal layer formed on the metal nanoparticle layer is not particularly limited, but is preferably silver, gold, copper, or nickel. Since the layer is preferably formed by a silver mirror reaction, the metal species constituting the metal layer is more preferably silver.

The metal layer-coated substrate of the present invention can be suitably produced by the method for producing the metal layer-coated substrate of the present invention described below.

The method for producing a metal layer-coated substrate according to the present invention comprises an aqueous solution comprising a hydrolysis catalyst, a chelate-forming functional group-containing silane force pulling agent, and a metal nanoparticle-forming metal salt. After contacting with the solution, by treating with a reducing agent, a metal nanoparticle interspersed or layered product is formed on the substrate via the chelating agent-functional group-containing silane force pulling agent. It is characterized in that a metal layer is formed on a nanoparticle interspersed or layered material.

As the base material used in the method for producing a metal layer-coated base material of the present invention, silica, ceramics, glass, various resins and the like can be used in the same manner as described in the explanation of the metal layer-coated base material of the present invention. Can be mentioned.

The hydrolysis catalyst used in the method for producing a metal layer-coated substrate of the present invention is not particularly limited. For example, acetic anhydride, glacial acetic acid, propionic acid, citrate, formic acid, oxalic acid and other organic acids, aluminum Examples thereof include aluminum chelate compounds such as alkyl acetates, and inorganic alkaline compounds such as aqueous ammonia. Among these, aqueous ammonia is preferable in consideration of the reactivity and cost with 3-aminopropyl trimethoxysilane, which is a preferred silane coupling agent.

The chelate-forming functional group-containing silane coupling agent used in the method for producing a metal layer-coated substrate of the present invention has a chelate-forming functional group at one end of the molecule as described above, and a silanol group and / or at the other end. Or it has a hydrolyzable functional group which gives a silanol group by hydrolysis.

Examples of the chelate-forming biofunctional group include those described above, but can also be provided in the form of a salt of each functional group. When the functional group is an acidic group such as 1 OH, 1 SH, 1 S 0 ₂ 0 H, 1 SOOH, 1 OPO (OH) ₂ , 1 COOH, the salt is an alkali metal such as sodium, potassium, or lithium. Salt or ammoyuum salt. On the other hand, if a basic group, such as single NH _2, as a salt thereof, hydrochloric acid, sulfuric, inorganic acids such as nitric acid, formic acid, acetic acid, propionic acid, and addition salts of organic acids such as Torifuruoro acetic acid.

In addition, examples of the hydrolyzable functional group include the same ones as mentioned in the explanation of the metal layer-coated substrate of the present invention.

Examples of the metal species constituting the metal nanoparticle-forming metal salt used in the method for producing a metal layer-coated substrate of the present invention include those mentioned in the description of the metal layer-coated substrate of the present invention. Like, gold, silver, copper, nickel, etc. can be mentioned. Examples of the metal salt include chloroauric acid, silver nitrate, copper sulfate, nickel sulfate and the like. The aqueous solution used in the method for producing a metal layer-coated substrate of the present invention is not particularly limited as long as it contains water as a main component, and may contain a water-miscible organic compound together with water. Here, examples of the water-miscible organic compound include lower alcohols such as methanol, ethanol, propanol, and butanol, and ketones such as acetone. In this case, the water-miscible organic compound may be mixed with water alone or in combination of two or more.

The reducing agent may be appropriately used in consideration of the redox potential of the metal component of the metal nanoparticle-forming metal salt to be used. The reducing agent is not particularly limited as long as it can be dissolved in an aqueous solution, and can be appropriately selected from conventionally known reducing agents. Examples of such reducing agents include borohydrides such as sodium tetrahydroborate (alkali metal borohydrides such as sodium borohydride, ammonium borohydrides, etc.), hydrazine compounds, Inorganic reducing agents such as hypochlorite and organic reducing agents such as formaldehyde, acetonitrile, citrate, and sodium citrate can be used. One of these reducing agents may be used alone, or two or more thereof may be used in combination.

