Antimicrobial agent dispersion, antimicrobial processed textile product, and method for manufacturing antimicrobial processed textile product

Abstract

To provide an antibacterial agent dispersion with superior storage stability over a long time, an antibacterial-processed fiber product, and a method for producing an antibacterial-processed fiber product.SOLUTION: An antibacterial agent dispersion includes: an antibacterial agent with silver supported on poorly soluble phosphate complex salt; a phosphoester represented by the formula (I) or (II) or a salt thereof (in the formulae (I) and (II), R1, R2, and R3 independently represent a C12-18 linear or branched alkyl group or alkenyl group, or a styrenated phenyl group, the salt is an alkali metal salt, alkaline-earth metal salt, ammonium salt or organic ammonium salt, and x, y, and z independently represent an integer of 4 or more and 18 or less); and a liquid dispersion medium.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to an antibacterial agent dispersion, an antibacterial processed fiber product, and a method for producing an antibacterial processed fiber product. [Background technology]

[0002] Conventionally, as inorganic antimicrobial agent particles capable of imparting antimicrobial properties to various substrates, antimicrobial agents are known that consist of silver supported on two or more sparingly soluble double phosphates from various metals, such as calcium, zinc, aluminum, magnesium, and copper (see Patent Document 1). In addition, aqueous dispersions in which antimicrobial double phosphates are dispersed in water are also known (see Patent Document 2).

[0003] However, aqueous dispersions of antimicrobial double phosphates have poor dispersion stability, and the double phosphate particles tend to settle in water. Furthermore, the settled double phosphates form coarse secondary particles through aggregation, making it difficult to return to a homogeneous dispersion even with shaking and stirring.

[0004] Furthermore, aqueous dispersions of antibacterial agents obtained by wet grinding using a grinding medium in the presence of an anionic surfactant, such as a polycarboxylic acid-based surfactant, are also known (see Patent Document 3). However, aqueous dispersions of antibacterial agents obtained in this way tend to become discolored, and there is a problem that the hue of the dispersion changes significantly over time. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 2524893 [Patent Document 2] Japanese Patent Publication No. 2009-23959 [Patent Document 3] Patent No. 3063019 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present disclosure aims to provide an antibacterial agent dispersion liquid with excellent long-term storage stability, an antibacterial processed fiber product, and a method for producing the antibacterial processed fiber product.

Means for Solving the Problems

[0007] The antibacterial agent dispersion liquid according to an embodiment of the present disclosure (A) an antibacterial agent containing a sparingly soluble phosphate double salt of two or more metals selected from the group consisting of calcium, zinc, aluminum, magnesium, and copper, and silver supported on the phosphate double salt, (B) a surfactant containing at least one selected from the group consisting of a phosphoric acid monoester represented by the general formula (I)

[0008]

Chemical formula

[0009] and its salts, a phosphoric acid diester represented by the general formula (II)

[0010]

Chemical formula

[0011] and its salts (in the formulas (I) and (II), R 1 , R 2 , R 3 are each independently a linear or branched alkyl group or alkenyl group having 12 to 18 carbon atoms, or a styrenated phenyl group, and the salt is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an organic ammonium salt, and x, y, and z are each independently an integer in the range of 4 or more and 18 or less).), (C) a liquid dispersion medium and

Advantages of the Invention

[0012] According to certain embodiments of the present disclosure, there are provided an antibacterial agent dispersion liquid with excellent long-term storage stability, an antibacterial processed fiber product, and a method for producing the antibacterial processed fiber product.

Brief Description of the Drawings

[0013] [Figure 1] FIG. 1 shows the relationship between the number of moles of added oxyethylene n of the surfactant in the examples and the 90% particle diameter of the antibacterial agent after storage for 30 days.

Embodiments for Carrying Out the Invention

[0014] (First Embodiment) The antibacterial agent dispersion liquid of the present embodiment contains (A) an antibacterial agent, (B) a surfactant, and (C) a liquid dispersion medium.

[0015] The antibacterial agent contains an insoluble phosphate double salt of two or more metals selected from the group consisting of calcium, zinc, aluminum, magnesium, and copper, and silver supported on the phosphate double salt.

[0016] The surfactant is monoester phosphate represented by the general formula (I) and its salts, and

[0017]

Chemical formula

[0018] at least one selected from the group consisting of diester phosphate represented by the general formula (II) and its salts. Here, in the formulas (I) and (II), R general formula (II)

[0019]

Chemical formula

[0020] and at least one selected from the group consisting of diester phosphate represented by the formula and its salts. Here, in the formulas (I) and (II), R 1 、R 2 、R 3Each of the elements is independently a linear or branched alkyl or alkenyl group having 12 to 18 carbon atoms, or a styrene-phenyl group; the salt is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an organic ammonium salt; and each of the elements x, y, and z is independently an integer in the range of 4 to 18.

