JP6583629B2 - Method for applying paint to fiber material, method for producing fiber material, and fiber material processing apparatus - Google Patents

Description

  The present invention relates to a method for applying a paint to a fiber material, a method for producing the fiber material, and a fiber material processing apparatus, and more specifically, a paint application that can be applied to dyeing of fiber material, antibacterial debromination, and the like. The present invention relates to a wearing method and a fiber material processing apparatus.

  The manufacturing industry such as the textile industry and the paper industry is a key industry that has greatly contributed to Japan (Japan), especially the regional economy, but in recent years it has faced fierce international competition accompanying the development of emerging countries. There is a need for further reductions in product quality and higher functionality and quality. In the textile industry, for example, the treatment of so-called dye wastewater generated in the dyeing process is an important issue. For example, when dyeing cellulose fibers such as cotton and rayon, a large amount of dye bath or washing water is generally used because the fibers are taken out and the excess dye is washed away after the fibers are put into a dye bath containing reactive dyes. It will be discharged as dyed wastewater. For such a problem, for example, it has been proposed to use a component derived from the genus Troy's family as a flocculant for purifying dyed wastewater (see Patent Document 1). In addition, the conventional dyeing methods have problems such as requiring a large amount of drying treatment and not being applicable to small lot and multi-product production. In particular, the fuel consumption necessary for the drying process has been improved by switching to fuel other than heavy oil and introducing energy-saving equipment, etc., but has reached 606,000 kL (2011) in terms of crude oil at the entire dyeing office. There is a need to reduce its usage.

  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 is mass spectrometry (see Patent Document 2) and high voltage. It is used for deposition of molecular compounds and the like (see Patent Document 3). 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.

JP 2013-006174 A Japanese Patent Laid-Open No. 06-215729 JP 2007-070738 A

As described in Patent Document 1, it is extremely important to appropriately purify the dye wastewater generated in the dyeing process of the fiber material, but it is also important to reduce the dye wastewater itself as much as possible. For example, improving the dyeing method or the like to increase the utilization efficiency of the dye or the like, or being applicable to small-lot and multi-product production leads to a reduction in manufacturing cost and environmental load.
In recent years, fibers having various functions such as antibacterial deodorizing action and flame retardancy have been demanded, and the treatment performed to give these functions is also the cause of the generation of a large amount of waste liquid. It has become.
This invention makes it a subject to provide the novel processing method and processing apparatus of the fiber material which can solve the problems in the above dyeing | staining, antibacterial debromination treatment, etc.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have included an electrolyte solution in the fiber material, and thus contain dyes, antibacterial agents, deodorants, etc., utilizing the electrospray phenomenon. The present invention was completed by finding that the applied paint can be efficiently applied to the fiber material.

That is, the present invention is as follows.
<1> A method for applying a paint to a fiber material, comprising: a preparation step of preparing a fiber material containing an electrolyte solution; and a spraying step of spraying the paint toward the fiber material by electrospray.
<2> The electrolyte solution according to <1>, wherein the electrolyte solution is a solution containing at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, aluminum salts, ammonium salts, and transition metal salts. Coating method.
<3> The preparation step includes at least one selected from the group consisting of immersing the fiber material in an electrolyte solution, spraying the electrolyte solution onto the fiber material, and dropping the electrolyte solution onto the fiber material. The coating method according to <1> or <2>, which is a process.
<4> The paint contains at least one selected from the group consisting of a dye, an antibacterial agent, a deodorant, a water / oil repellent, a flame retardant, a bleaching agent, a softener, a paste, and an antifouling agent. The coating method according to any one of <1> to <3>, which is a solution.
<5> When the fiber material contains a reducing agent and the paint is a solution containing metal ions, the paint containing metal ions is sprayed on the fiber material in the spraying step, and the metal ions The coating method according to any one of <1> to <4>, wherein the reducing agent reacts to produce metal particles in the fiber material.
<6> The coating according to any one of <1> to <5>, wherein the spraying step includes spraying one type or two or more types of paints using two or more electrospray sprayers. How to wear.
<7> The spraying step according to <6>, wherein the spraying step includes a step of moving the fiber material and / or the electrospray sprayer to spray one or more types of paints continuously. How to paint.
<8> The coating method according to any one of <1> to <7>, wherein the preparation step and the spraying step are continuously performed by moving the fiber material containing the electrolyte solution.
<9> The coating method according to any one of <1> to <8>, wherein the fiber material is yarn, woven fabric, nonwoven fabric, knitted fabric, paper, or film.
<10> A method for producing a fiber material, comprising at least one step selected from the group consisting of the following (1) to (8).
(1) A dyeing treatment step including dyeing a fiber material by applying a paint containing a dye by the applying method according to any one of <1> to <9>.
(2) A coating material containing an antibacterial agent and / or deodorant is applied by the coating method according to any one of <1> to <9> to impart an antibacterial action and / or a deodorizing action to the fiber material. An antibacterial debromination process comprising:
(3) Water-repellent / water-repellent, comprising applying a paint containing a water- and oil-repellent by the coating method according to any one of <1> to <9> to impart a water / oil repellent action to the fiber material. Oiling process.
(4) A flame retardant treatment step of applying a paint containing a flame retardant by the coating method according to any one of <1> to <9> to make the fiber material difficult to burn.
(5) A bleaching treatment step including bleaching the fiber material by applying a paint containing a bleaching agent by the coating method according to any one of <1> to <9>.
(6) A softening treatment step comprising applying a paint containing a softening agent by the coating method according to any one of <1> to <9> to impart flexibility to the fiber material.
(7) A gluing treatment step including gluing a fiber material by applying a paint containing a gluing agent by the coating method according to any one of <1> to <9>.
(8) An antifouling treatment step comprising applying a paint containing an antifouling agent by the coating method according to any one of <1> to <9> to impart an antifouling action to the fiber material.
<11> The method for producing a fiber material according to <10>, further including 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.
<12> An electrolyte solution contact mechanism that performs at least one selected from the group consisting of immersing the fiber material in the electrolyte solution, spraying the electrolyte solution onto the fiber material, and dropping the electrolyte solution onto the fiber material, An electrospray sprayer that sprays paint onto a fiber material containing an electrolyte solution, and a fiber material feed mechanism for moving the fiber material containing the electrolyte solution to a spray destination of the electrospray sprayer And fiber material processing equipment.
<13> The fiber material processing apparatus according to <12>, comprising two or more electrospray sprayers.
<14> The electrospray sprayer according to <12> or <13>, comprising an electrospray sprayer that sprays at least one paint selected from the group consisting of the following (1) to (8) as the electrospray sprayer. Textile material processing equipment.
(1) A paint containing a dye.
(2) A paint containing an antibacterial agent and / or a deodorant.
(3) A paint containing a water / oil repellent.
(4) A paint containing a flame retardant.
(5) A paint containing a bleaching agent.
(6) A paint containing a softening agent.
(7) A paint containing a paste.
(8) A paint containing an antifouling agent.

  According to the present invention, a paint can be efficiently applied to a fiber material. Therefore, by applying to dyeing, antibacterial debromination treatment, etc., it is possible to reduce waste liquid generated for these treatments and to omit drying treatment, etc., and to be applicable to small lot and multi-product production. As a result, the manufacturing cost of the textile product and the reduction of the environmental load are reduced.

