Method for producing antibacterial / antifungal fiber structure, and antibacterial / antifungal fiber structure

Abstract

The present invention provides: a method for producing an antibacterial / antifungal fiber structure having excellent washing durability, in which an antibacterial / antifungal component is directly fixed to a fiber structure so that it is possible to suppress the deterioration in air permeability and texture of fibers, avoid adverse effects of formalin release on the environment and human bodies, and also suppress the deterioration in strength of the fiber structure; and an antibacterial / antifungal fiber structure produced by the method. The method comprises: a processing liquid preparation step for preparing a processing liquid 6 that contains an antibacterial / antifungal composition and does not contain a film-formable compound; and a processing liquid heating step for adhering the processing liquid 6 to a fiber structure 2 and heating the resultant product at 100-230°C for 0.5 minute or longer under ambient pressure or under pressurized conditions. The antibacterial / antifungal composition contains a metal oxide (A), the fiber structure 2 comprises synthetic fibers, and the antibacterial / antifungal component is directly fixed at a ratio of 0.02 part by mass or more per 100 parts by mass of the fiber structure 2.

Description

Manufacturing method for antibacterial and antifungal fiber structure, antibacterial and antifungal fiber structure

[0001] The present invention relates to a method for producing an antibacterial and antifungal fiber structure, and to an antibacterial and antifungal fiber structure. More specifically, the present invention relates to a method for producing an antibacterial and antifungal fiber structure in which an antibacterial and antifungal component is directly fixed to the surface of the fiber structure without using a film-forming compound (so-called resin binder), thereby enabling sufficient antibacterial and antifungal properties to be exhibited with only a small amount of the antibacterial and antifungal component, without significantly impairing the texture of the fiber structure, and to the antibacterial and antifungal fiber structure obtained thereby.

[0002] In recent years, various household and industrial products, including clothing, have been proposed that incorporate antibacterial and antifungal components directly to impart antibacterial and antifungal properties to the product itself. However, simply applying an antibacterial or other chemical agent to the product itself easily removes the agent through washing, and various methods for sustaining the antibacterial and antifungal effects on textile products have been investigated. One such method, for example, involves immobilizing the antibacterial and antifungal compound by forming a resin coating on the fiber surface or between fibers using a polymer emulsion film-forming compound together with the antibacterial and antifungal compound (see Patent Document 1). Furthermore, to prevent the antibacterial and antifungal compound from leaching from the substrate (e.g., plastic, cloth, or fiber) to which it is attached, an antibacterial and antifungal agent in the form of an immobilized antibacterial / metal composite has been proposed (see Patent Document 2). Furthermore, a coating agent using a binder to impart heat-retaining, antibacterial, deodorizing, and deodorizing properties, and a processed fiber obtained by processing the same have been proposed (see Patent Document 3).

[0003] Special table publication No. 2009-538319 Publication of patent application No. 2009-512015 Publication of patent application No. 07-41082

[0004] However, methods using a film-forming compound such as a polymer emulsion as a binder to adhere and fix antibacterial and antifungal compounds to fibers through a resin coating have problems with the formation of a resin coating, which reduces the breathability and feel of the fiber and often causes discoloration, making them unsuitable for clothing and interior applications. Another problem is that the resin coating peels off due to friction and other factors, reducing the antibacterial and antifungal properties, resulting in short-term performance. Furthermore, film-forming compounds used to form the coating (e.g., melamine-based compounds and glyoxal-based compounds) have concerns about the adverse effects on the environment and human body due to the release of formalin. On the other hand, products made by kneading and spinning raw materials containing antibacterial agents into fibers improve the wash durability of the antibacterial and antifungal properties, but the antibacterial and antifungal agents are contained in the interior, which does not contribute to the effects, resulting in a high content of antibacterial and antifungal agents and increased costs. Another problem is that the strength of the yarn tends to decrease due to the antibacterial and other agents.

[0005] Therefore, in this invention, under the above circumstances, the antibacterial and antifungal component is not fixed to the fiber structure by a resin coating or by incorporating the antibacterial and antifungal component into the raw material for spinning, but the antibacterial and antifungal component is directly fixed to the fiber structure, thereby preventing deterioration of the breathability and feel of the fiber, suppressing discoloration, and preventing the adverse effects of formalin release on the environment and human body. The invention also provides a method for producing an antibacterial and antifungal fiber structure with excellent washing durability, and the antibacterial and antifungal fiber structure obtained thereby.

[0006] The present inventors conducted extensive research to develop a method for imparting antibacterial and antifungal properties with water resistance and washing durability to resin molded articles used in various industrial materials, household products (including clothing), and the like. As a result, they discovered that by preparing a processing solution by adding a metal oxide (A), which has traditionally been known as an antibacterial and antifungal agent, to a predetermined concentration in a solvent such as water, and then contacting the processing solution with a textile structure and subjecting it to a heat treatment for a predetermined period of time, the metal oxide (A) can be directly fixed to the surface of the textile structure without the need to form a resin coating using a film-forming compound. They also discovered that the metal oxide (A) fixed to the textile structure exhibits excellent antibacterial and antifungal properties, making it possible to impart antibacterial and antifungal properties with excellent water resistance and washing durability to various textile structures.

