JPWO2015060342A1 - Metal particle attachment method, antibacterial debromination method, fiber material production method, and metal particle attachment device - Google Patents

Abstract

It is an object of the present invention to provide a method capable of simply and uniformly attaching metal particles. By spraying droplets containing metal ions or a reducing agent with an electrospray sprayer to form metal particles, the metal particles can be uniformly and easily attached to the object.

Description

  TECHNICAL FIELD The present invention relates to a method for attaching metal particles, an antibacterial debromination method, a method for producing fiber materials, and a metal particle attaching device, and more specifically, metal particles such as silver and gold are easily and uniformly applied in the manufacturing process of industrial products. It relates to a method that can be attached to an object.

In recent years, people's awareness of health and hygiene has been increasing, and products that have been given antibacterial and deodorizing effects in various fields of clothing, food and housing are actively sold. In particular, fiber materials used in the fields of clothing, bedding, interiors, etc. have many opportunities to be in direct contact with the body, and various antibacterial / debromating techniques relating to these materials have been developed.
As typical components having antibacterial action, metal ions such as silver and copper have been known for a long time, and antibacterial agents using these metal ions have been put into practical use. For example, an example in which a special phosphate compound having silver ions is used as an antibacterial agent has been reported (see Patent Document 1). Further, as a fiber material having an antibacterial action, a fiber in which a layered compound containing metal ions such as silver and copper is similarly mixed with a thermoplastic polymer has been reported, and it is disclosed that it is excellent in washing durability and the like. (See Patent Document 2).

  On the other hand, by applying a high voltage between a nozzle filled with a liquid and a counter electrode, a phenomenon called “electrospray” in which the liquid is sprayed toward the counter electrode as a charged droplet is mass spectrometry (patented) It is used for depositing polymer compounds and the like (see Patent Document 4). The electrospray phenomenon is suitable for mass spectrometry of fragile compounds such as biopolymers because it can be ionized without the need for high temperature conditions, and the solvent easily evaporates. Since it can be sprayed, it is known that it is suitable for forming nanoparticles, carbon nanofibers and the like.

Japanese Patent Laid-Open No. 03-083905 Japanese Patent Laid-Open No. 05-051812 Japanese Patent Laid-Open No. 06-215729 JP 2007-070738 A

By applying an antibacterial agent containing metal ions such as silver and copper, or by kneading and mixing with fibers, the method that imparts antibacterial action is poor in versatility and can easily apply metal components uniformly. There are problems such as not. In addition, in the method of immersing the fiber in the antibacterial agent solution, there is a problem that antibacterial processing is performed even on an unnecessary portion, or the waste liquid treatment of the antibacterial agent solution is costly.
For example, in the manufacturing process of industrial products, if metal particles such as silver and copper can be easily and uniformly attached to the target, and if metal particles can be attached only to the necessary parts of the product, antibacterial action and deodorant action It can be an important technology that leads to a reduction in the manufacturing cost of products with high quality.
That is, an object of the present invention is to provide a method capable of simply and uniformly attaching metal particles.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors sprayed droplets containing metal ions or a reducing agent with an electrospray sprayer to form metal particles uniformly, The inventors have found that metal particles can be easily attached and completed the present invention.

That is, the present invention is as follows.
<1> a second component that is sprayed with a droplet containing a first component on an object to be attached by an electrospray sprayer, and / or contained in a droplet that is included in the object to be attached and / or sprayed by another electrospray sprayer; A method for attaching metal particles, comprising a reaction step of reacting to form metal particles.
<2> A reaction step of spraying droplets containing the first component with an electrospray sprayer and reacting with the second component contained in the droplets sprayed with another electrospray sprayer to form metal particles, and A method for attaching metal particles, comprising a spraying step of spraying the metal particles formed in the reaction step toward an object to be attached.
<3> The method for attaching metal particles according to <1> or <2>, wherein the reaction step is a step of forming metal particles in a closed space.
<4> The method for attaching metal particles according to any one of <1> to <3>, wherein the object to be attached is a fiber material.
<5> The metal according to any one of <1> to <4>, wherein the metal particles are at least one selected from the group consisting of copper particles, silver particles, palladium particles, platinum particles, and gold particles. Particle attachment method.
<6> The method for attaching metal particles according to any one of <1> to <5>, wherein the metal particles are particles having an average particle diameter of 1 to 100 nm.
<7> An antibacterial / debromating method, wherein an antibacterial action and / or a deodorizing action is imparted to the object to be attached by a method of attaching metal particles to any one of <1> to <6>.
<8> A method for producing a fiber material, comprising an antibacterial / debromide treatment step for imparting an antibacterial action and / or a deodorizing action to the fiber material by the antibacterial / deodorization method according to <7>.
<9> The method according to <8>, further including at least one process selected from the group consisting of a spinning process, a stretching process, a spinning process, a weaving process, a bleaching process, a pasting process, a scouring process, and a dyeing process. A method for producing a fiber material.
<10> At least one selected from the group consisting of immersing the adhesion target in the second component solution, spraying the second component solution onto the adhesion target, and dropping the second component solution onto the adhesion target. Second component solution contact mechanism to be performed, electrospray sprayer for spraying droplets containing the first component on the attachment target containing the second component, and moving the attachment target containing the second component to the spray destination of the electrospray sprayer A metal particle adhering apparatus comprising an attachment object feeding mechanism for causing the metal particle to adhere.
<11> An electrospray sprayer that sprays droplets containing the first component, an electrospray sprayer that sprays droplets containing the second component, and the sprayed first and second components react to form. A metal particle adhering apparatus comprising a spraying mechanism for spraying metal particles toward an object to be attached.

  According to the present invention, metal particles can be easily and uniformly attached to an object, and the manufacturing cost of a product having an antibacterial action or a deodorizing action can be reduced.