In the method for producing a metal layer-coated substrate according to the present invention, the formation of a dot or layered product of metal nanoparticles is performed by using a substrate, a hydrolysis catalyst, a chelate-forming functional group-containing silane coupling agent, and metal nanoparticles. This is done by contacting with an aqueous solution containing a forming metal salt and then treating with a reducing agent. As a specific method, a solution (liquid B) containing a chelate-forming functional group-containing silane coupling agent and a metal nanoparticle-forming metal salt is added to an aqueous solution (liquid A) containing a base material and a hydrolysis catalyst. After stirring, a solution containing the reducing agent (solution C) is dropped into this mixed solution, followed by heating and stirring.

The temperature at the time of mixing and stirring the liquid A and the liquid B is preferably 10 to 40 ° C., and the stirring time is preferably 1 to 30 minutes. The heating temperature after adding the C liquid dropwise to the mixed liquid of the A liquid and the B liquid is preferably 30 to 70 ° C, and the heating time is preferably 2 to 5 hours. The amount of the hydrolysis catalyst used relative to 1 mol of the chelate-forming functional group-containing silane coupling agent is preferably 0.5 to 5.0 mol, and more preferably 1.5 to 2.5 mol. The amount of the metal nanoparticle-forming metal salt used per 1 mol of the chelate-forming functional group-containing silane coupling agent is preferably from 0.05 to 0.05 mol, and from 0.15 to More preferably, it is 0.025 mol. Furthermore, the amount of the reducing agent used relative to 1 mol of the metal nanoparticle-forming metal salt is preferably 0.025 to 0.25 mol, and 0.07 5 to 0.125 mol. More preferably.

In the method for producing a metal layer-coated substrate of the present invention, as a final step, a metal layer is formed on the interspersed or layered material of metal nanoparticles.

As the metal forming the metal layer, silver, gold, copper, nickel, or the like can be used as described above.

As the method for forming the metal layer, the electroless plating method is preferable, and the silver mirror reaction is particularly preferable in view of the progress and stability of the reaction.

As described above, when the metal nanoparticles are uniformly deposited on the substrate to form a layer, the metal layer does not necessarily have to be covered on the entire surface of the metal nanoparticle layer. In the method for producing a metal-coated substrate of the present invention, a metal nanoparticle interspersed or layered material stabilized with a silane coupling agent is formed on the substrate, and then the metal layer is formed by an electroless plating method. By forming, a metal layer can be formed on the base material without the need for an activation treatment step for the base material surface, which is essential for general electroless plating. In addition, when a layered product of metal nanoparticles is formed on a substrate, even if an unformed portion of an electroless plating layer, which is a metal layer, is formed on the metal nanoparticle layer, the substrate and the metal layer Since the metal nanoparticle layer exists between the two, the obtained metal layer-coated base material does not expose the base material surface, and can ensure stable conductivity. In addition, the metal layer-coated substrate can be produced at a low cost and with a simple process, with little influence on the environment, without using special equipment or equipment. Example EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

Example 1 (Production example of silver layer coated silli force particles)

(1) Formation of gold nanoparticle layer on Siri force particles

In a 50 OmL Erlenmeyer flask, 10 g of silica particles (average particle size 6.4 μπι) was added, 63 g of isopropyl alcohol (IPA) was added, and sonicated for 10 minutes. Further, 63 g of methanol was added and stirred for 10 minutes with a magnetic stirrer, and 5 Og of 25% aqueous ammonia solution was added and stirred for 10 minutes at 30 ° C. in an oil path (this solution is referred to as solution A).

Chloroauric acid (HAuCl ₄ · 4H ₂ 0) 0.25 g of methanol 5 OmL was added and stirred with a magnetic stirrer for 10 minutes, then 3-amaminoprovir trimethoxysilane 4.5 raL was added and stirred for another 10 minutes ( This solution is designated as solution B).