It is a conceptual diagram showing the state which is spraying the coating material toward the fiber material by electrospray. (A) It is a conceptual diagram showing the aspect which moves a fiber material and sprays one type or two or more types of coating materials continuously. (B) It is a conceptual diagram showing the aspect which sprays the coating material of 1 type or 2 types or more to the same position of a fiber material. (C) It is a conceptual diagram showing the aspect sprayed, moving an electrospray sprayer. (A) It is a conceptual diagram showing the aspect which is performing the spraying process continuously, after immersing a fiber material in an electrolyte solution as a preparatory process. (B) It is a conceptual diagram showing the aspect which is performing the spraying process continuously, after spraying an electrolyte solution on a fiber material as a preparatory process. (C) It is a conceptual diagram showing the aspect which is performing the spraying process continuously, after dripping an electrolyte solution to a fiber material as a preparatory process. (A) It is the photograph which shows the state which is spraying the ethanol of Example 1 (drawing substitute photograph). (B) It is a photograph which shows the state which is spraying the ethanol of the comparative example 1 (drawing substitute photograph). (C) It is the conceptual diagram showing a mode that the droplet sprayed from the nozzle converges toward a cotton thread. (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 photograph which shows the state which is spraying the dyeing | staining solution of Example 2 (drawing substitute photograph). (A) It is a conceptual diagram of the apparatus used in Example 3. FIG. (B) It is an overhead view of the electrospray sprayer part of the apparatus used in Example 3. (C) It is the photograph which shows the state which is spraying the dyeing solution of Example 3 (drawing substitute photograph). It is a photograph of the cotton yarn dyed in multiple colors according to Example 3 (drawing substitute photograph). It is a photograph which shows the state which is spraying the dyeing | staining solution of the comparative example 2 (drawing substitute photograph). (A) It is a conceptual diagram of the apparatus used in Example 4. FIG. (B) It is an overhead view of the electrospray sprayer part of the apparatus used in Example 4. 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 4 (drawing substitute photograph). (B) It is the scanning electron micrograph of the cotton yarn which attached the metal silver particle by Example 4 (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. (A) It is a conceptual diagram of the apparatus used in Example 6. FIG. (B) It is the photograph of the silk thread dyed with plants by Example 6 (drawing substitute photograph). (A) It is a conceptual diagram of the apparatus used in Example 7. FIG. (B) It is the photograph of the cotton thread dyed by gradation by Example 7 (drawing substitute photograph). (A) It is a conceptual diagram of the apparatus used in Example 8. FIG. (B) It is the photograph of the silk thread dyed by gradation by Example 8 (drawing substitute photograph). (A) It is a conceptual diagram of the apparatus used in Example 9. FIG. (B) It is the photograph of the cotton thread dyed deeply by Example 9 (drawing substitute photograph). It is a photograph of the paper yarn dye | stained by Example 10 (drawing substitute photograph). It is the photograph of the cotton yarn dye | stained using various reactive dyes (drawing substitute photograph).

  In describing the details of the method for applying a coating material to a fiber material, the method for producing the fiber material, and the fiber material processing apparatus according to the embodiment of the present invention, a specific example will be described. However, it departs from the spirit of the present invention. As long as it does not, it is not limited to the following content, It can change suitably and can implement.

<Method of applying paint to fiber material>
The method for applying a paint to a fiber material which is one embodiment of the present invention (hereinafter sometimes abbreviated as “the coating method of the present invention”) is a preparation step (hereinafter referred to as a fiber material containing an electrolyte solution). , And may be abbreviated as “preparation step”), and a spraying step of spraying the paint toward the fiber material by electrospraying (hereinafter sometimes abbreviated as “spraying step”). .
As a result of repeated research on new processing methods for fiber materials that can be applied to dyeing, antibacterial debromination treatment, etc., the present inventors have utilized the electrospray phenomenon by including an electrolyte solution in the fiber materials. The present inventors have found that a coating material containing a dye, an antibacterial agent, a deodorant and the like can be efficiently applied to a fiber material. In the electrospray phenomenon, a high voltage is applied between a nozzle filled with a liquid and a counter electrode, and an electric field is generated between the nozzle and the counter electrode, whereby the liquid becomes charged droplets on the counter electrode. However, when the spray target is an insulator such as a fiber material, there is a problem that an electric field is hardly generated between the nozzle and the paint, and the paint cannot be applied efficiently. . The inventors of the present invention can apply an electrospray phenomenon by generating an electric field between the fiber material and the nozzle by adding an electrolyte solution to the fiber material to impart conductivity. Was found. The electric field between the nozzle and the fiber material is, for example, using a power source, setting the nozzle side to a positive potential and the fiber material side to 0 kV or a negative potential, or setting the nozzle side to a negative potential and the fiber material side to 0 kV or It can be generated by setting it to a positive potential. In addition, since it is sufficient if there is a potential gradient between the nozzle and the fiber material, for example, (nozzle potential)> (fiber material potential)> 0 is set, or 0V> (fiber material potential)> (nozzle potential) The electrospray phenomenon can also be caused when the potential is set. Such an electrospray phenomenon is a method in which a paint can be applied efficiently because generated charged droplets are attracted (focused) to an object to be sprayed by an electric field. Therefore, by applying to dyeing, antibacterial debromination treatment, etc., it is possible to reduce waste liquid generated for these treatments and to omit drying treatment, etc., and to be applicable to small lot and multi-product production. Thus, it can be said that this leads to a reduction in the manufacturing cost and environmental load of the textile product. Further, for example, when the coating method of the present invention is used for dyeing fiber materials, the electrolyte solution also serves as a fixing agent (also referred to as “dyeing aid”) for fixing the dye to the fiber material. It becomes a very efficient dyeing method.
In the present invention, the “fiber material” means a thread-like material containing a polymer compound as a constituent component, or a material in which this is bundled (cotton, woven fabric, non-woven fabric, paper, etc.), a specific material, The difference between natural and synthetic fibers, the form of the material, etc. are not particularly limited. Further, the present invention does not exclude the use of the above-described coating method in a state of being processed into clothing, paper products, etc., and the above-described coating method is applied to a product in which a material form as a fiber material is maintained. Utilization is also included in the coating method of the present invention.
In addition, “spraying the paint toward the fiber material by electrospray” means that the paint is sprayed on the fiber material by utilizing the electrospray phenomenon, that is, the paint is filled in the nozzle of the sprayer, It means that an electric field is generated between the fiber material to be sprayed and the paint is sprayed toward the fiber material (hereinafter, a device for spraying paint using the electrospray phenomenon is referred to as “electro It may be abbreviated as “spray sprayer”.) In addition, the conceptual diagram of the state which is spraying the coating material toward the fiber material by electrospray is shown in FIG. 1 (101 is the fiber material containing the electrolyte solution, 102 is the nozzle of the electrospray sprayer, and 103 is sprayed. The paint 104 represents the distance between the nozzle of the electrospray sprayer and the fiber material, and the fiber material 101 and the nozzle of the electrospray sprayer are connected via an electrode, a conductor, a power source and the like. Usually, an electrospray sprayer has a nozzle for determining the spraying direction, and a power source for generating an electric field between the nozzle and the fiber material to be sprayed (voltage control device, etc., electrodes for connecting the nozzle and the fiber material) (Including conductors, etc.) At least provided (Note that when two or more electrospray sprayers are used, one power supply may be shared, and not all electrospray sprayers have separate power supplies. May be.) Also, the nozzle itself is made of a conductive material, or an electrode (for example, platinum wire) is installed in the nozzle, and the nozzle and the fiber material to be sprayed are each supplied with a power source (voltage control device, etc.) By applying a voltage, the electric field is generated between the nozzle and the fiber material.