(A) It is a conceptual diagram showing the reaction process which sprays the droplet which contains a 1st component on an attachment object with an electrospray sprayer, and makes it react with the 2nd component contained in an attachment object, and forms a metal particle. (B) A droplet containing the first component is sprayed by an electrospray sprayer, and is attached to a reaction field that forms metal particles by reacting with a second component contained in a droplet sprayed by another electrospray sprayer. It is a conceptual diagram showing the reaction process of attaching a metal particle by installing object. (C) It is the photograph which shows a mode that the droplet sprayed from the electrospray sprayer converges toward a cotton thread (drawing substitute photograph). (D) It is the conceptual diagram showing a mode that the droplet sprayed from the electrospray sprayer converges toward a cotton thread. A reaction step in which droplets containing a first component are sprayed by an electrospray sprayer and reacted with a second component contained in a droplet sprayed by another electrospray sprayer to form metal particles, and the formed metal particles It is a conceptual diagram showing the spraying process which sprays toward the attachment object. (A) It is a conceptual diagram showing the reaction process which forms a metal particle in the closed space, and makes it adhere to the attachment object. (B) It is a conceptual diagram showing the reaction process which forms a metal particle in the closed space, and the spraying process which sprays the metal particle formed from the opening part of the closed space toward the attachment object. (A) It is a conceptual diagram showing the aspect which is performing the reaction process continuously, after immersing the attachment object in the 2nd component solution as a reaction preparation process. (B) It is a conceptual diagram showing the aspect which is performing the reaction process continuously, after spraying a 2nd component solution on the attachment object as a reaction preparation process. (C) It is a conceptual diagram showing the aspect which is performing the reaction process continuously, after dripping a 2nd component solution to the attachment object as a reaction preparation process. 1 is a conceptual diagram of an apparatus used in Example 1. FIG. FIG. 2 is a scanning electron micrograph of a cotton cloth with metallic silver particles attached according to Example 1, wherein (A) is 1000 times and (B) 3000 times (drawing substitute photo). It is an Ag mapping image by EDAX of the cotton cloth which attached the metallic silver particle by Example 1, (A) is an original image, (B) is an Ag mapping image (drawing substitute photograph). (A) It is a conceptual diagram of the apparatus used in Example 2. FIG. (B) It is an overhead view of the electrospray sprayer part of the apparatus used in Example 2. It is a conceptual diagram of the apparatus which water-washes a cotton thread. (A) The left side is a photograph showing the cotton yarn before the attachment of the metallic silver particles, and the right side is a photograph showing the cotton yarn attached with the metallic silver particles according to Example 2 (drawing substitute photograph). (B) It is the scanning electron micrograph of the cotton yarn which attached the metal silver particle by Example 2 (drawing substitute photograph). It is a conceptual diagram showing an aspect in which cotton yarn passes through a water tank containing an electrolyte solution, a dyeing process, a functional material addition (antibacterial debromination process), and a gluing process in order of a heating and drying apparatus. It is a graph showing the relationship between the feeding speed of cotton yarn and the amount of metal silver particles attached.

  In describing the details of the metal particle deposition method, antibacterial debromination method, fiber material production method, and metal particle deposition apparatus according to embodiments of the present invention, specific examples will be described. The present invention is not limited to the following contents as long as they do not deviate from the above, and can be implemented with appropriate modifications.

<Method of attaching metal particles>
In the method for attaching metal particles according to one embodiment of the present invention, a droplet containing the first component is sprayed on an object to be attached by an electrospray sprayer, and the droplet is included in the object to be attached and / or sprayed by another electrospray sprayer. A reaction step of reacting with the second component contained in the droplets to form metal particles (hereinafter, this mode may be abbreviated as “attachment method 1”).
In addition, another method for attaching metal particles, which is one embodiment of the present invention, is included in a droplet sprayed with a droplet containing the first component by an electrospray sprayer and sprayed by another electrospray sprayer. A reaction step of reacting with the second component to form metal particles, and a spraying step of spraying the metal particles formed in the reaction step toward the object to be attached (hereinafter referred to as “attachment method 2”). May be abbreviated as ")."
As a result of intensive investigations for the method of attaching metal particles such as silver and gold that can be applied to the manufacturing process of industrial products, etc., the inventors have obtained a liquid containing metal ions or a reducing agent by an electrospray sprayer. It has been found that metal particles can be uniformly and simply attached to an object by spraying droplets to form metal particles. "Electrospray sprayer" is a phenomenon in which a high voltage is applied between a nozzle filled with a liquid and a counter electrode to generate an electric field, whereby the liquid is sprayed as charged droplets toward the counter electrode. Is a spraying device that uses very small charged droplets, so that metal particles and their raw materials can be dispersed, and as a result, the metal particles can be uniformly attached to the target. Become. Further, since the metal particles are formed by spraying, there is an advantage that the method can be easily performed as compared with a method of dipping or applying.
In the present invention, the “electrospray sprayer” is not particularly limited as long as it is a spraying device that utilizes the electrospray phenomenon, but usually generates a nozzle and an electric field for determining the spraying direction. Power supply (voltage control device, etc., including electrodes, conductors, etc. for connecting the nozzle and the object to be attached (or the nozzle of another electrospray sprayer)) (including two or more electrospray sprayers) ), One power supply may be shared, and not all electrospray sprayers may have separate power supplies. The nozzle itself is made of a conductive material, or an electrode (for example, a platinum wire) is installed in the nozzle and connected to a power source (voltage control device, etc.) to apply a voltage. It is a mechanism that generates an electric field.
Further, “first component” and “second component” mean that one of them is a metal ion and the other is a reducing agent. That is, when the “first component” is a metal ion, the “second component” is a reducing agent, and when the “first component” is a reducing agent, the “second component” is a metal ion. Means.