[0007] That is, the present invention has the following aspects. [1] A method for producing an antibacterial and antifungal fiber structure in which a metal oxide (A) contained in an antibacterial and antifungal composition is directly fixed to the surface of the fiber structure, the method comprising: a processing solution preparation step of preparing a processing solution containing the antibacterial and antifungal composition but not containing a film-forming compound; and a processing solution heating step of applying the processing solution to the fiber structure and heating it at 100 to 230°C under normal pressure or pressure for 0.5 minutes or more, thereby directly fixing the metal oxide (A) in an amount of 0.02 parts by mass or more per 100 parts by mass of the fiber structure. [2] A method for producing an antibacterial and antifungal fiber structure according to [1], in which the metal oxide (A) is spot-fixed to the surface of the fiber structure. [3] A method for producing an antibacterial and antifungal fiber structure according to [1] or [2], in which the metal oxide (A) is at least one compound selected from the group consisting of zinc oxide, titanium oxide, silver oxide, and copper oxide. [4] The method for producing an antibacterial and antifungal fiber structure according to any one of [1] to [3], wherein the antibacterial and antifungal composition further contains an isothiazolin-based compound (B). [5] The method for producing an antibacterial and antifungal fiber structure according to [4], wherein the isothiazolin-based compound (B) is at least one compound selected from the group consisting of 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and 1,2-benzisothiazolin-3-one. [6] The method for producing an antibacterial and antifungal fiber structure according to [4] or [5], wherein in the antibacterial and antifungal composition, the mass ratio (B / A) of the isothiazolinone compound (B) to the metal oxide (A) is set to 0.01 to 0.25. [7] The method for producing an antibacterial and antifungal fiber structure according to any of [1] to [6], wherein the metal oxide (A) is composed of 50 mass % or more of particles having a particle diameter of 100 to 400 nm.[8] The method for producing an antibacterial and antifungal fiber structure according to any one of [1] to [7], wherein the film-forming compound is at least one selected from the group consisting of acrylic compounds, urethane compounds, silicone compounds, epoxy compounds, polyester compounds, and melamine compounds. [9] The method for producing an antibacterial and antifungal fiber structure according to any one of [1] to [8], wherein the processing solution contains phosphoric acid and / or citric acid.

[10] The method for producing an antibacterial and antifungal fiber structure according to any one of [1] to [9], wherein the processing solution has a pH in the range of 3 to 6.

[11] An antibacterial and antifungal fiber structure in which the metal oxide (A) is directly fixed in an amount of 0.02 parts by mass or more per 100 parts by mass of the fiber structure, the antibacterial and antifungal fiber structure having an antibacterial activity value of 2.0 or more and an antifungal activity value of 1 or more.

[12] The antibacterial and antifungal fiber structure according to

[11] , wherein the fiber structure contains synthetic fibers.

[13] The antibacterial and antifungal fiber structure according to

[11] or

[12] , which, after 10 washes by a standard washing method (a method for washing SEK-marked fiber products), has an antibacterial activity value of 2.0 or more and an antifungal activity value of 1 or more.

[14] The antibacterial and antifungal fiber structure according to any one of

[11] to

[13] , which, after 50 washes by a high-temperature accelerated washing method (a method for washing SEK-marked fiber products), has an antibacterial activity value of 2.0 or more and an antifungal activity value of 1 or more.

[15] The antibacterial and antifungal fiber structure according to any one of

[11] to

[14] , which, after 10 washes by a standard washing method (a method for washing SEK-marked fiber products), has a deodorizing rate of 50% or more against at least one odor selected from the group consisting of ammonia, acetic acid, and isovaleric acid.

[16] The antibacterial and antifungal fiber structure according to any one of

[11] to

[15] , wherein an isothiazolinone compound (B) is directly fixed to a fiber structure having synthetic fibers, and the ratio of the isothiazolinone compound (B) to 1 part by mass of the metal oxide (A) is set to 0.01 to 0.25 parts by mass.

[17] The antibacterial and antifungal fiber structure according to any one of

[11] to

[16] , wherein the metal oxide (A) is composed of particles having a particle diameter of 100 to 400 nm in an amount of 50% by mass or more.

[0008] The method for producing an antibacterial and antifungal fiber structure of the present invention can directly fix the antibacterial and antifungal component to the fiber structure without using a resin coating to fix the antibacterial and antifungal component to the fiber structure or incorporating the antibacterial and antifungal component into the spinning raw material. This prevents deterioration of the breathability and feel of the fiber structure, reduces the risk of discoloration, and prevents the film-forming compound used to form the resin coating from adversely affecting the environment and human body. This allows for the production of an antibacterial and antifungal fiber structure with excellent washing durability. Furthermore, the antibacterial and antifungal fiber structure of the present invention exhibits antibacterial and antifungal properties, as well as deodorizing properties, and these deodorizing, antibacterial, and antifungal properties are water-resistant and wash-durable. Furthermore, the antibacterial and antifungal fiber structure can be repeatedly washed, wiped with water, and laundered without losing its deodorizing, antibacterial, and antifungal properties, which has the advantage of allowing the antibacterial and antifungal fiber structure to be kept clean for a long period of time.

[0009] Fig. 1(a) is a diagram illustrating the manufacturing process of this embodiment, and Fig. 1(b) is a diagram illustrating another manufacturing process of this embodiment. Fig. 2(a) is a diagram illustrating the surface of the fiber structure used in this embodiment, observed with an electron microscope, and Fig. 2(b) is a diagram illustrating the detection of zinc present on the surface. Fig. 3(a) is a diagram illustrating the surface of the fiber structure used in this embodiment, observed with an electron microscope, and Fig. 3(b) is a diagram illustrating the detection of zinc present on the surface. Fig. 4(a) is a diagram illustrating the surface of a conventional fiber structure, observed with an electron microscope, and Fig. 4(b) is a diagram illustrating the detection of zinc present on the surface. Fig. 4 is a graph comparing the XRD diffraction of the antibacterial and antifungal component of this embodiment and zinc oxide.