(Preparation process)
The preparation process according to the present invention prepares a fiber material to be used in the spraying process to be described later, and the specific preparation method is not particularly limited. Even if a fiber material containing an electrolyte solution is obtained, or an electrolyte The fiber material containing the solution may be prepared by itself. Also, the preparation method when the fiber material containing the electrolyte solution is prepared by itself is not particularly limited. For example, the method of immersing the fiber material in the electrolyte solution, the method of spraying the electrolyte solution onto the fiber material, and the electrolyte solution as the fiber material The method of dripping is mentioned. As a preparatory process according to the present invention, at least one selected from the group consisting of immersing the fiber material in an electrolyte solution, spraying the electrolyte solution onto the fiber material, and dropping the electrolyte solution onto the fiber material, It is preferable that it is a process including.

The type, concentration, content, etc. of the electrolyte in the electrolyte solution contained in the fiber material are not particularly limited, and can be appropriately set according to the type of paint to be applied, the type of fiber material, etc. (for example, the fiber material) Depending on the type, a neutral electrolyte or an alkaline electrolyte can be selected.)
The types of electrolytes include sodium carbonate, sodium acetate, sodium sulfate, sodium hydroxide, sodium chloride, magnesium chloride, aluminum sulfate, aluminum carbonate, potassium carbonate, potassium acetate, potassium sulfate, potassium chloride, calcium chloride, potassium alum, etc. Examples include alkali metal salts, alkaline earth metal salts, and aluminum salts; ammonium salts such as ammonium carbonate, ammonium acetate, ammonium sulfate, ammonium hydroxide, and ammonium chloride; and transition metal salts such as iron chloride and iron sulfate. It is done. Among these, it is preferable to contain at least one selected from the group consisting of sodium carbonate, sodium acetate, sodium sulfate, sodium hydroxide, aluminum sulfate, aluminum carbonate, ammonium acetate, potassium alum, and iron sulfate.
The concentration of the electrolyte solution is usually 0.001% by mass or more, preferably 0.1% by mass or more, more preferably 2.5% by mass or more, and usually 20.0% by mass or less, preferably 15.0% by mass. Hereinafter, it is more preferably 10.0% by mass or less. When it is within the above range, the paint can be applied efficiently.
The content of the electrolyte solution contained in the fiber material (the mass of the electrolyte solution in 100% by mass of the fiber material) is usually 300% by mass or more, preferably 400% by mass or more, more preferably 500% by mass or more, and usually 1000% by mass. % Or less, preferably 850 mass% or less, more preferably 700 mass% or less. When it is within the above range, the paint can be applied efficiently.

The fiber material prepared in the preparation process according to the present invention may contain a reducing agent. Although details will be described later, for example, the fiber material contains a reducing agent, and by spraying a paint containing metal ions in the spraying process according to the present invention, the metal ions and the reducing agent react to form a metal in the fiber material. Particles can be generated.
Examples of the reducing agent include sodium borohydride, lithium aluminum hydride, sulfite, nitrite, hydrazine, ascorbic acid and its salt, oxalic acid and its salt, and these reducing agents are used as electrolytes. Therefore, instead of the above-described electrolyte, a solution in which these reducing agents are dissolved may be used as the electrolyte solution.

  The fiber material prepared in the preparation process according to the present invention does not necessarily need to contain the electrolyte solution on the entire surface, and may partially contain the electrolyte solution. The electrospray method can also be applied to partially applying a coating material on a fiber material because droplets sprayed on a charged portion are attracted.

  The dipping method in the case where the preparation step according to the present invention includes dipping the fiber material in the electrolyte solution is not particularly limited, and examples thereof include a method of dipping the fiber material in a liquid tank in which the electrolyte solution is charged. . Moreover, the spraying method in the case of spraying the electrolyte solution onto the fiber material is not particularly limited, and examples thereof include a method of spraying the electrolyte solution onto the fiber material using a known sprayer such as a spray gun. Furthermore, the dropping method in the case of including dropping the electrolyte solution onto the fiber material is not particularly limited, but a method of dropping the electrolyte solution onto the fiber material using a known dropping device may be mentioned.

(Spraying process)
The spraying process according to the present invention is a process of spraying paint by electrospray toward the fiber material prepared by the above-mentioned preparation process, but the structure of the electrospray sprayer to be used is not particularly limited and is publicly known. Can be appropriately selected. Usually, the nozzle itself is made of a conductive material, or an electrode (for example, a platinum wire) is installed in the nozzle so that the paint filled in the electric field generated by applying voltage is in contact. ing.
The diameter of the spray nozzle of the nozzle of the electrospray sprayer 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 0.5 mm or less, more Preferably it is 0.3 mm or less. When it is within the above range, the paint can be applied efficiently.

  The spraying process according to the present invention is a process of spraying the paint toward the fiber material by electrospray. However, since the sprayed paint is attracted to the fiber material by the generated electric field, the fiber material is not necessarily the nozzle of the electrospray sprayer. It is not necessary to exist in the spray direction. However, the fiber material is preferably present in a range within 45 ° from the spray direction of the nozzle of the electrospray sprayer, and more preferably in a range within 30 °. When it is within the above range, the paint can be applied efficiently.

  The distance between the nozzle of the electrospray sprayer and the fiber material in the spraying process according to the present invention (the shortest distance between the nozzle tip of the electrospray sprayer and the fiber material) 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. When it is within the above range, the paint can be applied efficiently.

The applied voltage (potential difference generated between the nozzle and the fiber material) in the spraying process according to the present invention 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. Below, more preferably 12 kV or less.
The potential applied to the nozzle is usually a positive potential, and the potential when the reference potential is grounded is usually +2.0 kV or more, preferably +3.0 kV or more, more preferably +4.5 kV or more. +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 fiber material 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.
When it is within the above range, the paint can be applied efficiently.

  The spray amount of the paint in the spraying process according to the present invention 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. When it is within the above range, the paint can be applied efficiently.

The components contained in the paint sprayed in the spraying process according to the present invention can be appropriately selected according to the purpose of application (application of the application method). Examples of the components contained in the paint include (a) fiber material May be classified into modification / function-imparting components and auxiliary components used to modify the fiber or to impart functions to the fiber material, (b) raw material compounds of substances formed in the fiber material, (c) solvents, etc. it can. Hereinafter, (a) to (c) will be described in detail.
(A) Modification / function-imparting component and auxiliary component “Modification / function-imparting component” means, for example, dyes (pigments) for dyeing fiber materials, antibacterial agents, deodorants, water / oil repellents, flame retardants It is intended to mean known components used for modifying fiber materials such as bleaching agents, softeners, glues, antifouling agents, etc., or for imparting functions to fiber materials. In addition, “auxiliary component” means, for example, a surfactant used for enhancing the dispersibility / fixing property of a dye, and an auxiliary component used for processing a fiber material such as an acid / base used for dyeing. Means. Specific types of dyes and the like are listed below, but the modification / function-imparting components used for the fiber material are widely available, and the coating method of the present invention is not limited to those listed below. The “dye” in the present invention includes “pigments” that are not soluble in a solvent.
・ Dyes (pigments)
Direct dye, acid dye (leveling, half-milling, milling), disperse dye (azo, quinone), reactive dye, cationic dye, vat dye, sulfur dye, naphthol dye / antibacterial agent, deodorant silver , Titanium oxide, Zinc oxide, Gold, Platinum, Copper, Zeolite, Charcoal, Triazine compound, Phenol compound, Chitin, Chitosan / Water / oil repellent Fluorine polymer compound, Silicon polymer compound, Polyolefin polymer organic Compounds / Flame retardants Phosphorus organic compounds, halogen compounds, ammonium sulfate, antimony oxide, aluminum hydroxide, sodium silicate (b) Raw material compounds “Raw materials” specifically refers to raw materials for substances formed in fiber materials Means a compound, for example, an inorganic solid compound such as silver or titanium oxide used as an antibacterial agent or deodorant as a fiber material It is an effective component for coating. Specific examples of the raw material compound include metal ions (metal salts), organic metal compounds, and oxidizing agents that oxidize or reduce metal ions and organic metal compounds, which are raw materials for inorganic solid compounds.
・ Metal ions (metal salts)
Silver nitrate (AgNO ₃ ), tetrachloroauric (III) acid (HAuCl ₄ ), hexachloroplatinic acid (H ₂ PtCl ₆ ), copper (II) chloride (CuCl ₂ )
・ Organic metal compounds Alkoxy silanes ・ Oxidizing agents Hydrogen peroxide, ozone, hydrochloric acid, sulfuric acid, reducing agents Sodium borohydride, lithium aluminum hydride, sulfites, nitrites, hydrazine, ascorbic acid and its salts, oxalic acid and its salts (C) Solvent The solvent used in the paint should be appropriately selected according to the components contained in the paint, 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 component contained in the paint sprayed in the spraying process according to the present invention is appropriately selected according to the type of the component and the like, but is usually 0.05% by mass or more, preferably 0.1% by mass or more. More preferably, it is 0.25% by mass or more, usually 2.0% by mass or less, preferably 1.5% by mass or less, more preferably 1.0% by mass or less. When it is within the above range, the paint can be applied efficiently.