(Attachment method 1)
In the attaching method 1, the droplet containing the first component is sprayed on the object to be attached by an electrospray sprayer, and the second component contained in the droplet that is included in the object to be attached and / or sprayed by another electrospray sprayer. FIG. 1A is a conceptual diagram showing a specific example of a state in which droplets are sprayed on an object to be attached by an electrospray sprayer. And (B).
For example, in FIG. 1A, the attachment object 101 includes the second component, and the droplet 103 sprayed by the electrospray sprayer 102 includes the first component. This is a mechanism in which the sprayed droplet 103 reaches the object 101 and the first component and the second component react on the surface of the object 101 to form and attach metal particles (the object 101 and the electrospray spray). The machine 102 is connected via an electrode, a conducting wire, a power source, etc.). In addition, although the specific spraying conditions of an electrospray sprayer are not specifically limited, Usually, it is preferable to produce an electric field between the adhesion target 101 and the electrospray sprayer 102. The electric field between the object to be attached and the electrospray sprayer is set, for example, using a power source, with the electrospray sprayer side set to a positive potential, the attachment target side set to 0 kV or a negative potential, or the electrospray sprayer side set to a negative potential. The potential can be generated by setting the attachment target side to 0 kV or a positive potential. In addition, since it is sufficient if there is a potential gradient between the object to be attached and the electrospray sprayer, for example, (potential of electrospray sprayer)> (potential of object to be attached)> 0 or 0V> (object to be attached) An electric field can also be generated when setting (potential)> (potential of electrospray sprayer). As shown in FIGS. 1C and 1D, the generated charged droplet 103 is attracted (focused) to the attachment target 101 by such an electric field, so that metal particles can be formed efficiently. It is.
On the other hand, in FIG. 1B, the droplet 103 sprayed by the electrospray sprayer 102 contains the first component, and the droplet 105 sprayed by another electrospray sprayer 104 contains the second component. It is out. The droplet 103 and the droplet 105 are attracted by electrostatic attraction and collide / associate so that the first component and the second component react in the vicinity of the attachment target 101 to form and attach metal particles (electro The spray sprayer 102 and the other electrospray sprayer 104 are connected via electrodes, conductors, a power source, and the like. The specific spraying conditions of the electrospray sprayer are not particularly limited, but it is usually preferable to generate an electric field between the electrospray sprayer 102 and another electrospray sprayer 104. The electric field between the electrospray sprayer 102 and another electrospray sprayer 104 is, for example, using a power source, with the electrospray sprayer 102 side being positive potential and the other electrospray sprayer 104 side being 0 kV or negative potential. Or by setting the electrospray sprayer 102 side to a negative potential and the other electrospray sprayer 104 side to 0 kV or a positive potential. Further, since it is sufficient if there is a potential gradient between the electrospray sprayer 102 and another electrospray sprayer 104, for example, (potential of electrospray sprayer 101)> (potential of another electrospray sprayer 104)> An electric field can also be generated when set to 0, or set to 0 V> (potential of another electrospray sprayer 104)> (potential of electrospray sprayer 101). By such an electric field, the droplet 103 and the droplet 105 are attracted to each other, and metal particles can be efficiently formed.

The attachment method 1 may include steps other than the above-described reaction step. For example, in order to react with the first component contained in the droplet, a reaction preparation step for adding the second component to the attachment target is performed. Inclusion.
The method of incorporating the second component in the reaction preparation step into the object of attachment is not particularly limited, but the object of attachment is in a solution in which the second component is dissolved in a solvent (hereinafter sometimes abbreviated as “second component solution”). Examples include a dipping method, a method of spraying the second component solution onto the object to be attached, and a method of dropping the second component solution onto the object to be attached.
The solvent used for dissolving the second component should be appropriately selected according to the type of the second component, but usually water is used from the viewpoint of cost. In addition to water, protic polar solvents such as methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol, butanol, acetic acid, formic acid; acetone, methyl ethyl ketone, acetonitrile, N, N-dimethylformamide, N, N-dimethyl Aprotic polar solvents such as acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide; hexane, cyclohexane, cyclohexanone, dichloromethane, dichloroethane, trichloroethane, chloroform, trichloroethylene, benzene, ethylbenzene, xylene, toluene, diethyl ether, 1,4 -Nonpolar solvents such as dioxane, methyl acetate, ethyl acetate, tetrahydrofuran, and methylene chloride. In addition, a solvent is not restricted to 1 type, You may use combining 2 or more types.
The concentration of the second component solution is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and usually 20.0% by mass or less, preferably 15.0%. It is at most mass%, more preferably at most 10.0 mass%.
The content of the second component solution contained in the object to be attached (the mass of the second component solution in 100% by weight of the object to be attached) is usually 300% by weight or more, preferably 400% by weight or more, more preferably 500% by weight or more. Usually, it is 1000 mass% or less, Preferably it is 850 mass% or less, More preferably, it is 700 mass% or less.
In addition, when the object to be attached is an insulator such as a fiber material, an electric field is hardly generated between the object to be attached and the electrospray sprayer, but the present inventors are an insulator such as a fiber material. In addition, it has been found that by including the second component solution, an electric field can be generated between the fiber material and the electrospray sprayer to efficiently form metal particles. This is because the second component generally serves as an electrolyte.

(Attachment method 2)
The attaching method 2 is a reaction step in which droplets containing a first component are sprayed by an electrospray sprayer and reacted with a second component contained in a droplet sprayed by another electrospray sprayer to form metal particles. And a spraying step in which the metal particles formed in the reaction step are sprayed toward the object to be attached. The droplets are sprayed by an electrospray sprayer, and the formed metal particles are directed to the attachment target. The conceptual diagram showing the specific example of the state which is spraying is shown in FIG.
For example, in FIG. 2, a droplet 203 sprayed by an electrospray sprayer 202 contains a first component and a droplet 205 sprayed by another electrospray sprayer 204 contains a second component. The droplet 203 and the droplet 205 are attracted by the electrostatic attraction and collide / associate, whereby the first component and the first component react to form metal particles, and the metal particles are attached by the gas from the spray nozzle 208. This is a mechanism for spraying and attaching to 201. In addition, although the specific spray conditions of an electrospray sprayer are not specifically limited, Usually, it is preferable to generate an electric field between the electrospray sprayer 202 and another electrospray sprayer 204. The droplet 203 and the droplet 205 are attracted to each other by the electric field, and metal particles can be efficiently formed.