[0010] The present invention will be described below based on examples of embodiments for carrying out the present invention, but the present invention is not limited to the embodiments described below.

[0011] As used herein, "x and / or y (x and y are any configuration)" refers to at least one of x and y, and can mean three things: x only, y only, or x and y. In this specification, when "X to Y" (X and Y are any numbers) is used, unless otherwise specified, it also means "X or more and Y or less," as well as "preferably greater than X" or "preferably smaller than Y." In this specification, when "X or more" (X is any number) or "Y or less" (Y is any number) is used, it also means "preferably greater than X" or "preferably less than Y." For numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. Furthermore, in the numerical ranges described herein, the upper or lower limit of the numerical range can also be replaced with the values ​​shown in the examples.

[0012] The method for producing the antibacterial and antifungal fiber structure of this embodiment and the antibacterial and antifungal fiber structure will be described in detail below.

[0013] (Textile structure) In this embodiment, the textile structure to which antibacterial and antifungal properties are to be imparted is the fiber itself or a material made from such fibers. The textile structure prepared before imparting antibacterial and antifungal properties may be in the form of the final product as is, or the textile structure may be modified or combined with other components to change its shape or configuration to form the final product.

[0014] Such fiber structures can be in various forms, such as spun yarns, knitted fabrics, woven fabrics, and nonwoven fabrics. Specific products include, for example, various types of clothing, socks, tights, sportswear, outdoor products, bedding, rugs, curtains, indoor cloths, and sanitary products such as bandages, gauze, and masks. In particular, the fiber structure of the present invention is suitable for application to sportswear, clothing, socks, tights, outdoor products, and bedding, because it has a pleasant feel, excellent antibacterial and antifungal properties, excellent washing durability, and no concerns about adverse effects on the environment or the human body.

[0015] The fiber structure used in this embodiment uses natural fibers, synthetic fibers, and blends thereof as its constituent fibers. Examples of the natural fibers include cotton, linen, silk, and wool. Of these, cotton is preferably used. Examples of the synthetic fibers include polyester resins, polyamide resins, acrylic resins, and polyurethane resins. Of these, polyethylene terephthalate, nylon, and acrylic are preferably used from the viewpoints of durability and weather resistance. The synthetic fibers also include semi-synthetic fibers such as cellulose resins and acetate resins, as well as composites and mixtures thereof.

[0016] The fiber structure used in this embodiment may be a mixture of natural or synthetic fibers with components other than synthetic fibers (metals, inorganic substances, etc.), or a blend of synthetic fibers with natural fibers such as cotton, acetate, rayon, wool, or silk. When the fiber structure of this embodiment contains fibers other than synthetic fibers, the content of such fibers is preferably 50% by mass or less of the total mass of the fiber structure, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoints of durability and weather resistance.

[0017] (Antibacterial and Antifungal Composition) The antibacterial and antifungal composition used in this embodiment contains a metal oxide (A), and preferably contains an isothiazolinone compound (B).

[0018] Examples of the metal oxide (A) include zinc oxide, titanium oxide, silver oxide, copper oxide, etc. Among these, zinc oxide is preferred.

[0019] Examples of the isothiazoline compound (B) include 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, etc. Among these, 1,2-benzisothiazolin-3-one is preferred.

[0020] In view of excellent dispersibility, the metal oxide (A) is preferably composed of particles having a particle diameter of 100 to 400 nm in an amount of 50 mass % or more. The particle diameter of the metal oxide (A) can also be calculated as the median diameter corresponding to a cumulative 50% in a particle size distribution measured using a laser diffraction particle size distribution analyzer in accordance with JIS R1629.

[0021] Furthermore, when an isothiazolinone compound (B) is used as the antibacterial and antifungal component, from the viewpoint of safety, the mass ratio (B / A) of the isothiazolinone compound (B) to the metal oxide (A) is preferably set to 0.01 to 0.25, more preferably 0.01 to 0.1, and even more preferably 0.01 to 0.05.

[0022] (Working Fluid) The working fluid used in this embodiment contains the antibacterial and antifungal composition but does not contain a film-forming compound. That is, the working fluid is obtained by diluting the antibacterial and antifungal composition to a predetermined concentration with an aqueous solvent (water or water to which a water-soluble organic solvent such as ethanol, n-propanol, or ethylene glycol has been added), with water being the preferred aqueous solvent. The film-forming compound is a compound used to fix various components by forming a resin film on the surface of a fiber structure or between fibers. Examples of such film-forming compounds include acrylic compounds, urethane compounds, silicone compounds, epoxy compounds, polyester compounds, and melamine compounds. In this embodiment, "not containing a film-forming compound" refers not only to a case where the working fluid does not contain any film-forming compound at all, but also to a case where the working fluid contains a trace amount of the film-forming compound that does not allow the film-forming compound to exhibit its properties.

[0023] The content of the antibacterial and antifungal composition in the processing liquid is set taking into consideration the mass of the fiber structure to be treated and the mass of the antibacterial and antifungal component contained in the antibacterial and antifungal composition, and typically the processing liquid contains the antibacterial and antifungal composition at a concentration of preferably 0.01 to 5 mass%, more preferably 0.02 to 2 mass%, and even more preferably 0.04 to 1 mass%. Setting the content within this range has the advantage that the concentration of the antibacterial and antifungal component in the processing liquid can be easily set within a desired range.