As a preferred embodiment of the spraying process according to the present invention, spraying a coating material containing metal ions onto the fiber material can be mentioned. For example, when the fiber material contains a reducing agent, by spraying a paint containing metal ions in the spraying process according to the present invention, the metal ions and the reducing agent react to generate metal particles in the fiber material. Can be made.
In addition, the kind (element), particle form, and the like of the metal particles generated in this manner are 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. . Such a metal is easy to be produced in a fiber material, and also exhibits an antibacterial action and / or a deodorizing action based on bacterial growth inhibition, so that the antibacterial action and / or deodorizing action is imparted to the fiber material. It can be used as a debromating method. Moreover, the average particle diameter of the metal particles to be generated 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.

The spraying process according to the present invention may be a process including spraying one type or two or more types of paints using two or more electrospray sprayers. As an aspect of spraying one type or two or more types of paints using two or more electrospray sprayers, for example, as shown in FIG. As shown in FIG. 2 (B), an embodiment in which the above-mentioned paint is sprayed (hereinafter sometimes abbreviated as “aspect of FIG. 2 (A)”) and one or more kinds of paints are applied to the fiber material. A mode of spraying to the same position (hereinafter sometimes abbreviated as “mode of (B) of FIG. 2”) is exemplified (201 in FIG. 2 is a fiber material containing an electrolyte solution, 202 is an electrospray sprayer, 203 represents a sprayed paint, and 204 represents a different kind of sprayed paint from 203).
The mode of (A) of FIG. 2 is, for example, the case where dyes of the same or different colors are continuously applied, the case where antibacterial agents and / or deodorants are applied continuously after the dyes are applied, etc. Can be used. 2A, in order to move the fiber material, the conductors and electrodes for applying a potential to the fiber material, such as a pantograph and an overhead wire of a railway vehicle, are not fixed to the fiber material. (For example, a voltage application electrode 507 in FIG. 5 is cited.)
As a more specific aspect, a dyeing method in which different color dyes are applied and the color and shade are continuously changed (gradation dyeing, see Examples 7 and 8), three primary colors, black, white, etc. are applied. It can be used for a dyeing method for adjusting the color tone by wearing, a dyeing method for applying the same color to darken the color (dark color dyeing, see Example 9), and the like. Further, in such a dyeing method, a shutter (for example, filter paper shutters 1609 and 1709 in Examples 7 and 8) and a power relay ON / OFF that temporarily blocks the sprayed paint from being applied to the fiber material. By using this, it is possible to perform more precise dyeing or the like by precisely adjusting the amount of paint to be applied.
The mode of (B) in FIG. 2 can be used when the same or different paint is applied simultaneously to the same position of the fiber material.

The spraying process according to the present invention may be a process including spraying while moving the electrospray sprayer. As an aspect which sprays, moving an electrospray sprayer, the aspect as shown to (C) of FIG. 2, for example (henceforth "the aspect of (C) of FIG. 2" may be abbreviated below) is mentioned.
The mode of (C) in FIG. 2 can be used, for example, when a paint is selectively applied or when a paint is preferentially applied.

  The coating method of the present invention is not particularly limited as long as it includes the above-mentioned preparation step and spraying step. In addition to the preparation step and spraying step, a washing step of washing away the electrolyte solution and / or paint from the fiber material Further, a drying step for drying the fiber material, a blending step for adding a reducing agent to the fiber material in addition to the electrolyte solution, and the like may be included. Moreover, the coating method of this invention is not restricted to the aspect in which a preparation process and a spraying process are each performed once each, A preparation process and a spraying process may each be performed in multiple times on both sides of another process. Furthermore, in the coating method of the present invention, the preparation process and the spraying process are individually performed, and for example, the preparation process and the spraying process are continuously performed by moving the fiber material containing the electrolyte solution, so-called line production. A method of a method may be used. By performing the preparation process and the spraying process continuously, the paint can be applied more efficiently. Note that “the preparation step and the spraying step are continuously performed by the movement of the fiber material” includes, for example, an embodiment shown in FIG. 3, and FIG. FIG. 3B shows a mode in which the spraying process is continuously performed after being immersed in the solution, and FIG. 3B is a mode in which the spraying process is continuously performed after the electrolyte solution is sprayed on the fiber material as a preparation process. (C) is a mode in which the electrolyte solution is dropped onto the fiber material as a preparation step, and then the spraying step is continuously performed (301 in FIG. 3 is the fiber material, 302 is a roller, 303 is an electrospray sprayer, 304 is a sprayed paint, 305 is a water tank, 306 is an electrolyte solution, 307 is a spray device for spraying the electrolyte solution, 308 is a sprayed electrolyte solution, 309 is a dropping device, 310 is a dropped electrolyte solution ).

(Fiber material)
The “fiber material” targeted by the coating method of the present invention is specific 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, nonwoven fabric, paper, etc.). The material, the difference between natural fiber and synthetic fiber, 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 preferably yarn, woven fabric, non-woven fabric, knitted fabric, paper, or film.

The coating method of the present invention can be applied to various treatments performed in the production process or processing process of a fiber material, and its use is not particularly limited. For example, it is used in the following methods (1) to (8). can do.
(1) A method for dyeing a fiber material by applying a paint containing a dye to dye the fiber material.
(2) An antibacterial / deodorizing method for a fiber material in which a coating material containing an antibacterial agent and / or a deodorant is applied to give the fiber material an antibacterial or deodorant effect.
(3) A method for imparting water / oil repellency to a fiber material by applying a paint containing a water / oil repellent to the fiber material.
(4) A method for flame-retarding a fiber material by applying a paint containing a flame retardant to make the fiber material difficult to burn.
(5) A method for bleaching a fiber material, in which a paint containing a bleaching agent is applied to bleach the fiber material.
(6) A method for softening a fiber material by applying a paint containing a softening agent to impart flexibility to the fiber material.
(7) A method for gluing a fiber material by applying a paint containing a gluing agent and gluing the fiber material.
(8) A method for antifouling a fiber material by applying a paint containing an antifouling agent to impart an antifouling action to the fiber material.
As a specific mode to which the coating method of the present invention is applied, there is a continuous processing treatment (hereinafter, sometimes abbreviated as “mode of FIG. 13”) as shown in FIG. (1301 in FIG. 13 is a fiber material before processing (for example, cotton yarn), 1302 is a water tank containing an electrolyte solution, 1303 is a dyeing treatment process, 1304 is a functional material addition (antibacterial debromination process), and 1305 is paste Processing step, 1306 represents an electrospray sprayer, and 1307 represents a heat drying apparatus.
The embodiment of FIG. 13 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, a functional material addition (antibacterial debromination process). The gluing treatment process is passed through the heating and drying apparatus in this order.