[0021] Industrially readily available phosphate ester surfactants are mixtures of monoesters and diesters, and the surfactant used in this embodiment can preferably be a mixture of the monoester represented by formula (I) and the diester represented by formula (II). However, the surfactant may contain only a monoester and / or a salt thereof, or only a diester and / or a salt thereof.

[0022] As mentioned above, the antibacterial agent is a particle of sparingly soluble double phosphate supported with silver, as described in, for example, Patent Documents 1 and 2. It is also available commercially. The antibacterial agent can be manufactured, for example, by the following method. First, oxides, hydroxides, or carbonates of two or more metals selected from the group consisting of calcium, zinc, aluminum, magnesium, and copper are prepared and reacted with phosphoric acid. Heating may be performed during the reaction as needed. This yields a slurry of sparingly soluble double phosphate. Next, silver nitrate is added to the obtained slurry and wet grinding is performed using a grinding medium. After this, the obtained slurry is filtered and the cake obtained by solid-liquid separation is recovered. The obtained cake is dried and ground to obtain an antibacterial powder.

[0023] The antibacterial agent preferably contains silver in a proportion of 0.5% to 5.0% by weight. Furthermore, the sparingly soluble phosphate double salt is preferably a phosphate double salt of calcium, zinc, and aluminum.

[0024] In the antibacterial agent dispersion of this embodiment, the antibacterial agent is dispersed in the liquid dispersion medium by using the specific phosphate ester-based anionic surfactant described above.

[0025] The above phosphate ester-based anionic surfactant specifically contains at least one selected from the group consisting of a phosphoric acid monoester represented by the formula (I) and its salt, and a phosphoric acid diester represented by the formula (II) and its salt. R 1 、R 2 、R 3 are each independently a linear or branched alkyl group or alkenyl group having 12 to 18 carbon atoms, or a styrenated phenyl group. x, y, and z are each independently an integer of 4 or more and 18 or less. Hereinafter, when collectively referring to R 1 、R 2 、R 3 they are referred to as R. Similarly, when collectively referring to x, y, and z they are referred to as n.

[0026] That is, the surfactant contains at least one selected from the group consisting of polyoxyethylene alkyl ether phosphoric acid monoester and its salt, polyoxyethylene alkenyl ether phosphoric acid monoester and its salt, polyoxyethylene styrenated phenyl ether phosphoric acid monoester and its salt, polyoxyethylene alkyl ether phosphoric acid diester and its salt, polyoxyethylene alkenyl ether phosphoric acid diester and its salt, and polyoxyethylene styrenated phenyl ether phosphoric acid diester and its salt.

[0027] Specific examples of the linear or branched alkyl group or alkenyl group having 12 to 18 carbon atoms include a dodecyl group (C12), a tridecyl group (C13), an isotridecyl group (C13), a myristyl group (C14), a cetyl group (C16), a stearyl group (C18), an oleyl group (C18), etc. As will be described below, when the carbon number of R is less than 12, or when the carbon number is greater than 18, the dispersion stability of the antibacterial agent in the antibacterial agent dispersion liquid is not sufficient, and the antibacterial agent particles aggregate and precipitate after storage for about 30 days.

[0028] Examples of styrene-phenyl groups include monostyrene-phenyl groups, distyrene-phenyl groups, and tristyrene-phenyl groups. When the phosphate ester surfactant contains polyoxyethylene styrene-phenyl ether phosphate diester and / or a salt thereof, the styrene-phenyl group may be one of monostyrene-phenyl groups, distyrene-phenyl groups, and tristyrene-phenyl groups, or two or more.

[0029] The number of moles of ethylene oxide added is preferably between 4 and 18. Similar to the number of carbon atoms, if the number of moles added is less than 4, or greater than 18, the dispersion stability of the antibacterial agent in the antibacterial agent dispersion is insufficient, and the antibacterial agent particles aggregate and settle after about 30 days of storage. More preferably, the number of moles of ethylene oxide added is between 4 and 16, and even more preferably between 4 and 10.