[0024] The processing liquid may contain a function-imparting component other than the antibacterial and antifungal composition, and among these, from the viewpoint of deodorizing and antibacterial properties, it is more preferable that the processing liquid contain an organic acid such as phosphoric acid or citric acid.The processing liquid preferably has a pH of 3 to 6, more preferably a pH of 4 to 5, from the viewpoint of improving the fixation rate of the antibacterial and antifungal component to the fiber structure.

[0025] In addition to the above, the processing solution may contain various additives, such as swelling agents, penetrating agents, emulsifying / dispersing agents, sequestering agents, leveling agents, softeners, suspending agents, migration inhibitors, carriers, dye-resistant agents, wrinkle-resistant agents, and texture-improving agents, as needed.

[0026] Furthermore, in the processing liquid, depending on the types of auxiliary agents and additives used, the material of the target fiber structure, etc., water-soluble organic solvents such as ethanol, n-propanol, ethylene glycol, etc. can be used together with or instead of water. In some cases, non-aqueous solvents can also be used.

[0027] 1(a), for example, an aqueous solvent is placed in a treatment tank 1, and the antibacterial and antifungal composition is added to the water, and other components are also added as needed, to prepare a working fluid 6 having a predetermined amount of antibacterial and antifungal components. That is, the aqueous solvent that forms the base of the working fluid is usually water, and if necessary, a working fluid 6 containing a small amount of a solvent or water-soluble substance may be used.

[0028] (Processing Liquid Heat Treatment Step) The method for applying the processing liquid to the fiber structure and the method for heating the processing liquid can be appropriately selected depending on the material of the fiber structure. For example, as shown in FIG. 1( a), a method in which a fiber structure 2 is immersed in a processing liquid 6 and heat-treated in that state at a predetermined temperature and a predetermined pressure can be mentioned. That is, the fiber structure 2 is immersed in the processing liquid 6 in the treatment tank 1, and then is pulled up while being gently squeezed by passing it through squeeze rolls 3, and then introduced into a heating device 4. The fiber structure 2 with a predetermined amount of the processing liquid 6 attached thereto is subjected to a heat treatment (so-called "pad drying process") at a predetermined temperature (140 to 230°C) for a predetermined time (0.5 minutes or more) while being moved within the heating device 4, and can then be dried via a dryer 5 as needed.

[0029] 1(b), for example, the fiber structure 2 is immersed in a processing liquid 6 and heat-treated in that state at a predetermined temperature and a predetermined pressure. That is, after the fiber structure 2 is immersed in the processing liquid 6 in this processing tank 1, it is heated under sealed conditions and subjected to a heat treatment (so-called "exhaustion processing") at a predetermined temperature (100 to 140°C) for a predetermined time (20 minutes or more) under pressure, and then dried as necessary.

[0030] To fix a predetermined amount of the antibacterial / antifungal component to the fiber structure, the concentration of the antibacterial / antifungal component in the processing liquid and the amount of the processing liquid applied relative to the amount of the target fiber structure material can be set. For example, to directly fix the antibacterial / antifungal component at a ratio of 0.02 parts by mass per 100 parts by mass of the fiber structure, 100 parts by mass of processing liquid containing 0.02 parts by mass of the antibacterial / antifungal component can be applied to 100 parts by mass of the fiber structure (100% wt.).

[0031] On the other hand, if the density of the fiber structure is high, applying a large amount of liquid may cause the fiber structure to become too heavy and unable to be sufficiently squeezed. Therefore, in such a case, it is preferable to apply a small amount of liquid (increase the mass of the antibacterial and antifungal component contained in the liquid) and set the mass of the antibacterial and antifungal component fixed to the fiber structure.

[0032] Another method for applying the processing liquid to a fiber structure is to apply the processing liquid to the fiber structure by immersion (impregnation), spraying, coating, etc. under normal pressure, and then squeezing it to a predetermined squeezing rate using a mangle or centrifuge, etc.

[0033] The antibacterial and antifungal fiber structure of this embodiment obtained in this manner is set so that the antibacterial and antifungal component is adhered in a ratio of 0.02 parts by mass or more, preferably 0.05 to 2 parts by mass, and more preferably 0.1 to 1 part by mass per 100 parts by mass of the fiber structure.

[0034] The heat treatment with the processing liquid attached to the fiber structure is carried out under normal pressure or under pressure. The heat treatment temperature is 140 to 230°C, preferably 140 to 180°C, and more preferably 140 to 160°C. If the heat treatment temperature is too low, the fiber structure will not be heated sufficiently, and the components will tend to be insufficiently fixed. Conversely, if the heat treatment temperature is too high, the fiber structure will tend to be damaged. The heat treatment time is 0.5 minutes or more, preferably 0.5 to 10 minutes, and more preferably 0.5 to 3 minutes. If the heat treatment time is too short, the fiber structure will not be heated sufficiently, and the components will tend to be insufficiently fixed. Conversely, if the heat treatment time is too long, the fiber structure will tend to be damaged.