<Method for producing fiber material>
As described above, the coating method of the present invention can be used, for example, in the above methods (1) to (8). However, a method for producing a fiber material including these methods as a treatment step is also an aspect of the present invention ( Hereinafter, it may be abbreviated as “the production method of the present invention”.
That is, the production method of the present invention includes at least one step selected from the group consisting of the following (1) to (8).
(1) A dyeing treatment step including dyeing a fiber material by applying a paint containing a dye by the applying method of the present invention.
(2) An antibacterial / debromating treatment step including applying an antibacterial agent and / or a deodorant-containing paint by the coating method of the present invention to impart an antibacterial and / or deodorant effect to the fiber material. .
(3) A water / oil repellent treatment step comprising applying a water / oil repellent containing paint by a coating method of the present invention to impart a water / oil repellent action to the fiber material.
(4) A flame retardant treatment step for making the fiber material difficult to burn by applying a paint containing a flame retardant by the coating method of the present invention.
(5) A bleaching treatment step including bleaching the fiber material by applying a paint containing a bleaching agent by the coating method of the present invention.
(6) A softening treatment step comprising applying a paint containing a softening agent by the coating method of the present invention to impart flexibility to the fiber material.
(7) A gluing treatment step including gluing a fiber material by applying a paint containing a gluing agent by the coating method of the present invention.
(8) An antifouling treatment step comprising applying a paint containing an antifouling agent by the coating method of the present invention to impart an antifouling action to the fiber material.

In addition to the steps (1) to (8) described above, the production method of the present invention is a known step performed in the production process of the fiber material, such as a spinning step (melt spinning, dry spinning, wet spinning), stretching step, It may include a spinning process, a knitting process, a scouring process, and the like. In particular, the production method of the present invention is a method suitable for continuously performing a step of applying a coating material to a fiber material such as the steps (1) to (8) described above, and further a step such as a spinning step. By performing continuously in combination, the productivity of the fiber material can be significantly 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.

<Fiber material processing equipment>
The coating method of the present invention, particularly the coating method in which the preparation step and the spraying step are continuously performed by moving the fiber material containing the electrolyte solution, is a method that can efficiently process the fiber material. The fiber material processing apparatus that can be used for such a coating method is also an embodiment of the present invention (hereinafter, may be abbreviated as “the fiber material processing apparatus of the present invention”).
That is, the fiber processing apparatus of the present invention is at least one selected from the group consisting of immersing a fiber material in an electrolyte solution, spraying the electrolyte solution onto the fiber material, and dropping the electrolyte solution onto the fiber material. Electrolyte solution contact mechanism for performing electrolysis, electrospray sprayer for spraying paint toward fiber material containing electrolyte solution, and fiber material for moving fiber material containing electrolyte solution to spray destination of electrospray sprayer A feed mechanism is provided.

  The electrolyte solution contact mechanism in the fiber material processing apparatus of the present invention is selected from the group consisting of immersing the fiber material in the electrolyte solution, spraying the electrolyte solution onto the fiber material, and dropping the electrolyte solution onto the fiber material. The apparatus to be used is not particularly limited as long as it is a mechanism for performing at least one kind, but, for example, the fiber material 301 is immersed in the immersion liquid tank 305 in which the electrolyte solution 306 is charged as shown in FIG. 3, a mechanism for spraying the electrolyte solution 308 onto the fiber material 301 using the spray device 307 as shown in FIG. 3B, and an electrolyte solution 310 using the dropping device 309 as shown in FIG. The mechanism etc. which are dripped in the fiber material 301 are mentioned.

  The fiber material processing apparatus of the present invention preferably includes two or more electrospray sprayers. When two or more electrospray sprayers are provided, it is possible to spray two or more kinds of paints, and the above-described embodiment of FIG. 2A and the embodiment of FIG. 2B can be performed. .

The type of paint to be sprayed by the electrospray sprayer in the fiber material processing apparatus of the present invention can be appropriately selected according to the processing purpose. For example, at least selected from the group consisting of the following (1) to (8) One type of paint is sprayed.
(1) A paint containing a dye.
(2) A paint containing an antibacterial agent and / or a deodorant.
(3) A paint containing a water / oil repellent.
(4) A paint containing a flame retardant.
(5) A paint containing a bleaching agent.
(6) A paint containing a softening agent.
(7) A paint containing a paste.
(8) A paint containing an antifouling agent.

  The fiber material feed mechanism in the fiber material processing apparatus of the present invention is not particularly limited as long as the apparatus is used as long as the fiber material containing the electrolyte solution can be moved to the spray destination of the electrospray sprayer. For example, a roller conveyor, a belt conveyor, etc. are mentioned.

The fiber material processing apparatus of the present invention is not particularly limited in other respects, but preferably has a structure in which the distance between the electrospray sprayer and the fiber material to be sprayed and the spray direction of the electrospray sprayer are variable. Since these are variable, various processing applications and processing conditions can be handled.
In addition, a power source (voltage control device or the like) that generates an electric field between the nozzle of the electrospray sprayer and the fiber material to be sprayed preferably has a variable applied voltage. Since the applied voltage is variable, it is possible to cope with various processing applications and processing conditions.
Moreover, it is preferable to provide a shutter that blocks the sprayed paint from being applied to the fiber material. By providing the shutter, the amount of paint to be applied can be precisely adjusted, and more precise dyeing or the like can be performed.

  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>
Asahi Spinning Co., Ltd. cotton yarn (material: cotton, thickness: No. 4 single yarn) was immersed in an aqueous sodium carbonate solution (concentration: 5% by mass) to prepare a cotton yarn containing an aqueous sodium carbonate solution.
Each of an electrospray sprayer using a glass capillary (caliber: 0.1 mm) with an electrode attached to the tip and a cotton yarn immersed in an aqueous sodium carbonate solution is connected to a high-voltage power supply device (the nozzle electrode is connected to the positive electrode, The cotton yarn was connected to the negative electrode, and the reference electrode was grounded.) Further, the cotton yarn was positioned in the spraying direction of the nozzle, and each was fixed so that the shortest distance between the nozzle tip and the cotton yarn was 30 mm. Then, a potential of +3.0 kV was applied to the electrode of the nozzle, and a potential of -1.4 kV (reference potential: ground) was applied to the cotton yarn, and ethanol spraying was started toward the cotton yarn. A photograph of the sprayed state is shown in FIG.

<Comparative Example 1>
Ethanol was sprayed toward the cotton yarn in the same manner as in Example 1 except that the cotton yarn was not immersed in an aqueous sodium carbonate solution (concentration: 5% by mass). A photograph of the sprayed state is shown in FIG.

  4A and 4B, when the cotton yarn is immersed in the electrolyte solution, the droplets are focused on the cotton yarn, whereas when the cotton yarn is not immersed in the electrolyte solution, the droplets are diffused over a wide range. Is clear. When the cotton yarn is immersed in an electrolyte solution, the cotton yarn becomes a conductor and an electric field is formed between the nozzle and the cotton yarn, so that it is considered that the charged droplets are focused on the cotton yarn.