The impregnation method 2 includes a spraying step in which the metal particles formed in the reaction step are sprayed toward the object to be attached. The spraying method, the type of spraying gas, the flow rate of the spraying gas, etc. in the spraying step are particularly limited. Not. Examples of the spraying method include a method of connecting a pipe to a compressor, a high-pressure cylinder, etc., and supplying a spraying gas. Examples of the spraying gas include air, nitrogen gas, oxygen gas, and nitrogen-oxygen mixed gas. .
The flow rate of the blowing gas is usually 5 L / min or more, preferably 7 L / min or more, more preferably 8 L / min or more, and usually 20 L / min or less, preferably 15 L / min or less, more preferably 12 L / min or less. is there.
Moreover, the reaction process and the spraying process are independent over time, that is, after the reaction process is finished, the spraying process may be performed sequentially, or the reaction process and the spraying process may be performed in parallel.

  The diameter of the spray port of the electrospray sprayers of the attachment methods 1 and 2 is usually 0.03 mm or more, preferably 0.05 mm or more, more preferably 0.1 mm or more, and usually 1.0 mm or less, preferably 0.00. It is 5 mm or less, more preferably 0.3 mm or less. Within the above range, metal particles can be efficiently formed.

The attaching method 1 is characterized in that the droplet containing the first component is sprayed on the object to be attached by an electrospray sprayer, but the object to be attached need not necessarily be present in the spraying direction of the electrospray sprayer. However, the object to be attached is preferably within a range of 45 ° from the spray direction of the nozzle of the electrospray sprayer, and more preferably within a range of 30 °. Within the above range, metal particles can be efficiently formed.
The spraying direction of the electrospray sprayer different from the electrospray sprayer in the attaching methods 1 and 2 does not necessarily have to be linear. However, the deviation in the spraying direction between the electrospray sprayer and another electrospray sprayer is preferably within a range of 45 °, and more preferably within a range of 30 °. Within the above range, metal particles can be efficiently formed.

The distance from the attachment target of the electrospray sprayer in the attachment method 1 (the shortest distance between the nozzle tip of the electrospray sprayer and the attachment target, 106 in FIG. 1) is usually 5 mm or more, preferably 7 mm or more, more preferably 10 mm or more. It is usually 40 mm or less, preferably 30 mm or less, more preferably 20 mm or less. Within the above range, metal particles can be efficiently formed.
The distance between the electrospray sprayer and another electrospray sprayer in the attachment methods 1 and 2 (distance between the nozzle tip of the electrospray sprayer and another electrospray sprayer, 107 in FIG. 1) is usually 10 mm or more, Preferably it is 14 mm or more, More preferably, it is 20 mm or more, Usually, 80 mm or less, Preferably it is 60 mm or less, More preferably, it is 40 mm or less. Within the above range, metal particles can be efficiently formed.

The applied voltage in the attaching methods 1 and 2 is usually 5.5 kV or more, preferably 6 kV or more, more preferably 7 kV or more, and usually 16 kV or less, preferably 15 kV or less, more preferably 12 kV or less.
In addition, when an electric field is generated between the attachment target and the electrospray sprayer, the potential applied to the electrospray spray is usually a positive potential, and the potential when the reference potential is grounded is usually +2.0 kV or more, Preferably, it is +3.0 kV or more, more preferably +4.5 kV or more, and usually +10.0 kV or less, preferably +8 kV or less, more preferably +7 kV or less. On the other hand, the potential applied to the attachment target is usually a negative potential, and the potential when the reference potential is grounded is usually −5 kV or more, preferably −4 kV or more, more preferably −3.5 kV or more. -0.5 kV or less, preferably -1 kV or less, more preferably -2 kV or less.
Within the above range, metal particles can be efficiently formed.

  The amount of droplets sprayed in the attachment methods 1 and 2 is usually 3 μL / min or more, preferably 5 μL / min or more, more preferably 7 μL / min or more, and usually 50 μL / min or less, preferably 30 μL / min or less. Preferably, it is 20 μL / min or less. Within the above range, metal particles can be efficiently formed.

  Although the other conditions of the reaction process in the attachment methods 1 and 2 are not specifically limited, It is preferable to form metal particles in a closed space. The “closed space” means a space surrounded by walls like the internal space of the box, and does not need to be a completely sealed space. For example, in FIGS. 3A and 3B, the internal space 310 of the container 309 corresponds to a “closed space”. 3A and 3B, the tip of the nozzle of another electrospray sprayer 304 and another electrospray sprayer 304 is disposed in the internal space 310 of the container 309, and the droplets 303 and liquid sprayed are sprayed. The droplets 305 are attracted by the electrostatic attraction and collide and meet to form metal particles in the space 310. In FIG. 3B, two openings 311 are provided in a direction perpendicular to the direction in which the two electrospray sprayers are arranged, and the attachment target 301 is located in front of one of the openings. It is arranged, and the structure is such that the gas can be efficiently blown by the object to be attached by blowing the gas from the blowing nozzle 308 through the other opening 311. When the metal particles are formed in such a closed space, scattering of the metal particles and the raw material forming the metal particles is suppressed, so that the metal particles can be efficiently attached.

(Metal particles)
The kind of metal (element) formed and attached in the attachment methods 1 and 2 is not particularly limited, but a noble metal having a smaller ionization tendency than hydrogen is preferable, and specifically, copper, silver, palladium, platinum, and gold are preferable. .
The physical properties such as the particle diameter of the metal particles formed and attached in the attachment methods 1 and 2 are not particularly limited. However, the attachment methods 1 and 2 are particularly useful for attaching metal nanoparticles, and have a specific average. The particle size is usually 100 nm or less, preferably 70 nm or less, more preferably 50 nm or less, and usually 1 nm or more, preferably 2 nm or more, more preferably 3 nm or more. The average particle diameter of the metal particles specifically means a volume average particle diameter, and can be measured by, for example, observation with an electron microscope or a dynamic light scattering method.