[0035] (Antibacterial / Anti-fungal Fiber Structure) In the present embodiment, the antibacterial / anti-fungal fiber structure has an antibacterial / anti-fungal component directly fixed to it in a proportion of 0.02 parts by mass or more per 100 parts by mass of a fiber structure containing synthetic fibers. However, it is practically difficult to determine the amount of the antibacterial / anti-fungal component fixed from the antibacterial / anti-fungal fiber structure alone. Therefore, in this embodiment, a predetermined amount of the antibacterial / anti-fungal component is directly fixed to the fiber structure by applying a predetermined amount of a processing liquid containing the antibacterial / anti-fungal component to the fiber structure and then performing a heat treatment under predetermined conditions.

[0036] Therefore, it can be said that the antibacterial and antifungal component is directly fixed to the antibacterial and antifungal fiber structure obtained by the manufacturing method of this embodiment at a ratio of 0.02 mass parts or more per 100 mass parts of the fiber structure.

[0037] Here, "the antibacterial / antifungal component is directly fixed to the fiber structure" means that the antibacterial / antifungal component is bonded to the surface of the fiber structure by a chemical bond, and does not mean that the antibacterial / antifungal component is attached and fixed to the fiber structure by a resin coating using a film-forming compound. Examples of the chemical bond include a covalent bond, an ionic bond, a hydrogen bond, and a coordinate bond.

[0038] The reason why the antibacterial and antifungal component is directly fixed to the fiber structure is not clear, but when the surface of the antibacterial and antifungal fiber structure of this embodiment was observed with an electron microscope, as shown in Figures 3(a) and 3(b), the fixation of the antibacterial and antifungal component was observed primarily in areas with high fiber surface area, such as areas of high fiber density where the warp and weft threads intersect in the fiber structure, and uneven areas on the surface of the fiber structure, and therefore it is presumed that the antibacterial and antifungal component is fixed by the interaction between the charge (+) of the antibacterial and antifungal component (e.g., zinc in zinc oxide) and the charge (COO-) of the synthetic fiber (e.g., polyester).

[0039] In this embodiment, the antibacterial and antifungal component is spot-fixed to the surface of the textile structure. Here, spot-fixed refers to the antibacterial and antifungal component being unevenly distributed rather than uniformly fixed to the surface of the textile structure, as shown in the electron microscope images in Figures 3(a) and 3(b). The amount of fixation is preferably 1 / 30 to 1 / 3 of the surface area of ​​the textile structure. It is particularly preferable that zinc oxide is unevenly fixed in the form of clumps measuring 50 nm to 1000 nm, as shown in Figure 3(b). In this embodiment, the antibacterial and antifungal component is firmly spot-fixed to the surface of the textile structure by chemical bonding, thereby improving washing durability.

[0040] On the other hand, when a film-forming compound is blended into the processing liquid, the metal oxide (A) is fixed in a state where it is encapsulated in a resin film, as shown in Figures 4(a) and 4(b). Therefore, the metal oxide (A) is spread thinly over the entire surface of the fiber structure and fixed in a state where it fills the gaps between the fibers, and usually a large area, typically half or more of the surface area of ​​the fiber structure, is covered with a film containing the metal oxide (A) therein.

[0041] The fact that the antibacterial and antifungal components are spot-fixed on the surface of the textile structure can be seen by comparing the textile structure before and after treatment. That is, as shown in Figures 2(a) and 2(b), nothing other than the textile structure (the antibacterial and antifungal components) is visible in the textile structure before treatment. However, as shown in Figures 3(a) and 3(b), the textile structure after treatment (the antibacterial and antifungal textile structure of this embodiment) shows that nothing other than the textile structure (the antibacterial and antifungal components) is partially fixed (spot-fixed) on its surface. Note that Figures 2 to 4 were all observed using an electron microscope at 1000x magnification. Also, Figures 2 to 4(a) are actual images, and Figures 2 to 4(b) are zinc atom mapping diagrams obtained by EDX (Energy Dispersive X-ray Spectroscopy). The fiber structure shown in Fig. 3(a) and Fig. 3(b) is the fiber structure shown in Example 9 described below.

[0042] In this embodiment, the antibacterial and antifungal component is mainly composed of metal oxide (A). That is, Fig. 5 shows the XRD diffraction charts obtained by superimposing the antibacterial and antifungal component shown in black in Fig. 3(b) and zinc oxide. As indicated by the downward arrows, these charts and peak shapes are nearly identical, indicating that the antibacterial and antifungal component and zinc oxide are nearly identical. Furthermore, although the peak heights become slightly lower with increasing washing frequency, similar peak shapes are still obtained, indicating that the antibacterial and antifungal component is firmly fixed (spot fixed) to the surface of the textile structure.

[0043] In this embodiment, the metal oxide (A) is directly fixed as the antibacterial and antifungal component in an amount of 0.02 parts by mass or more per 100 parts by mass of the fiber structure. From the viewpoint of antibacterial properties, however, the amount is preferably 0.05 to 2 parts by mass, and more preferably 0.1 to 1 part by mass.

[0044] In this embodiment, the isothiazolinone compound (B) is preferably directly fixed as the antibacterial and antifungal component in an amount of 0.0006 part by mass or more per 100 parts by mass of the fiber structure. From the viewpoint of safety, the amount is more preferably 0.0006 to 0.05 parts by mass, even more preferably 0.001 to 0.05 parts by mass, and even more preferably 0.005 to 0.05 parts by mass.

[0045] Furthermore, when an isothiazolinone compound (B) is used as an antibacterial and antifungal component, from the viewpoint of safety, the mass ratio (B / A) of the isothiazolinone compound (B) directly fixed to the fiber structure to the metal oxide (A) is preferably set to 0.01 to 0.25, more preferably 0.01 to 0.1, and even more preferably 0.01 to 0.05.