<Example 2>
The lower end of Asahi Spinning Co., Ltd. cotton yarn (material: cotton, thickness: No. 4 single yarn) with a total length of 2m or more is fixed to the take-up roll, cotton yarn, electrospray sprayer, immersion bath, voltage application electrode, etc. 5 is arranged as shown in the conceptual diagram of FIG. 5 (501 in FIG. 5 is cotton yarn, 502 is an electrospray sprayer, 503 is a sprayed dye solution, 504 is a sodium carbonate solution, 505 is a dipping bath, and 506 is A roller, 507 represents a voltage application electrode, and 508 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. The distance is fixed to be 30 mm. The electrospray sprayer is filled with a dye solution (Remazol RED RU-N, concentration: 0.5% by mass, manufactured by Dystar Japan).
In this embodiment, the cotton yarn is wound up so that the preparation step of immersing the cotton yarn in the electrolyte solution and the spraying step of spraying the dye solution toward the cotton yarn by an electrospray sprayer can be performed continuously. Hereinafter, details of the preparation process and the spraying process will be described.

(Preparation process)
The immersion tank is filled with a sodium carbonate aqueous solution (concentration: 5% by mass), and the cotton yarn is soaked in the sodium carbonate aqueous solution for about 5 seconds and then moved to the spray destination of the electrospray sprayer. Wound up (content of sodium carbonate aqueous solution in cotton yarn: 400% by mass).

(Spraying process)
The dye solution filled from the electrospray sprayer was sprayed toward the cotton yarn that passed through the aqueous sodium carbonate solution to dye the cotton yarn. In addition, spraying was performed by grounding a cotton yarn to the electrode of the nozzle at 5.0 kV. A photograph of the state where the dye solution is sprayed is shown in FIG.

  From FIG. 6, it is clear that the dye solution sprayed from the electrospray sprayer is focused toward the cotton yarn. In addition, the droplets scattered off the cotton yarn are also focused on the cotton yarn so as to be guided by the electric field. In addition, when the utilization efficiency of the dye solution was calculated from the result of measuring the mass and concentration of the sprayed dye solution and the concentration of the dye eluate from the dyed yarn, 37% by mass of the dye solution was applied to the cotton yarn. You can see that it was used. In addition, the droplets scattered without being focused can be collected behind the fiber material, and the amount thereof can be incinerated.

<Example 3>
As shown in the conceptual diagrams shown in FIGS. 7A and 7B, the dye solution was sprayed in the same manner as in Example 2 except that two electrospray sprayers were used to continuously spray two types of dye solutions. In FIG. 7A or FIG. 7B, 701 is cotton yarn, 702 is an electrospray sprayer, 703 is a sprayed dye solution, 704 is an electrospray sprayer, and 705 is sprayed. Dye solution, 706 is a sodium carbonate solution, 707 is a dipping bath, 708 is a roller, 709 is a voltage application electrode, and 710 is a winding roll. A photograph of the state where the dye solution is sprayed is shown in FIG.

  As shown in FIG. 8, by using two or more electrospray sprayers, multicolor dyeing can be performed continuously on one cotton yarn, and gradation dyeing can be performed by adjusting the applied potential and cotton yarn feed rate. It is clear that this processing is possible.

<Comparative example 2>
The dye solution was sprayed from the electrospray sprayer toward the cotton yarn in the same manner as in Example 2 except that it was not immersed in a sodium carbonate solution (concentration: 5.0% by mass). A photograph of the state in which the dye solution is sprayed is shown in FIG. When the cotton yarn is not immersed in the electrolyte solution, it is clear that the dye solution sprayed from the electrospray sprayer diffuses over a wide area and is not sufficiently applied to the cotton yarn.

<Example 4>
The lower end of Asahi Spinning Co., Ltd. cotton yarn (material: cotton, thickness: No. 4 single yarn) having a total length of 2 m or more is fixed to a take-up roll, and the cotton yarn, electrospray sprayer, immersion bath, etc. are shown in FIG. 10100 is cotton thread, 1002 is an electrospray sprayer, 1003 is a sprayed silver nitrate aqueous solution, 1004 is an ascorbic acid aqueous solution, 1005 is a dipping bath, 1006 is a roller, and 1007 is a voltage. Application electrode, 1008 represents a take-up 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)).
This aspect is an aspect in which the preparation process for dipping the cotton thread in the electrolyte solution and the spraying process for spraying the silver nitrate aqueous solution toward the cotton thread by an electrospray sprayer can be performed continuously by winding the cotton thread. Hereinafter, details of the preparation process and the spraying process will be described.

(Preparation process)
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 aqueous 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 aqueous solution in the cotton yarn: 400% by mass).

(Spraying process)
The silver nitrate aqueous solution filled from the electrospray sprayer was sprayed 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. 11 (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.) (1111 in FIG. 11 is processed yarn, 1112 is cotton yarn (for bath ratio adjustment), 1113 is a pot, 1114 is a sample fixing bracket, and 1115 is washed. Water 1116 represents a hot water solution (ethylene glycol)).
A photograph of the cotton yarn before and after spraying is shown in FIG. 12 (A), and a scanning electron micrograph of the cotton yarn after spraying is shown in FIG. 12 (B). It is clear that the cotton yarn is colored black due to the metal silver particle attachment, and fine particles are applied to the surface of the cotton yarn.
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.
The fiber material contains a reducing agent such as ascorbic acid (which also serves as an electrolyte), and metal particles are generated in the fiber material by spraying a paint containing metal ions such as silver nitrate solution. Obviously you can.

<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 4, 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 4. 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 by using the coating method of the present invention, metallic silver particles can be firmly attached to the fiber material without using a binder (binder / binder). When the binder used for the surface processing of the fiber material is used, the exposed area of the fixing substance such as the metallic silver particles is reduced, so that the effect is considered to be reduced, but the coating method of the present invention is used. By doing so, it can be considered “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 4 was evaluated. The antibacterial property was evaluated using a method according to JIS L1902 (bacterial solution absorption method) and 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 are shown in Table 1. In addition, the cotton yarn (referred to as Example 5) 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 3). 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.

<Example 6 (plant dyeing)>
Fix the lower end of Jiangsu Spcc Silk Group Co., Ltd. silk thread (material: silk, thickness: 120Nm double thread) to take-up roll, silk thread, electrospray spray 15A is arranged conceptually as shown in FIG. 15A (1501 in FIG. 15A is silk thread, 1502 is an electrospray sprayer, 1503 is a sprayed dye solution, 1504 Is an electrolyte solution, 1505 is a dipping bath, 1506 is a roller, 1507 is a voltage application electrode, and 1508 is a winding roll. The electrospray sprayer uses a glass capillary (caliber: 0.1 mm) with an electrode attached to the tip as a nozzle, and the silk thread is located on the spraying direction (horizontal direction) of the nozzle, Each is fixed so that the shortest distance between the tip of the nozzle and the silk thread is 20 mm. The electrospray sprayer is filled with liquid vegetable dyes (Suou liquid, Enju liquid (Tanaka direct dye)), liquid plant dyes: ethanol / water = 1/1 (volume ratio).
The immersion tank is filled with a mordant solution (potassium alum or iron (II) sulfate aqueous solution concentration: 1% by mass), and the silk thread is immersed in the mordant solution for about 2 seconds, and then the spray destination of the electrospray sprayer The silk thread was wound up at a speed of 1 m / min so as to move to (content of the mordanting solution of silk thread: 400% by mass).
Liquid vegetable dye was sprayed from an electrospray sprayer toward the silk thread that passed through the mordant solution. The spraying was performed by applying +5.0 kV to the electrode of the nozzle and -3.0 kV (reference potential: ground) to the silk thread.
The sprayed silk thread is collected, baked at 90 ° C for 5 minutes, and washed with water using the apparatus shown in Fig. 11 (condition: after collecting 12 yards of silk thread, put it in a pot of a dyeing tester and rotate it. While washing with water, silk thread: water = 1: 20) and drying (condition: constant temperature drying at 60 ° C.). A photograph of the silk thread is shown in FIG.