(First component, second component)
As described above, one of “first component” and “second component” means that one is a metal ion and the other is a reducing agent.
The type of metal ion should be appropriately selected according to the type of metal particles to be attached, and examples of the raw material to be a metal ion source include a ligand complex, a metal salt, or a hydrate thereof. Specific examples include silver nitrate (AgNO ₃ ), tetrachloroauric (III) acid (HAuCl ₄ ), hexachloroplatinic acid (H ₂ PtCl ₆ ), and copper (II) chloride (CuCl ₂ ).
On the other hand, the type of the reducing agent is not particularly limited as long as it can reduce the metal ion to be used, and specifically, inorganic such as sodium borohydride, lithium aluminum hydride, sulfite, nitrite and the like. And organic reducing agents such as hydrazine, ascorbic acid and salts thereof, and oxalic acid and salts thereof.
The solvent used for dissolving the first component and / or the second component should be appropriately selected according to the type of the component, but water is usually used from the viewpoint of cost. In addition to water, protic polar solvents such as methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol, butanol, acetic acid, formic acid; acetone, methyl ethyl ketone, acetonitrile, N, N-dimethylformamide, N, N-dimethyl Aprotic polar solvents such as acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide; hexane, cyclohexane, cyclohexanone, dichloromethane, dichloroethane, trichloroethane, chloroform, trichloroethylene, benzene, ethylbenzene, xylene, toluene, diethyl ether, 1,4 -Nonpolar solvents such as dioxane, methyl acetate, ethyl acetate, tetrahydrofuran, and methylene chloride. In addition, a solvent is not restricted to 1 type, You may use combining 2 or more types.
The concentration of the first component or the second component contained in the solution sprayed by the electrospray sprayer is appropriately selected according to the type of the component, but is usually 0.001% by mass or more, preferably It is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, Usually, 2.0 mass% or less, Preferably it is 1.5 mass% or less, More preferably, it is 1.0 mass% or less. Within the above range, metal particles can be efficiently formed.

(Subject to attachment)
There are no particular limitations on the type (type of article, material, etc.), form, etc. of the target of attachment of the metal particle attachment method of the present invention, and the method can be applied to attachment to a wide range of articles. In particular, it is suitable for the attachment of metal particles having antibacterial and deodorizing effects such as silver and gold, and therefore, it is preferable to use fiber materials for which the demand for antibacterial and deodorization is high. The “fiber material” in the present invention is a specific material, natural material, as long as it is a thread-like material containing a polymer compound as a constituent component, or a material bundled with the material (cotton, woven fabric, non-woven fabric, paper, etc.). The difference between the fibers and the synthetic fibers, the form of the material, etc. are not particularly limited. For example, the types of fiber materials include plant fibers such as hemp and cotton, animal fibers such as wool and silk, regenerated fibers such as rayon, polyamide synthetic fibers, polyester synthetic fibers, acrylic synthetic fibers, and polyvinyl alcohol synthetics. Examples thereof include fibers, polyolefin-based synthetic fibers, polyurethane-based synthetic fibers, cellulose-based semi-synthetic fibers, and protein-based semi-synthetic fibers. The fiber material is more preferably a yarn, woven fabric, non-woven fabric, knitted fabric, paper, or film.

<Antimicrobial debromination method>
The method for attaching metal particles of the present invention can be widely applied to the technical field using metal particles, but utilizes antibacterial action and antibacterial action on metal to be attached using antibacterial action of metal and deodorizing action based on bacterial growth inhibition. And / or use as an antibacterial debromination method that imparts a deodorizing action. Note that an antibacterial / debromating method for imparting an antibacterial action and / or a deodorizing action to an object to be attached by the metal particle attaching method of the present invention is also an embodiment of the present invention.
In the method for attaching metal particles of the present invention, the metal particles can be firmly attached to the object to be attached, and therefore, an antibacterial debromination method can be used without using a binder (binding agent / linking agent) for fixing the metal particles. It has good features. Further, when a binder used for fiber surface processing or the like is used, the exposed area of the metal silver particles is reduced, and thus the effect is considered to be reduced. However, the method for attaching metal particles of the present invention is used. Therefore, it is considered that a fiber material superior in antibacterial property can be produced because it can be “binder-free”. Therefore, the antibacterial debromination method which is one embodiment of the present invention is preferably a method which does not use a binder.

<Method for producing fiber material>
As described above, the method for attaching metal particles of the present invention can be used, for example, as an antibacterial and deodorizing method that imparts an antibacterial action and / or deodorizing action to an object to be attached. The manufacturing method of the fiber material included as the bromination treatment step is also an embodiment of the present invention (hereinafter sometimes abbreviated as “the manufacturing method of the present invention”). In addition to the antibacterial debromination process described above, the production method of the present invention is a known process performed in the fiber material production process, for example, spinning process (melt spinning, dry spinning, wet spinning), stretching process, spinning process. A process, a weaving process, a scouring process, etc. may be included. In particular, the method for attaching metal particles of the present invention is a method suitable for continuously performing antibacterial debromination treatment of a fiber material, and further by continuously performing a combination of steps such as a spinning step. Productivity can be remarkably increased.
That is, the production method of the present invention preferably further includes at least one process selected from the group consisting of a spinning process, a stretching process, a spinning process, a knitting process, and a scouring process.