[0046] The antibacterial and antifungal fiber structure of this embodiment has the antibacterial and antifungal component directly fixed to it at a ratio of 0.02 mass parts or more per 100 mass parts of the fiber structure, and therefore has the following antibacterial and antifungal properties.

[0047] (Deodorizing Properties) The composition has deodorizing properties against alkaline odors (e.g., odors caused by ammonia) and / or acidic odors (e.g., odors caused by acetic acid and isovaleric acid), and the deodorizing rate for at least one of the odors of ammonia, acetic acid, and isovaleric acid is 50% or more, and preferably 70% or more. (Antibacterial Properties) The composition has an antibacterial activity value of 2.0 or more against at least one of Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, Klebsiella pneumoniae, Bacillus subtilis, Bacillus cereus, Escherichia coli, Salmonella, and Pseudomonas aeruginosa, which are particularly common bacteria that cause food poisoning and infectious diseases. (Antifungal Properties) The composition has an antifungal activity value of 1 or more against at least one of Aspergillus niger, Penicillium niger, Aspergillus niger, Trichophyton niger, and Candida, which are particularly common fungi that cause deterioration of objects and infectious diseases. More preferably, the value is 2 or more.

[0048] The evaluation of the deodorizing property is carried out in accordance with the performance test method for deodorizing processed textile products (ISO 17299-3 gas chromatography method) as follows. 2 Each test piece was cut into 1 / 4" pieces to prepare sample pieces, and 5 μL of the odor component prepared for each odor was poured into a 500 mL Erlenmeyer flask containing the sample pieces. After 2 hours, the flask was vigorously stirred and the odor concentration was measured using a gas chromatograph. At this time, the same procedure was performed without adding the sample pieces, and the odor concentration measured was used as the blank test concentration. The deodorizing rate (%) was calculated based on the following formula. Therefore, the larger the deodorizing rate (%), the better the deodorizing properties. Deodorizing rate (%) = (1 - (sample piece concentration) / (blank test concentration)) x 100

[0049] The antibacterial properties were evaluated by the following method in accordance with JIS L1902. Specifically, the target bacteria were inoculated into a standard piece (a fiber structure that does not exhibit antibacterial activity) and a sample piece obtained by cutting the target fiber structure, and the number of viable bacteria on each piece was measured after culturing at 37°C for 18 to 24 hours. The antibacterial activity value was calculated from the obtained viable bacteria counts according to the following formula. Antibacterial activity value = (LogCt - LogCo) - (LogTt - LogTo) F: Growth value of standard specimen = (LogCt - LogCo) LogCo: Common logarithm of the arithmetic mean of the viable bacterial count on the standard specimen immediately after inoculation with the test bacteria LogCt: Common logarithm of the arithmetic mean of the viable bacterial count on the standard specimen after 18 hours of culture LogTo: Common logarithm of the arithmetic mean of the viable bacterial count on the sample specimen immediately after inoculation with the test bacteria LogTt: Common logarithm of the arithmetic mean of the viable bacterial count on the sample specimen after 18 hours of culture

[0050] The antifungal properties were evaluated by the following method in accordance with JIS L1921. Specifically, the antifungal properties were evaluated by measuring the amount of ATP contained in the target fungi using the target fungi. First, a liquid medium containing suspended spores of the target fungi was inoculated onto the obtained fiber structure and cultured at 25°C for 42 hours. The amount of ATP after culture was then measured, and the antifungal activity value was calculated by comparing it with the similar test value (ATP amount) of an untreated fiber structure.

[0051] The antibacterial and antifungal fiber structure of this embodiment has an excellent texture because the antibacterial and antifungal components are directly fixed to the fiber structure, and has deodorizing, antibacterial, and antifungal properties that are durable through washing.The deodorizing, antibacterial, and antifungal properties can be maintained with almost no loss even after 10 washes using the standard washing method (washing method for SEK-marked fiber products) specified by the Japan Textile Evaluation Technology Council, a general incorporated association, and even after 50 washes using the high-temperature accelerated washing method (washing method for SEK-marked fiber products).

[0052] The washing method for SEK Mark textile products is a method for confirming the washing durability of SEK Mark textile products certified by the Japan Textile Evaluation Technology Council. The standard washing method conforms to JIS L1930 (home washing test method for textile products), and the high-temperature accelerated washing method involves washing at a high temperature of 80°C, simulating repeated commercial washing.

[0053] According to this embodiment, the antibacterial and antifungal components are fixed directly to the fiber structure without using a resin coating, which prevents deterioration in the breathability and feel of the fiber, prevents the harmful effects of formalin release on the environment and the human body, and prevents a decrease in the strength of the fiber structure, making it possible to produce an antibacterial and antifungal fiber structure with excellent washing durability without using special manufacturing equipment. Therefore, the antibacterial and antifungal fiber structure of this embodiment can be suitably used in clothing and non-clothing applications such as clothing and bedding that come into direct contact with the skin, gloves, hats, futon covers, curtains, tents, etc.

[0054] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. In the examples, "parts" and "%" are by mass.

[0055] <Antibacterial and antifungal compositions> First, antibacterial and antifungal compositions I to IV were prepared, each containing the following components in the formulations shown in Table 1 below: Metal oxide (A): zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd. (particle diameter 100 to 200 nm) Isothiazolin-based compound (B): 1,2-benzisothiazolin-3-one, manufactured by Arcsada Co., Ltd. Dispersant: Newcol (polyoxyethylene alkyl ether), manufactured by Nippon Nyukazai Co., Ltd.