<Example 7 (gradation dyeing (cotton))>
The bottom end of Asahi Spinning Co., Ltd. cotton yarn (material: cotton, thickness: No. 20 single yarn) with a total length of 2 m or more is fixed to a winding roll, and the cotton yarn, electrospray sprayer, immersion bath, etc. are shown in FIG. (1601 in FIG. 16A is cotton yarn, 1602 is an electrospray sprayer, 1603 is a sprayed dye solution, 1604 is an electrolyte solution, 1605 is an immersion bath, 1606 Represents a roller, 1607 represents a voltage application electrode, 1608 represents a take-up roll, and 1609 represents a filter paper shutter. The three electrospray sprayers use a glass capillary (caliber: 0.1 mm) with an electrode attached to the tip as a nozzle, and cotton yarn is arranged in parallel on the spraying direction (horizontal direction) of the nozzle. And the shortest distance between the tip of the nozzle and the cotton yarn is fixed to 20 mm. Three electrospray sprayers include three dye solutions (Remazol RED RU-N, manufactured by Dystar Japan, concentration: 5% by mass, Remazol BLUE RU-N, concentration: 5% by mass, Remazol YELLOW RU-N. , Concentration: 5% by mass). The dye sprayed from the electrospray sprayer was blocked by a filter paper shutter to shade the color.
In this embodiment, the cotton yarn is wound up so that the preparation step of immersing the cotton yarn in the electrolyte solution and the spraying step of spraying the dye solution toward the cotton yarn by an electrospray sprayer can be performed continuously. Hereinafter, details of the preparation process and the spraying process will be described.

(Preparation process)
The immersion tank is filled with a sodium carbonate aqueous solution (concentration: 5% by mass), and the cotton yarn is soaked in the sodium carbonate aqueous solution for about 5 seconds and then moved to the spray destination of the electrospray sprayer. Wound up (content of sodium carbonate aqueous solution in cotton yarn: 400% by mass).

(Spraying process)
Three colors of the dye solution filled from the electrospray sprayer were sprayed in order toward the cotton yarn that passed through the aqueous sodium carbonate solution. In addition, it sprayed by applying +4.0 kV to the electrode of a nozzle and -3.7 kV to a cotton thread. A photograph of the silk thread is shown in FIG.

<Example 8 (gradation dyeing (silk))>
Fix the lower end of Jiangsu Spcc Silk Group Co., Ltd. silk thread (material: silk, thickness: 120Nm double thread) to take-up roll, silk thread, electrospray spray 17A is arranged as shown in the conceptual diagram of FIG. 17A (1701 in FIG. 17A is silk thread, 1702 is an electrospray sprayer, 1703 is a sprayed dye solution, 1704 Is an electrolyte solution, 1705 is a dipping liquid tank, 1706 is a roller, 1707 is a voltage application electrode, 1708 is a take-up roll, and 1709 is a filter paper shutter. The three electrospray sprayers use a glass capillary (caliber: 0.1 mm) with an electrode attached to the tip as a nozzle, and the silk thread is juxtaposed in the spraying direction (horizontal direction) of the nozzle. The shortest distance between the nozzle tip and the silk thread is 20 mm. Three electrospray sprayers include three dye solutions (Kayanol Milling Blue BW, Nippon Kayaku Co., Ltd., concentration: 1% by mass, Kayanol Milling Red 3BW, concentration: 1% by mass, Kayanol Milling YELLOW BW, Concentration: 1% by mass). The dye sprayed from the electrospray sprayer was blocked by a filter paper shutter to shade the color.
This aspect is an aspect in which the preparation process of immersing the silk thread in the electrolyte solution and the spraying process of spraying the dye solution toward the silk thread by an electrospray sprayer can be performed continuously by winding the silk thread. Hereinafter, details of the preparation process and the spraying process will be described.

(Preparation process)
The immersion tank is filled with an aqueous ammonium acetate solution (concentration: 0.01M). The silk thread is immersed in the aqueous ammonium acetate solution for about 5 seconds and then moved to the spray destination of the electrospray sprayer. Wound up (content of ammonium acetate aqueous solution in silk: 400% by mass).

(Spraying process)
Three colors of the dye solution filled from the electrospray sprayer were sprayed in order toward the silk thread that passed through the aqueous ammonium acetate solution. In addition, it sprayed by applying +4.0 kV to the electrode of a nozzle and -3.7 kV to a silk thread. A photograph of the silk thread is shown in FIG.

<Example 9 (dark color dyeing)>
The bottom end of Asahi Spinning Co., Ltd. cotton yarn (material: cotton, thickness: No. 20 single yarn) with a total length of 2 m or more is fixed to a winding roll, and the cotton yarn, electrospray sprayer, immersion bath, etc. are shown in FIG. (1) in FIG. 18A is cotton thread, 1802 is an electrospray sprayer, 1803 is a sprayed dye solution, 1804 is an electrolyte solution, 1805 is an immersion bath, 1806 Represents a roller, 1807 represents a voltage application electrode, and 1808 represents a winding roll. The three electrospray sprayers use a glass capillary (caliber: 0.1 mm) with an electrode attached to the tip as a nozzle, and cotton yarn is arranged in parallel on the spraying direction (horizontal direction) of the nozzle. And the shortest distance between the tip of the nozzle and the cotton yarn is fixed to 20 mm. Moreover, all the three electrospray sprayers are filled with the same dye solution (Remazol RED RU-N, concentration: 5% by mass, manufactured by Dystar Japan).
In this embodiment, the cotton yarn is wound up so that the preparation step of immersing the cotton yarn in the electrolyte solution and the spraying step of spraying the dye solution toward the cotton yarn by an electrospray sprayer can be performed continuously. Hereinafter, details of the preparation process and the spraying process will be described.

(Preparation process)
The immersion tank is filled with a sodium carbonate aqueous solution (concentration: 5% by mass), and the cotton yarn is soaked in the sodium carbonate aqueous solution for about 5 seconds and then moved to the spray destination of the electrospray sprayer. Wound up (content of sodium carbonate aqueous solution in cotton yarn: 400% by mass).

(Spraying process)
The dye solution filled from the electrospray sprayer was sprayed in order toward the cotton yarn that passed through the aqueous sodium carbonate solution. In addition, it sprayed by applying +4.0 kV to the electrode of a nozzle and -3.2 kV to a silk thread. A photograph of the silk thread is shown in FIG.

<Example 10 (paper yarn dyeing)>
Fig. 5 shows the paper thread, electrospray sprayer, immersion bath, etc. in Fig. 5 with the lower end of Daigo Fiber Co., Ltd. paper thread (material: paper, thickness 41Nm single thread) with a total length of 2m or more fixed to the take-up roll. 501 is cotton thread, 502 is an electrospray sprayer, 503 is a sprayed dye solution, 504 is a sodium carbonate solution, 505 is a dipping bath, 506 is a roller, and 507 is A voltage application electrode 508 represents a winding roll). The electrospray sprayer uses a glass capillary (caliber: 0.1 mm) with an electrode attached to the tip as a nozzle, and the paper thread is arranged in parallel on the spraying direction (horizontal direction) of the nozzle. It is positioned and fixed so that the shortest distance between the tip of the nozzle and the paper thread is 20 mm. The electrospray sprayer is filled with a dye solution (Remazol RED RU-N, concentration: 5% by mass, manufactured by Dystar Japan).
In this embodiment, the paper yarn is wound up so that the preparation step of immersing the paper yarn in the electrolyte solution and the spraying step of spraying the dye solution toward the paper yarn by an electrospray sprayer can be performed continuously. Hereinafter, details of the preparation process and the spraying process will be described.

(Preparation process)
The immersion tank is filled with an aqueous sodium carbonate solution (concentration: 5% by mass), and the paper thread is immersed in the aqueous sodium carbonate solution for about 5 seconds and then moved to the spray destination of the electrospray sprayer. The yarn was wound up (content of sodium carbonate aqueous solution in paper yarn: 400% by mass).