As a specific aspect to which the production method of the present invention is applied, there is a continuous processing treatment as shown in FIG. 11 (hereinafter sometimes abbreviated as “the aspect of FIG. 11”). (1101 in FIG. 11 is a fiber material before processing (for example, cotton yarn), 1102 is a water tank containing an electrolyte solution, 1103 is a dyeing treatment step, 1104 is a functional material addition (antibacterial debromination treatment) step, and 1105 is glued. Processing step 1106 represents an electrospray sprayer, and 1107 represents a heat drying apparatus.
The aspect of FIG. 11 is a method of a line production system in which a cotton thread (fiber material) is moved using a roller, and the cotton thread is a water tank containing an electrolyte solution, a dyeing process, an antibacterial debromination process, and a gluing process. Are passed in the order of the heating and drying apparatus.

<Metal particle attachment device>
The method for attaching metal particles of the present invention, particularly a reaction step of spraying droplets containing the first component onto the object to be attached by an electrospray sprayer and reacting with the second component contained in the object to be attached to form metal particles. The attaching method is a method capable of efficiently attaching metal particles, but a metal particle attaching device that can be used in such an attaching method is also an embodiment of the present invention (hereinafter abbreviated as “metal particle attaching device 1”). There is a case.)
That is, the metal particle attaching apparatus 1 is selected from the group consisting of immersing the object to be attached in the second component solution, spraying the second component solution onto the object to be attached, and dropping the second component solution onto the object to be attached. A second component solution contact mechanism that performs at least one of the above, an electrospray sprayer that sprays droplets containing the first component onto the attachment target containing the second component, and the electrospray spraying of the attachment subject containing the second component An attachment target feeding mechanism for moving to a spray destination of the machine is provided.

Also, a reaction step of spraying droplets containing the first component with an electrospray sprayer and reacting with a second component contained in droplets sprayed with another electrospray sprayer to form metal particles, and formation An attachment method including a spraying step of spraying the metal particles toward the object to be attached is also a method capable of efficiently attaching the metal particles. A metal particle attaching apparatus that can be used for such an attachment method is also included in the present invention. (It may be abbreviated as “metal particle attaching device 2” hereinafter).
That is, the metal particle deposition apparatus 2 includes an electrospray sprayer that sprays droplets including the first component, an electrospray sprayer that sprays droplets including the second component, and the sprayed first and second components. It has a spraying mechanism for spraying metal particles formed by the reaction toward the object to be attached.

  The second component solution contact mechanism in the metal particle attaching apparatus 1 includes immersing the object to be attached in the second component solution, spraying the second component solution onto the object to be attached, and dropping the second component solution onto the object to be attached. The apparatus to be used is not particularly limited as long as it is a mechanism that performs at least one selected from the group consisting of, for example, an immersion liquid in which a second component solution 414 is charged as shown in FIG. A mechanism for immersing the adhesion target 401 in the tank 413, a mechanism for spraying the second component solution 414 onto the adhesion target 401 using the spraying device 415 as shown in FIG. 4B, as shown in FIG. For example, a mechanism of dropping the second component solution 414 to the attachment target 401 by using the dropping device 416 may be used.

  The attachment target feeding mechanism in the metal particle attaching apparatus 1 is not particularly limited as long as it is a mechanism that can move the attachment target including the second component to the spray destination of the electrospray sprayer. A conveyor, a belt conveyor, etc. are mentioned.

  The spraying mechanism in the metal particle deposition apparatus 2 is not particularly limited as long as the mechanism can spray the metal particles formed by the reaction of the sprayed first component and the second component toward the deposition target. However, for example, a gas source such as a compressor and a high-pressure cylinder, a pipe, a nozzle, and the like are combined.

The metal particle attaching apparatus 1 is not particularly limited in other respects, but preferably has a structure in which the distance between the electrospray sprayer and the object to be attached and the spraying direction of the electrospray sprayer are variable. Since these are variable, various conditions can be dealt with.
The metal particle impregnating apparatus 2 is also not particularly limited in other respects, but preferably has a structure in which the distance between the electrospray sprayers and the spray direction of the electrospray sprayers are variable. Since these are variable, various conditions can be dealt with.
In addition, it is preferable that the power source (voltage control device or the like) generated by the electric field of the electrospray sprayer has a variable applied voltage. Since the applied voltage is variable, various conditions can be handled.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Example 1>
Attached white cloth (material: cotton, for JIS L 0803 dyeing fastness test size: 10 cm × 10 cm) Two electrospray sprayers were arranged as shown in the conceptual diagram of FIG. 5 (501 in FIG. 5 is cotton cloth, 502 Is a sprayed silver nitrate solution, 504 is an electrospray sprayer nozzle, 505 is a sprayed ascorbic acid solution, 508 is a spray nozzle, and 509 is an acrylic hood). The two electrospray sprayers use glass capillaries (diameter: 0.1 mm) each having an electrode attached to the tip as a nozzle, and the tip of the nozzle is an acrylic hood that surrounds the spray area. Placed inside and fixed facing each other (distance between nozzles of two electrospray sprayers: 40 mm). One electrospray sprayer has a silver nitrate solution (silver ion concentration: 0.1 mol / L, solvent: ethanol / water = 4/1 (volume ratio)), and the other electrospray sprayer has ascorbine. An acid solution (ascorbic acid concentration: 0.1 mol / L, solvent: ethanol / water = 4/1 (volume ratio)) is filled. Furthermore, the acrylic hood is provided with two openings in a direction perpendicular to the direction in which the two electrospray sprayers are arranged, and after placing an attached white cloth in front of one of the openings, The structure is such that gas is blown onto the attached white cloth by blowing gas from the other opening.
The electrode of the electrospray sprayer nozzle filled with the silver nitrate solution is +7.0 kV, and the electrode of the electrospray sprayer nozzle filled with the ascorbic acid solution is -2.8 kV (reference potential: ground). Electric potential was applied, and nitrogen gas was blown in through 2.0 L / min from one opening of the acrylic hood, and spraying of the silver nitrate solution and ascorbic acid solution and blowing of nitrogen gas onto the attached white cloth were simultaneously performed for 3 minutes. .