[0056]

[0057] <Textile Structures> The following textile structures were prepared as target textile structures: Cotton: Cotton cloth (100% cotton), manufactured by Irozome Co., Ltd. PET: Polyester tropical (100% PET), manufactured by Irozome Co., Ltd. Nylon: Nylon 66 jersey (100% nylon), manufactured by Irozome Co., Ltd.

[0058] Example 1 Antibacterial and antifungal fiber structure (0 times) A ​​processing solution containing 1 part antibacterial and antifungal composition I and 99 parts water was prepared, and a fiber structure (PET) was immersed in a processing solution tank filled with the processing solution. The fiber structure was then pulled up while being squeezed through squeeze rolls so that 100 parts by mass of the processing solution was used for 100 parts by mass of the fiber structure (squeezing rate: 100%), and the fiber structure was heat-treated at 180°C for 1 minute while moving through a pin tenter (PT-2A, manufactured by Tsujii Senki Co., Ltd.) to obtain an antibacterial and antifungal fiber structure (0 times). Antibacterial and antifungal fiber structure (HL 5 times) The antibacterial and antifungal fiber structure (0 times) was washed five times at 40°C according to the standard washing method specified in the "SEK Mark Textile Product Washing Method" and then air-dried overnight to obtain an antibacterial and antifungal fiber structure (HL 5 times). <Antibacterial / Anti-fungal Fiber Structure (HL 10 Times)> The antibacterial / anti-fungal fiber structure (0 times) was washed 10 times at 40°C according to the standard washing method specified in the "SEK Mark Textile Product Washing Method", and then air-dried overnight to obtain an antibacterial / anti-fungal fiber structure (HL 10 times). <Antibacterial / Anti-fungal Fiber Structure (KL 50 Times)> The antibacterial / anti-fungal fiber structure (0 times) was washed 50 times at 80°C according to the high-temperature accelerated washing method specified in the "SEK Mark Textile Product Washing Method", and then air-dried overnight to obtain an antibacterial / anti-fungal fiber structure (KL 50 times).

[0059] Examples 2 to 19, Comparative Example 1 Antibacterial and antifungal fiber structures were obtained at 0 times, 5 times with HL, 10 times with HL, and 50 times with KL in the same manner as in Example 1, except that the composition of the processing liquid, the heating step, and the fiber structure were as shown in Tables 2 to 4. In Comparative Example 1, a urethane binder (urethane-based compound) was used as the film-forming compound.

[0060] The obtained example products and comparative example products were evaluated for texture and discoloration by the methods described below, and tests were also conducted for deodorizing properties against acetic acid, antibacterial properties against Klebsiella pneumoniae, and antifungal properties against Trichophyton by the same methods, and the deodorizing rate, antibacterial activity value, and antifungal activity value were calculated. The obtained antibacterial activity value and antifungal activity value were evaluated for antibacterial, antifungal, and deodorizing properties based on the indices described below. These results are also shown in Tables 2 to 4 below. Note that texture and discoloration were measured and evaluated only for the antibacterial and antifungal fiber structures (0 times).

[0061] <Feel> A sensory evaluation was carried out by 10 monitors. That is, the feel, hardness, and other textures of the fiber structures before and after treatment were compared by directly touching them, and the feel of the fiber structure before treatment was evaluated based on the following index, with the most common evaluation among the 10 monitors being used as the evaluation. ◯ (very good): The feel after treatment is the same as or better than before treatment. × (poor): The feel after treatment is worse than before treatment.

[0062] <Color Change> A sensory evaluation was conducted by 10 monitors. That is, the color shades of the fiber structures before and after treatment were visually observed, and the change in color shade compared to the fiber structure before treatment was evaluated based on the following index, with the most common evaluation among the 10 monitors being used as the evaluation. ◯ (very good): The color shade after treatment is the same as or better than before treatment. × (poor): The color shade after treatment is worse than before treatment.

[0063] <Antibacterial properties> Evaluation was made according to the "SEK Mark Textile Product Certification Standards" of the Japan Textile Evaluation Technology Council, as follows: ◯ (very good): antibacterial activity value of 2.0 or more × (poor): antibacterial activity value of less than 2.0

[0064] <Antifungal properties> The antifungal activity value was evaluated based on the following index: ◎ (excellent)... "2" or more, representing 1 / 100 of the growth value of an untreated fiber structure ○ (very good)... "1" or more and less than "2", representing 1 / 10 of the growth value of an untreated fiber structure × (poor)... untreated fiber structure has a growth value of less than "1"

[0065] <Deodorizing property> Measurements were made in accordance with the performance test method for deodorizing processed textile products (ISO 17299-3 gas chromatography method) and evaluated based on the following indices: ◎ (excellent): 70% or more ○ (very good): 50% or more but less than 70% × (poor): less than 50%

[0066]

[0067]

[0068]

[0069] Furthermore, the amount of each component fixed to the antibacterial and antifungal fiber structures obtained in each Example and Comparative Example was calculated and is shown in Tables 5 to 7 below.