(Spraying process)
The dye solution filled from the electrospray sprayer was sprayed toward the paper yarn that passed through the aqueous sodium carbonate solution to dye the paper yarn. In addition, spraying was performed by grounding a paper thread to the electrode of the nozzle at 5.0 kV. A photograph of the paper thread is shown in FIG.

  Pictures of cotton yarns dyed with other reactive dyes are shown in FIG. It is clear that the coating method of the present invention can be used for dyeing various fiber materials such as cotton, silk and paper. It is also clear that it can be applied to various types of dyes.

  The coating method of the present invention can efficiently apply a paint to fiber materials such as yarns, woven fabrics, nonwoven fabrics, papers, etc., so that it can be dyed, antibacterial debrominated, water and oil repellent, flame retardant It can be used for chemical treatment, bleaching treatment, softening treatment and the like.

DESCRIPTION OF SYMBOLS 101 Fiber material containing electrolyte solution 102 Nozzle of electrospray sprayer 103 Sprayed paint 104 Distance between electrospray sprayer nozzle and fiber material 201 Fiber material containing electrolyte solution 202 Electrospray sprayer 203 Sprayed Sprayed paint of a type different from paint 204 203 301 Fiber material 302 Roller 303 Electrospray sprayer 304 Sprayed paint 305 Liquid bath for immersion 306 Electrolyte solution 307 Spraying device for spraying electrolyte solution 308 Sprayed electrolyte solution 309 Dripping device 310 Dropped electrolyte solution 501 Cotton yarn 502 Electrospray sprayer 503 Sprayed dye solution 504 Sodium carbonate solution 505 Liquid bath for immersion 506 Roller 507 Electrode for voltage application 508 Winding Roll 701 Cotton yarn 702 Electrospray sprayer 703 Sprayed dye solution 704 Electrospray sprayer 705 Sprayed dye solution 706 Sodium carbonate solution 707 Soaking bath 708 Roller 709 Voltage application electrode 710 Winding roll 1001 Cotton yarn 1002 Electro Spray sprayer 1003 Sprayed silver nitrate aqueous solution 1004 Ascorbic acid aqueous solution 1005 Immersion bath 1006 Roller 1007 Voltage application electrode 1008 Winding roll 1111 Work yarn 1112 Cotton yarn (for bath ratio preparation)
1113 Pot 1114 Fixing metal fitting 1115 Washing water 1116 Hot water bath solution (ethylene glycol)
1301 Textile material before processing 1302 Water tank containing electrolyte solution 1303 Dyeing process 1304 Functional material addition (antibacterial debromination process) 1305 Gluing process 1306 Electrospray sprayer 1307 Heating and drying apparatus 1501, 1701
Silk thread 1502, 1602, 1702, 1802
Electrospray sprayer 1503, 1603, 1703, 1803
Sprayed dye solution 1504, 1604, 1704, 1804
Electrolyte solution 1505, 1605, 1705, 1805
Immersion bath 1506, 1606, 1706, 1806
Rollers 1507, 1607, 1707, 1807
Voltage application electrodes 1508, 1608, 1708, 1808
Winding rolls 1601, 1801
Cotton thread 1609, 1709
Filter paper shutter

Claims (13)

A method for applying a paint to a fiber material, comprising: a preparation step of preparing a fiber material containing an electrolyte solution; and a spraying step of spraying the paint toward the fiber material by electrospray,
When the fiber material contains a reducing agent and the paint is a solution containing metal ions, the paint containing metal ions is sprayed on the fiber material in the spraying step, so that the metal ions and the reduction are reduced. A method of applying a paint to a fiber material, wherein the agent reacts to form metal particles in the fiber material.   The coating method according to claim 1, wherein the spraying step includes spraying one type or two or more types of paints using two or more electrospray sprayers.   The coating method according to claim 2, wherein the spraying step includes a step of continuously spraying one or more types of paints by moving the fiber material and / or the electrospray sprayer. . The electrolyte solution, alkali metal salts is a solution containing at least one alkaline earth metal salts, aluminum salts, selected from the group consisting of ammonium salts and transition metal salts, claim 1-3 The coating method according to one item. The preparation step is a step including at least one selected from the group consisting of immersing the fiber material in an electrolyte solution, spraying the electrolyte solution onto the fiber material, and dropping the electrolyte solution onto the fiber material. The coating method as described in any one of Claims 1-4 . The paint is a solution containing at least one selected from the group consisting of a dye, an antibacterial agent, a deodorant, a water / oil repellent, a flame retardant, a bleach, a softener, a paste, and an antifouling agent. The coating method according to any one of claims 1 to 5 . The coating method according to any one of claims 1 to 6 , wherein the preparation step and the spraying step are continuously performed by moving the fiber material containing the electrolyte solution. The fiber material, yarn, woven fabric, a nonwoven, knit, paper, or film, the coating method according to any one of claims 1-7. The manufacturing method of a fiber material characterized by including the at least 1 sort (s) of process selected from the group which consists of following (1)-(8).
(1) A dyeing process comprising applying a paint containing a dye by the applying method according to any one of claims 1 to 8 and dyeing the fiber material.
(2) A coating material containing an antibacterial agent and / or deodorant is applied by the coating method according to any one of claims 1 to 8 to impart an antibacterial action and / or a deodorizing action to the fiber material. An antibacterial debromination process comprising:
(3) Water repellent and water repellent comprising applying a paint containing a water and oil repellent by the coating method according to any one of claims 1 to 8 to impart a water and oil repellent action to the fiber material. Oiling process.
(4) A flame retardant treatment step of applying a paint containing a flame retardant by the coating method according to any one of claims 1 to 8 to make the fiber material difficult to burn.
(5) A bleaching treatment step including bleaching a fiber material by applying a paint containing a bleaching agent by the coating method according to any one of claims 1 to 8 .
(6) A softening treatment step including applying a paint containing a softening agent by the coating method according to any one of claims 1 to 8 to impart flexibility to the fiber material.
(7) A gluing treatment step including gluing a fiber material by applying a paint containing a gluing agent by the coating method according to any one of claims 1 to 8 .
(8) An antifouling treatment step comprising applying a paint containing an antifouling agent by the coating method according to any one of claims 1 to 8 to impart an antifouling action to the fiber material. Furthermore, the manufacturing method of the fiber material of Claim 9 including the at least 1 sort (s) of process selected from the group which consists of a spinning process, a drawing process, a spinning process, a knitting process, and a scouring process.   Selected from the group consisting of immersing the fiber material in an electrolyte solution containing a reducing agent, spraying the electrolyte solution containing the reducing agent onto the fiber material, and dropping the electrolyte solution containing the reducing agent onto the fiber material Electrolyte solution contact mechanism for performing at least one of the above, an electrospray sprayer for spraying a paint containing metal ions toward the fiber material containing the electrolyte solution, and the electrospray for the fiber material containing the electrolyte solution A fiber material processing apparatus comprising a fiber material feed mechanism for moving to a spray destination of a sprayer. The fiber material processing apparatus according to claim 11 , comprising two or more electrospray sprayers. The fiber material processing apparatus according to claim 11 or 12 , comprising an electrospray sprayer that sprays at least one paint selected from the group consisting of the following (1) to (8) as the electrospray sprayer.
(1) A paint containing a dye.
(2) A paint containing an antibacterial agent and / or a deodorant.
(3) A paint containing a water / oil repellent.
(4) A paint containing a flame retardant.
(5) A paint containing a bleaching agent.
(6) A paint containing a softening agent.
(7) A paint containing a paste.
(8) A paint containing an antifouling agent.