[0030] In this embodiment, the above-mentioned phosphate ester surfactant may be a neutralized salt. Examples of ions that form a neutralized salt with the acidic group of phosphoric acid include metal ions such as sodium ions, potassium ions, calcium ions, and magnesium ions, as well as ammonium ions. Additionally, organic ammonium ions derived from organic amines such as ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, isopropylethanolamine, diisopropanolamine, 2-amino-2-methylpropanol, 2-(dimethylamino)-2-methylpropanol, morpholine, N-methylmorpholine, and N-ethylmorpholine can also be mentioned.

[0031] Silver, the active ingredient in antibacterial agents, dissolves in water and other liquids, and the silver ions in the water react with microorganisms to exert its antibacterial effect. Therefore, even in antibacterial agent dispersions, silver dissolves slightly into the liquid dispersion medium and exists as silver ions. It is preferable that surfactants do not exhibit reactions or interactions that cause undesirable effects with silver ions in the liquid dispersion medium. For example, it is preferable that surfactants do not produce significant discoloration through reactions or interactions with silver ions. The antibacterial agent dispersion of this embodiment is white and shows little color change over time. As will be explained below, surfactants represented by formula (I) or formula (II) above do not produce discoloration (chromatic colors and achromatic colors other than white) through reactions or interactions with silver ions. Therefore, even when textile products are treated with antibacterial processing using the antibacterial agent dispersion of this embodiment, discoloration that would affect the design of the textile products is suppressed.

[0032] The antibacterial agent dispersion of this embodiment preferably contains a surfactant in a ratio of 0.1 parts by weight to 20 parts by weight per 100 parts by weight of antibacterial agent. If the proportion of surfactant is less than 0.1 parts by weight, it will not effectively disperse the antibacterial agent in the liquid dispersion medium, and the particles may aggregate and become coarser or settle over time during storage. Furthermore, if the proportion of surfactant exceeds 20 parts by weight, the friction fastness of textile products processed using such an antibacterial agent aqueous dispersion may decrease.

[0033] The antibacterial agent is dispersed in a liquid dispersion medium in the presence of a surfactant. Water is typically used as the liquid dispersion medium. However, if necessary, hydrophilic organic solvents such as alcohol, methyl ethyl ketone, and dimethylformamide, or hydrophobic organic solvents such as toluene may be used, or a mixture of water and an organic solvent may be used as the liquid dispersion medium.

[0034] There are no particular restrictions on the amount of antibacterial agent added to an antibacterial agent dispersion. As long as the antibacterial agent is dispersed in the liquid dispersion medium during the manufacture of the antibacterial agent dispersion and no precipitate has formed, any amount of antibacterial agent may be added. Generally, the amount of antibacterial agent added to an antibacterial agent dispersion is in the range of 20% by weight or more and 50% by weight or less.

[0035] It should be noted that certain surfactants, such as benzalkonium chloride, are known to have antibacterial properties. Based on the inventors' investigations, the phosphate ester surfactants described above are not considered to possess antibacterial properties sufficient to warrant observation. Further details will be explained in the following examples.

[0036] The antimicrobial agent dispersion of this embodiment may contain other additives in addition to the antimicrobial agent, surfactant, and liquid dispersion medium. For example, the antimicrobial agent dispersion of this embodiment may further contain at least one selected from the group consisting of anionic surfactants, nonionic surfactants, and cationic surfactants, other than the surfactants represented by formulas (I) and (II).

[0037] Other anionic surfactants not listed above include, for example, alkyl sulfate salts, sulfonates such as alkylbenzene sulfonates and alkylnaphthalene sulfonates, higher alcohol phosphate salts, sulfate salts of arylated phenol ethylene oxide adducts, sulfosucrates of arylated phenol ethylene oxide adducts, higher alcohol sulfate salts, alkali metal salts and ammonium salts of hydrolysates of diisobutylene-maleic anhydride copolymers, alkali metal salts and ammonium salts of hydrolysates of styrene-maleic anhydride copolymers, alkali metal salts and ammonium salts of half-esterified diisobutylene-maleic anhydride copolymers, alkali metal salts and ammonium salts of half-esterified styrene-maleic anhydride copolymers, alkali metal salts and ammonium salts of styrene-(meth)acrylic acid copolymers, and metal salts and ammonium salts of polyacrylates.

[0038] Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants such as arylated phenol alkylene oxide adducts, alkylphenol alkylene oxide adducts, higher alcohol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol aliphatic ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, and fatty acid amide alkylene oxide adducts, as well as polyhydric alcohol-type nonionic surfactants such as alkyl glycosides and sucrose fatty acid esters.

[0039] Examples of cationic surfactants include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamines, and polyethylene polyamine derivatives.