[0070]

[0071]

[0072]

[0073] As shown in Tables 2 to 7, Examples 1 to 19 exhibited good texture, no discoloration, and deodorizing, antibacterial, and antifungal properties with high washing durability. On the other hand, Comparative Example 1, to which a film-forming compound was added, exhibited antibacterial properties but was inferior in texture and further discolored, making it unsuitable for use in clothing, bedding, and other items that come into direct contact with the skin. While the results for acetic acid were shown for the evaluation of deodorizing properties, similar trends were observed for ammonia and isovaleric acid. While the results for Klebsiella pneumoniae were shown for the evaluation of antibacterial properties, similar trends were observed for Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, Bacillus subtilis, Bacillus cereus, Escherichia coli, Salmonella enterica, and Pseudomonas aeruginosa. Furthermore, although the results for Trichophyton fungi were shown for the evaluation of antifungal properties, similar trends were observed for Aspergillus niger. Furthermore, although the results for fiber structures containing PET, nylon, and cotton were shown, similar trends were also observed for those containing acrylic.

[0074] Although the above examples show specific embodiments of the present invention, the examples are merely illustrative and should not be construed as limiting. Various modifications that are obvious to those skilled in the art are intended to fall within the scope of the present invention.

[0075] The antibacterial and antifungal fiber structure of the present invention is highly safe and has antibacterial and antifungal properties that are durable to washing, and therefore can be suitably used in clothing, bedding, and other items that come into direct contact with the skin.

[0076] REFERENCE SIGNS LIST 1 Treatment tank 2 Fiber structure 3 Squeeze roll 4 Heating device 5 Dryer 6 Processing liquid

Claims

1. A method for producing an antibacterial and antifungal fiber structure in which a metal oxide (A) contained in an antibacterial and antifungal composition is directly fixed to the surface of the fiber structure, the method comprising: a processing liquid preparation step of preparing a processing liquid containing the antibacterial and antifungal composition but not containing a film-forming compound; and a processing liquid heating step of applying the processing liquid to the fiber structure and heating it at 100 to 230°C under normal pressure or pressure for 0.5 minutes or more, wherein the metal oxide (A) is directly fixed in a proportion of 0.02 parts by mass or more per 100 parts by mass of the fiber structure.

2. The method for producing an antibacterial and antifungal fiber structure according to claim 1, wherein the metal oxide (A) is spot-fixed to the surface of the fiber structure.

3. A method for producing an antibacterial and antifungal fiber structure according to claim 1 or 2, wherein the metal oxide (A) is at least one compound selected from the group consisting of zinc oxide, titanium oxide, silver oxide, and copper oxide.

4. A method for producing an antibacterial and antifungal fiber structure according to any one of claims 1 to 3, wherein the antibacterial and antifungal composition further contains an isothiazolinone compound (B).

5. A method for producing an antibacterial and antifungal fiber structure according to claim 4, wherein the isothiazolin compound (B) is at least one compound selected from the group consisting of 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and 1,2-benzisothiazolin-3-one.

6. A method for producing an antibacterial and antifungal fiber structure according to claim 4 or 5, wherein in the antibacterial and antifungal composition, the mass ratio (B / A) of the isothiazolinone compound (B) to the metal oxide (A) is set to 0.01 to 0.

25.

7. A method for producing an antibacterial and antifungal fiber structure according to any one of claims 1 to 6, wherein the metal oxide (A) is composed of particles having a particle diameter of 100 to 400 nm in an amount of 50 mass % or more.

8. A method for producing an antibacterial and antifungal fiber structure according to any one of claims 1 to 7, wherein the film-forming compound is at least one selected from the group consisting of acrylic compounds, urethane compounds, silicone compounds, epoxy compounds, polyester compounds, and melamine compounds.

9. A method for producing an antibacterial and antifungal fiber structure according to any one of claims 1 to 8, wherein the processing liquid contains phosphoric acid and / or citric acid.

10. A method for producing an antibacterial and antifungal fiber structure according to any one of claims 1 to 9, wherein the pH of the processing liquid is in the range of 3 to 6.

11. An antibacterial and antifungal fiber structure in which the metal oxide (A) is directly fixed at a ratio of 0.02 parts by mass or more per 100 parts by mass of the fiber structure, and the antibacterial and antifungal fiber structure has an antibacterial activity value of 2.0 or more and an antifungal activity value of 1 or more.

12. The antibacterial and antifungal textile structure according to claim 11, wherein said textile structure comprises synthetic fibers.

13. The antibacterial and antifungal fiber structure according to claim 11 or 12, which has an antibacterial activity value of 2.0 or more and an antifungal activity value of 1 or more after 10 washes using the standard washing method (washing method for SEK-marked fiber products).

14. An antibacterial and antifungal fiber structure according to any one of claims 11 to 13, which has an antibacterial activity value of 2.0 or more and an antifungal activity value of 1 or more after 50 washes using a high-temperature accelerated washing method (washing method for SEK-marked fiber products).

15. An antibacterial and antifungal fiber structure according to any one of claims 11 to 14, which has a deodorizing rate of 50% or more for at least one odor of ammonia, acetic acid, or isovaleric acid after 10 washes using the standard washing method (washing method for SEK-marked fiber products).

16. The antibacterial and antifungal fiber structure according to any one of claims 11 to 15, wherein an isothiazolinone compound (B) is directly fixed to a fiber structure having synthetic fibers, and the ratio of the isothiazolinone compound (B) to 1 part by mass of the metal oxide (A) is set to 0.01 to 0.25 parts by mass.

17. An antibacterial and antifungal fiber structure according to any one of claims 11 to 16, wherein the metal oxide (A) is composed of particles having a particle diameter of 100 to 400 nm in an amount of 50 mass % or more.

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