Sodium tetraborate (NaBH ₄ ) (0.17 g) was charged with methanol (5 OmL) and stirred with a magnetic stirrer for 10 minutes (this solution is referred to as solution C).

After adding solution B to solution A and stirring at 30 ° C for 5 minutes, when solution C was slowly added dropwise, the reaction system turned red. After dropping C droplets, the oil bath was heated to 65 ° C and stirred for 3 hours. Stirring was stopped, methanol classification was performed three times, and then suction filtration was performed to collect silica particles on which a gold nanoparticle layer was formed, followed by drying in an oven at 70 ° C. for 3 hours. The resulting particles were red.

An electron microscope (SEM) photograph of the resulting gold nanoparticle layer-forming silica particles is shown in Fig. 1. From Fig. 1, it can be seen that the gold nanoparticles are uniformly attached to the entire surface of the silica particles.

(2) Formation of silver layer on gold nanoparticle layer

To 1 g of the gold nanoparticle layer-forming silica particles obtained in (1) above, 200 mL of water was added and subjected to ultrasonic treatment for 10 minutes, then 0.65 g of silver nitrate was added, and the mixture was stirred with a magnetic stirrer for 10 minutes. After adding 13 mL of 25% ammonia aqueous solution, 20 mL of 0.24 mmol / L formalin aqueous solution was added and stirred for 5 minutes. Precipitated silver layer coating force Oven 70 after collecting particles by suction filtration and washing with methanol. Dry with C for 3 hours.

An electron microscope (SEM) photograph of the resulting silver layer-coated silica particles is shown in FIG. Figure 2 shows that a layer of silver is laminated on the entire surface of the gold nanoparticle layer. Using a micro compression tester, measure the electrical resistance of 20 silver layer-coated silica particles and determine the average value. It was. The results obtained are shown in Table 1 together with the standard deviation.

table 1

From the results in Table 1, the silver layer-coated silica particles obtained in Example 1 have a low average electrical resistance value of 3.9 Ω, a standard deviation of 2.2, and stable conductivity. I know. Example 2 (Production example of silver layer-coated polyimide particles)

3 g of polyimide particles (manufactured by Sumitomo Betalite Co., Ltd .: average particle size 0.5 μηι) were placed in a 50 OmL Erlenmeyer flask, and 6 g of isopropyl alcohol (IPA) was added and sonicated for 10 minutes. Further, 63 g of methanol was added and stirred with a magnetic stirrer for 10 minutes, 50 g of 25% aqueous solution was added, and the mixture was stirred for 10 minutes at 30 ° C. in an oil bath (this solution is referred to as solution A).

Chloroauric acid (HAuCl ₄ · 4H ₂ 0) 0.5 Og methanol 5 OmL was added and stirred with a magnetic stirrer for 10 minutes, then 3-amaminopropyltrimethoxysilane 7. OmL was added and stirred for another 10 minutes ( This solution is designated as solution B).

Methanol 5 OmL was added to 0.23 g of sodium tetrahydroborate (NaBH ₄ ), and the mixture was stirred with a magnetic stirrer for 10 minutes (this solution is referred to as solution C).

After adding solution B to solution A and stirring at 30 ° C for 5 minutes, when solution C was slowly added dropwise, the reaction system turned reddish purple. After dropping C droplets, the oil path was heated to 65 ° C and stirred for 3 hours. Stop stirring, perform methanol classification three times, and then suction filter to obtain gold nanoparticles The silica particles on which the child layer was formed were collected and dried in an oven at 70 ° C. for 3 hours. The obtained particles were reddish purple.

After adding 30 OmL of water to 0.5 g of the obtained gold nanoparticle layer-forming polyimide particles and sonicating for 15 minutes, 0.667 g of silver nitrate was added, and the mixture was stirred with a magnetic stirrer for 10 minutes. After adding 2 OmL of 25% aqueous ammonia, 3 OmL of 0.24 mmol / L formalin aqueous solution was added and stirred for 5 minutes. Precipitated silver layer-coated polyimide particles were collected by suction filtration, washed with methanol, and then dried in an oven at 70 ° C for 3 hours.