The attached white cloth that has been sprayed and sprayed is collected, dried, and subjected to morphological observation and qualitative analysis by characteristic X-ray using a scanning electron microscope. As a result, metallic silver particles are formed on the surface of the cotton yarn constituting the attached white cloth. (See FIGS. 6 and 7).
Silver droplets containing silver nitrate and droplets containing ascorbic acid are sprayed by an electrospray sprayer, respectively, and metallic silver particles are formed on the attached white cloth by spraying them onto the attached white cloth. Obviously, it can be attached.
In such an embodiment, a positively charged droplet is sprayed from the nozzle 502 of the electrospray sprayer and a negatively charged droplet is sprayed from the nozzle 504 of the other electrospray sprayer. An electric field is formed between the nozzle 502 and the nozzle 504, and the droplets of the respective charges follow the electric field, the positively charged droplets from the high potential to the low potential side, and the negatively charged droplets from the low potential. Move to the high potential side. A positively charged droplet and a negatively charged droplet collide at a midpoint between the two nozzles, the chemical components of each other react, and the droplet after the collision becomes electrically neutral. When nitrogen gas is sprayed from the spray nozzle 508, the positively charged and negatively charged droplets are carried to the object to be attached 501 while colliding, and uniformly applied. In addition, such spraying has an advantage of increasing the reaction efficiency because the collision probability between a positively charged droplet and a negatively charged droplet is increased.

<Example 2>
The bottom end of Asahi Spinning Co., Ltd. cotton yarn (material: cotton, thickness: No. 4 single yarn) with a total length of 2 m or more is fixed to the winding roll, and the cotton yarn, electrospray sprayer, immersion bath, etc. are shown in FIG. Arranged as shown in the conceptual diagram (801 in FIG. 8A or 8B is cotton thread, 802 is a nozzle of an electrospray sprayer, 803 is a sprayed silver nitrate solution, 804 is an ascorbic acid solution, and 805 is for dipping. (Liquid tank, 806 represents a roller, 807 represents a voltage application electrode, and 808 represents a winding roll.) The electrospray sprayer uses a stainless steel nozzle with a spray port diameter of 0.1 mm, and the cotton thread is positioned on the spraying direction (horizontal direction) of the nozzle, the tip of the nozzle and the shortest of the cotton thread. Each is fixed so that the distance is 20 mm. The electrospray sprayer is filled with a silver nitrate solution (silver ion concentration: 0.1 mol / L, solvent: ethanol / water = 4/1 (volume ratio)).
An ascorbic acid solution (ascorbic acid concentration: 0.1 mol / L, solvent: ethanol / water = 4/1 (volume ratio)) is placed in the immersion bath, and the cotton yarn is placed in the ascorbic acid solution for about 2 seconds. After soaking, the cotton yarn was wound up at a speed of 1 m / min so as to move to the spray destination of the electrospray sprayer (content of ascorbic acid solution in the cotton yarn: 400% by mass).
The silver nitrate solution was sprayed from an electrospray sprayer toward the cotton yarn that passed through the ascorbic acid solution. Spraying was performed by applying +6.0 kV to the electrode of the nozzle and -3.0 kV (reference potential: ground) to the cotton yarn.
The sprayed cotton yarn is collected and washed with water using the apparatus shown in FIG. 9 (condition: after collecting 12 yards of cotton yarn, it is placed in a pot of a dyeing tester and washed with water. Cotton yarn: water = 1: 20) and drying (condition: constant temperature drying at 60 ° C.) (921 in FIG. 9 is processed yarn, 922 is cotton yarn (for bath ratio adjustment), 923 is a pot, 924 is a sample fixing bracket, and 925 is washed. Water, 926 represents a hot water bath solution (ethylene glycol)).

A photograph of the cotton yarn before and after spraying is shown in FIG. 10 (A), and a scanning electron micrograph of the cotton yarn after spraying is shown in FIG. 10 (B). It is clear that the cotton yarn is colored black due to the metallic silver particles. Further, silver was eluted from the cotton yarn with 1N nitric acid, and the eluate was measured with an atomic absorption analyzer. As a result, silver ions were detected, and it was confirmed that metallic silver was formed on the surface of the cotton yarn.
By spraying droplets containing silver nitrate with an electrospray sprayer, it is apparent that metal silver particles are formed and attached by reacting with ascorbic acid contained in the cotton yarn to be attached.

<Metal silver particle adhesion strength evaluation test>
Except for changing the feeding speed (winding speed) of the cotton yarn, cotton yarns to which metallic silver particles were attached were prepared in the same manner as in Example 2, and the amount of metallic silver particles attached was measured before and after washing with water. The amount of metallic silver particles attached was determined by eluting silver with nitric acid and measuring the amount of silver ions in the solution with an atomic absorption analyzer, as in Example 2. A graph showing the relationship between the feed rate of the cotton yarn and the amount of metal silver particles attached is shown in FIG. As the feed rate of cotton yarn increases, the amount of metal silver particles attached tends to decrease. However, the difference in the amount of metal silver particles attached before and after cleaning is reduced, so that the excess metal silver particles that tend to fall off are suppressed and firmly attached. It is considered that the metallic silver particles attached to are selectively formed. In addition, it is clear that the metal silver particles can be firmly attached to the object to be attached without using a binder (binder / linking agent) by using the method for attaching metal particles of the present invention. For example, when a binder used for fiber surface processing or the like is used, the exposed area of the fixing substance such as metallic silver particles is reduced, so that the effect is considered to be reduced. By using the method, it can be made “binder-free”, so that it is considered that a fiber material superior in antibacterial properties can be produced.