An electron microscope (SEM) photograph of the obtained silver layer-coated polyimide particles is shown in FIG. Figure 3 shows that a layer of silver is laminated on the entire surface of the gold nanoparticle layer. Example 3 (Example of production of silver layer-coated titanium oxide powder)

Titanium oxide powder (Ishihara Sangyo Co., Ltd .: ST-01) 5 g was placed in a 30 OmL Erlenmeyer flask, and 31.5 g of isopropyl alcohol (IPA) was added!] And sonicated for 10 minutes. Further, 31.5 g of methanol was added, and the mixture was stirred with a magnetic stirrer for 10 minutes, 25 g of 25% aqueous ammonia solution was added, and the mixture was stirred for 10 minutes at 30 ° C. in an oil bath (this solution is referred to as solution A).

Chloroauric acid (HAuCl ₄ · 4H ₂ 0) Add 0.2 mL of methanol to 5 OmL and stir with a magnetic stirrer for 10 minutes, then add 2.2 mL of 3-amaminoprovirtrimethoxysilane and stir for an additional 10 minutes. (This solution is referred to as solution B).

Sodium tetrahydroborate (NaBH ₄ ) (0.092 g) was mixed with 5 OmL of methanol and stirred with a magnetic stirrer for 10 minutes (this solution is referred to as solution C).

After adding solution B to solution A and stirring at 30 ° C for 5 minutes, when solution C was slowly added dropwise, the reaction system turned reddish purple. After dropping C droplets, the oil bath was heated to 65 ° C and stirred for 3 hours. Stirring was stopped and methanol classification was performed three times, and then suction filtration was performed to collect oxy-titanium powder on which a gold nanoparticle layer was formed, followed by drying in an oven at 70 ° C. for 3 hours. The obtained particles were reddish purple. After adding 300 mL of water to 3.0 g of the obtained gold nanoparticle layer-formed acid-titanium powder and sonicating for 15 minutes, 0.67 g of silver nitrate was added, and then using a magnetic stirrer. Stir for 0 min. After adding 2 O mL of 25% aqueous ammonia, 0.24% ₀ 1 / formalin aqueous solution was added with 3 O mL and stirred for 5 minutes. The precipitated silver layer-coated titanium oxide particles were collected by suction filtration, washed with methanol, and then collected by drying in an oven 70 for 3 hours.

As a result of observing the obtained gold nanoparticle layer-formed titanium oxide powder with an electron microscope (SEM), it was found that a layer made of silver was laminated on the entire surface of the gold nanoparticle layer. Example 4 (Example of production of silver layer-coated polypropylene powder)

A silver-coated polypropylene powder was obtained in the same manner as in Example 3, except that titanium oxide was changed to 5 g of polypropylene powder (Prime Polymer Co., Ltd.).

As a result of observing the obtained silver-coated polypropylene powder with an electron microscope (SEM), it was found that a layer made of silver was laminated on the entire surface of the gold nanoparticle layer. Example 5 (Example of production of silver layer-coated glass plate)

A silver-coated glass plate was obtained in the same manner as in Example 3 except that titanium oxide was changed to a microslide glass plate (manufactured by Matsunami Glass Industry Co., Ltd.) 1 X 1 cm ² in an Erlenmeyer flask and immersed.

As a result of observing the obtained silver-coated glass plate with an electron microscope (SEM), it was found that a layer made of silver was laminated on the entire surface of the gold nanoparticle layer. Example 6 (Example of production of silver layer-coated hollow fiber nylon 12)

In Example 3, the same procedure was followed except that titanium oxide was changed to hollow fiber nylon 1 2 (Ube Industries, Ltd.) with an inner diameter of 48 mm, an outer diameter of 5 O mm, and a length of 2 cm. Nylon 1 2 was obtained.

As a result of observing the obtained silver-coated hollow fiber nylon 12 with an electron microscope (SEM), it was found that a layer made of silver was laminated on the entire surface of the gold nanoparticle layer. Example Ί (Example of production of silica particles with gold nanoparticles using 3-mercaptoprovir trimethoxysilane)

The same operation was performed except that 4.5 mL of 3-aminoprovir trimethoxysilane was changed to 4.5 mL of 3-mercaptoprovir trimethoxysilane in Example 1 (1). When compared with the gold nanoparticle layer-forming silica particles obtained in Example 1 (1), a sample in which agglomerated gold nanoparticles adhered to the silica particles was obtained. The SEM photograph is shown in Fig. 4. Example 8 (Example in which a silver layer is not laminated on a part of a gold nanoparticle layer)

200 g L of water was added to 1 g of the gold nanoparticle layer-forming silica particles obtained in Example 1 (1), sonicated for 10 minutes, 0.44 g of silver nitrate was added, and the mixture was stirred with a magnetic stirrer for 10 minutes. did. After adding 8.2 mL of 25% aqueous ammonia solution, 12.6 mL of 0.24 mmol / L formalin aqueous solution was added and stirred for 5 minutes. The precipitated silver layer-coated silli force particles were collected by suction filtration, washed with methanol, and then dried in an oven at 70 ° C for 3 hours.

An electron microscope (SEM) photograph of the obtained silver layer-coated silica particles is shown in FIG. Figure 5 shows that a silver layer is not laminated on a part of the gold nanoparticle layer.

The electrical resistance value of 20 silver layer-coated silica particles was measured with a micro compression tester, and the average value was obtained. The results obtained are shown in Table 2 together with the standard deviation.

Table 2

From the results shown in Table 2, the silver layer-coated silica particles obtained in Example 8 have no silver layer laminated on a part of the gold nanoparticle layer. It can be seen that the resistance is as low as 11.8 Ω. Example 9 (Production example of silver layer coated soda lime glass beads)

(1) Formation of gold nanoparticle layer on soda-lime glass beads

A gold nanoparticle layer was formed on the soda lime glass beads in the same manner as in Example 1 (1) except that soda lime glass beads (particle size 5 to 63 μm) were used instead of the silli force particles. .

(2) Formation of silver layer on gold nanoparticle layer

Using the gold nanoparticle layer-forming soda-lime glass beads, a silver layer was formed on the entire surface of the gold nanoparticle layer in the same manner as in Example 1 (2).

Figure 6 shows an electron microscope (SEM) photograph of the obtained silver layer-coated soda-lime glass beads.

The electrical resistance value of 20 silver layer coated soda lime glass beads was measured with a micro compression tester, and the average value was obtained. The results obtained are shown in Table 3 together with the standard deviation.

Table 3

From the results in Table 3, it can be seen that the silver layer-covered soda-lime glass beads obtained in Example 9 have a low average electrical resistance value of 14.3 Ω. Example 10 (Example of production of silver layer-coated silli force particles)

(1) Formation of gold nanoparticle layer on Siri force particles

A gold nanoparticle layer on silica particles in the same manner as in Example 1 (1) except that N-2 (aminoethinole) 3-aminopropyltrimethoxysilane was used instead of 3-aminomino trimethoxysilane. Formed. Fig. 7 shows an electron microscope (SEM) photograph of the resulting gold nanoparticle layer-forming silicon force particles. As compared with the gold nanoparticle layer-forming silica particles obtained in Example 1 (1), it can be seen that the agglomerated gold nanoparticles are adhered on the silica particles.

(2) Formation of silver layer on gold nanoparticle layer A silver layer was formed on the entire surface of the gold nanoparticle layer in the same manner as in Example 1 (2) using the gold nanoparticle layer-forming silica particles. Example 1 1 (Example of production of silver layer-coated silli force particles)

(1) Formation of silver nanoparticle layer on Siri force particles

Instead of chloroauric acid _{_{(HAuC 1 4 · 4H 2 0}} ) 0. 23 g of silver nitrate 0. 48 g, N a BH ₄ except that the 0. 1 07 g was changed to the 0. 092 g Example 1 (1 ) To obtain silver nanoparticle layer-formed silica particles. Fig. 8 shows an electron microscope (SEM) photograph of the resulting silver nanoparticle layer-forming silica particles.