<Antimicrobial evaluation test>
The antibacterial property of the cotton yarn impregnated with the metallic silver particles of Example 2 was evaluated. In addition, the antibacterial evaluation used the method according to JISL1902 (the antibacterial test method and antibacterial effect of a textile product), and used Staphylococcus aureus IFO12732 as bacteria.
Specifically, 0.15 g of cotton yarn is put in a vial, inoculated with 0.2 ml of a test bacterial solution, cultured at 35 ° C. for 18 hours, and then 10 ml of sterilized water is added to wash out the bacteria from the cotton yarn. The number of bacteria was measured by a luminescence measurement method (ATP method), and bacteriostatic activity value and bactericidal activity value were calculated according to the following formulas.
Bacteriostatic activity value = {log (standard yarn, viable count after culture)-log (standard yarn, viable count immediately after inoculation)}-{log (processed yarn, viable count after culture)-log (processed yarn, viable count immediately after inoculation) Number of bacteria)}
Bactericidal activity value = log (standard thread, viable count immediately after inoculation)-log (processed thread, viable count after culture)
The bacteriostatic activity value is a logarithm of the number of viable bacteria in the standard yarn after 18 hours of cultivation divided by the number of viable bacteria in the processed yarn after 18 hours of cultivation. The bactericidal activity value is a logarithm of the number of viable bacteria in the standard yarn immediately after inoculation divided by the number of viable bacteria in the processed yarn after 18 hours of cultivation. It is said that there is.
The results of the evaluation test are shown in Table 1. In addition, the cotton yarn (referred to as Example 3) in which the feed rate (winding speed) of the cotton yarn was changed from 1 m / min to 2 m / min and the standard cotton yarn not attached with metallic silver particles (referred to as Comparative Example 1). The results are also shown in Table 1.
From the results, it is clear that the cotton yarn with metal silver particles attached is excellent in antibacterial properties.

  The method for attaching metal particles according to the present invention can be used for antibacterial debromination treatment and the like because silver particles or gold particles having antibacterial and / or deodorizing effects can be attached efficiently.

DESCRIPTION OF SYMBOLS 101 Object to be attached 102 Electrospray sprayer nozzle 103 Sprayed droplets 104 Another electrospray sprayer nozzle 105 Sprayed droplets 106 Distance between electrospray sprayer nozzle and target 107 Two electrospray sprays 201 The distance between the nozzles of the machine 201 The object of application 202 The nozzle of the electrospray sprayer 203 The sprayed droplet 204 The nozzle of another electrospray sprayer 205 The sprayed droplet 207 The distance between the nozzles of two electrospray sprayers 208 Spray nozzle 301 Attachment target 302 Electrospray sprayer nozzle 303 Sprayed droplets 304 Another electrospray sprayer nozzle 305 Sprayed droplets 308 Spray nozzle 309 Container 310 Closed space 311 Opening 401 Attachment target 402 Electrospray sprayer nozzle 403 Sprayed liquid droplet 412 Roller 413 Immersion liquid tank 414 Second component solution 415 Spraying device for spraying second component solution 416 Dripping device 501 Cotton cloth 502 Nozzle of electrospray sprayer 503 Sprayed silver nitrate solution 504 Electrospray sprayer nozzle 505 Sprayed ascorbic acid solution 508 Spray nozzle 509 Acrylic hood 801 Cotton yarn 802 Electrospray sprayer nozzle 803 Sprayed silver nitrate solution 804 Ascorbic acid solution 805 Immersion bath 806 Roller 807 Electrode for voltage application 808 Winding roll 921 Processing yarn 922 Cotton yarn (for bath ratio adjustment)
923 Pot 924 Sample fixing bracket 925 Washing water 926 Hot water bath solution (ethylene glycol)
DESCRIPTION OF SYMBOLS 1101 Fiber material before a process 1102 Water tank containing electrolyte solution 1103 Dyeing process 1104 Antibacterial debromination process 1105 Gluing process 1106 Electrospray sprayer 1107 Heat drying apparatus

Claims (11)

  The droplet containing the first component is sprayed on the object to be attached by an electrospray sprayer, and reacted with the second component contained in the droplet included in the object to be attached and / or sprayed by another electrospray sprayer. A method for attaching metal particles, comprising a reaction step of forming metal particles. A reaction step in which droplets containing the first component are sprayed by an electrospray sprayer and reacted with a second component contained in droplets sprayed by another electrospray sprayer to form metal particles, and the reaction step A method for attaching metal particles, comprising a spraying step of spraying the metal particles formed in step 1 to an object to be attached.   The method for attaching metal particles according to claim 1 or 2, wherein the reaction step is a step of forming metal particles in a closed space.   The method for attaching metal particles according to any one of claims 1 to 3, wherein the object to be attached is a fiber material.   5. The metal particle attachment according to claim 1, wherein the metal particles are at least one selected from the group consisting of copper particles, silver particles, palladium particles, platinum particles, and gold particles. Method.   The method for attaching metal particles according to any one of claims 1 to 5, wherein the metal particles are particles having an average particle diameter of 1 to 100 nm.   An antibacterial / debromating method characterized by imparting an antibacterial action and / or deodorizing action to the object to be attached by the metal particle attaching method according to any one of claims 1 to 6.   A method for producing a fiber material, comprising an antibacterial and / or deodorization treatment step for imparting an antibacterial action and / or a deodorizing action to the fiber material by the antibacterial and debromination method according to claim 7.   The fiber material according to claim 8, further comprising at least one process selected from the group consisting of a spinning process, a stretching process, a spinning process, a weaving process, a bleaching process, a pasting process, a scouring process, and a dyeing process. Production method.   Secondly, performing at least one selected from the group consisting of immersing the attachment target in the second component solution, spraying the second component solution onto the attachment target, and dropping the second component solution onto the attachment target. A component solution contact mechanism, an electrospray sprayer that sprays droplets containing a first component onto an attachment target containing a second component, and a method for moving the attachment target containing a second component to a spray destination of the electrospray sprayer An apparatus for attaching metal particles, comprising an attachment target feeding mechanism.   An electrospray sprayer that sprays droplets containing the first component, an electrospray sprayer that sprays droplets containing the second component, and metal particles formed by the reaction between the sprayed first component and the second component An apparatus for attaching metal particles, comprising a spraying mechanism for spraying toward an object to be attached.