(2) Formation of silver layer on silver nanoparticle layer

A silver layer was formed on the entire surface of the silver nanoparticle layer in the same manner as in Example 1 (2) using the silver nanoparticle layer-forming silica particles. Example 12 (Production example of gold layer-coated silli force particles)

500 g L of water was added to 1 g of the gold nanoparticle layer-forming silica particles obtained in Example 1 (1) and subjected to ultrasonic treatment for 10 minutes, followed by addition of 0.25 g of chloroauric acid, and an aqueous solution. 2.5 to make it alkaline. /. 5 ml of an aqueous ammonia solution was added and stirred with a magnetic stirrer for 10 minutes. A reducing agent, 1.87 mmol / L tetrakishydroxymethyl phosphine chloride aqueous solution 250 mL was slowly added dropwise. The precipitated gold layer-coated silica particles were collected by suction filtration, washed with methanol, and then dried in an oven at 70 ° C for 3 hours.

An electron microscope (SEM) photograph of the resulting gold layer-coated silica particles is shown in FIG. The electrical resistance value of 10 gold layer-coated silica particles was measured with a micro compression tester, and the average value was obtained. The results obtained are shown in Table 4 together with the standard deviation.

Table 4

From the results of Table 4, it can be seen that the gold layer-coated silica particles obtained in Example 12 have a low average electrical resistance value of 22.2 Ω. Industrial applicability

According to the present invention, a metal layer-coated substrate having stable conductivity can be provided, and the metal layer-coated substrate is inexpensive and simple without using special equipment and equipment. In this way, it is possible to provide a manufacturing method with little influence on the environment. The metal-coated substrate of the present invention can be used for a conductive material, an electromagnetic shielding material, and the like.

Claims

The scope of the claims

1. Substrate, interspersed or layered metal nanoparticles formed on the substrate via a chelate-forming functional group-containing silane coupling agent, and interspersed or layered metal nanoparticles A metal layer-coated substrate comprising a metal layer formed on an object.

2. The metal layer-coated substrate according to claim 1, wherein the substrate comprises at least one selected from the group consisting of silica, ceramics and glass.

3. The metal layer-coated substrate according to claim 1 or 2, wherein the shape of the substrate is one selected from the group consisting of a spherical shape, a rod shape, a plate shape, a needle shape, a hollow shape and an unspecified shape.

4. The metal layer-coated substrate according to claim 3, wherein the shape of the substrate is a fine particle shape having an average particle size of 0.1 to L0 m.

5. The metal layer coating according to any one of claims 1 to 4, wherein the chelate-forming functional group is a functional group having at least one atom selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom. Base material.

6. The chelate-forming functional group is at least one selected from the group consisting of one SH, —CN, one NH ₂ , one S 0 ₂ OH, — SOOH, one hundred P (OH) ₂ and one COOH. 6. The metal layer-coated substrate according to claim 5, which is a functional group.

7. The metal layer-coated substrate according to any one of claims 1 to 6, wherein the metal nanoparticles are nanoparticles composed of at least one metal selected from the group consisting of gold, silver, copper and nickel. .

8. The metal layer-coated substrate according to any one of claims 1 to 7, wherein the metal layer is a layer made of silver.

9. The substrate is contacted with an aqueous solution containing a hydrolysis catalyst, a chelate-forming functional group-containing silane coupling agent and a metal nanoparticle-forming metal salt, and then treated with a reducing agent on the substrate. A metal nanoparticle interspersed or layered product is formed via a chelate-forming functional group-containing silane coupling agent, and then a metal layer is formed on the metal nanoparticle interspersed or layered product. A method for producing a metal layer-coated substrate.

10. The method for producing a metal layer-coated substrate according to claim 9, wherein the metal layer is formed by an electroless plating method.