[0040] Furthermore, the antimicrobial agent dispersion may contain, in addition to the surfactants mentioned above, protective colloidal agents such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, guar gum, xanthan gum, and starch paste as dispersion aids to enhance storage stability and disperse the antimicrobial double phosphate, to the extent that its antimicrobial performance is not inhibited.

[0041] In the antibacterial agent dispersion of this embodiment, the particle size of the antibacterial agent can affect its dispersion stability. The smaller the particle size of the antibacterial agent, the better its dispersion stability. On the other hand, the larger the particle size, the lower the dispersion stability of the antibacterial agent, and the more likely it is to settle in the liquid dispersion medium and form clumps, so-called hard cakes. For this reason, when an antibacterial agent dispersion containing large-particle antibacterial agents is incorporated into, for example, a coating composition, a thin coating film made from such a composition may develop an undesirable appearance, or if used in an adhesive layer, it may reduce the adhesive strength.

[0042] Furthermore, depending on the type of surfactant selected as the dispersant, the resulting antimicrobial dispersion may have small particle sizes immediately after production, but the particles may aggregate during storage, resulting in larger particle sizes. In this case, the aforementioned problems may also occur.

[0043] From this perspective, in the antibacterial agent dispersion of this embodiment, the 90% particle size by volume of the antibacterial agent is preferably 1.5 μm or less, and more preferably 0.1 μm or more and 1.0 μm or less.

[0044] The antibacterial agent dispersion of this embodiment can be obtained by dispersing an antibacterial agent with a 90% volume particle diameter of 1.5 μm or less, more preferably 0.1 μm or more and 1.0 μm or less, in a liquid dispersion medium. Furthermore, since aggregation of the antibacterial agent is suppressed during storage after production, this antibacterial agent dispersion can maintain a 90% particle diameter at approximately the same level as at the time of production.

[0045] The antimicrobial agent dispersion of this embodiment can be produced by weighing and mixing the above-mentioned antimicrobial agent, surfactant, and liquid dispersion medium, along with additives selected as needed, and dispersing the antimicrobial agent in the liquid dispersion medium. There are no particular restrictions on the production method, but for example, the antimicrobial agent dispersion of this embodiment can be obtained by weighing and mixing the above-mentioned antimicrobial agent, surfactant, and liquid dispersion medium, along with additives selected as needed, and dispersing the antimicrobial agent in the liquid dispersion medium using a propeller stirrer or homogenizer. To adjust the particle size of the antimicrobial agent, a mill filled with media such as glass beads may be used as needed.

[0046] The antimicrobial agent dispersion of this embodiment contains a surfactant represented by formula (I) or formula (II), which suppresses aggregation and precipitation of antimicrobial agent particles even during long-term storage, thus providing excellent storage stability. In particular, the number of carbon atoms in R and the number of moles of ethylene oxide added (n) in formulas (I) and (II) are within a predetermined range, making it possible to stably disperse antimicrobial agent particles in the liquid dispersion medium for a long period of time. Furthermore, the surfactant represented by formula (I) or formula (II) does not cause discoloration through reaction or interaction with silver ions dissolved in the liquid dispersion medium. Therefore, even when antimicrobial processing is applied to textile products using the antimicrobial agent dispersion of this embodiment, discoloration that would affect the design of the textile products can be suppressed.

[0047] (Second Embodiment) The antibacterial processed textile product of this embodiment comprises a textile product and an antibacterial agent and a surfactant attached to the textile product. The antibacterial agent and surfactant were contained in the antibacterial agent dispersion, and are attached to the textile product by treating it with the antibacterial agent dispersion. If the antibacterial agent dispersion used for antibacterial processing contains other additives, those additives may also be attached to the textile product.

[0048] The amount of antibacterial agent adhering to antibacterial processed textiles can vary depending on the specifications, intended use, and type of textile. For example, the amount of antibacterial agent adhering to antibacterial processed textiles is in the range of 0.01% by weight or more and 5% by weight or less. If the amount is less than 0.01% by weight, it may not be possible to impart sufficient antibacterial properties to the textile. Furthermore, if the amount exceeds 5% by weight, the textile may become hard after antibacterial processing, potentially reducing its texture and aesthetic appeal.

[0049] The amount of surfactant attached to antibacterial treated textiles is arbitrary. From the viewpoint of reducing the impact on the texture and other properties of the textiles, a smaller amount is preferable.

[0050] Examples of fibers that make up textile products include synthetic fibers such as polyester, nylon, acrylic, and polyurethane; semi-synthetic fibers such as acetate; regenerated fibers such as rayon; natural fibers such as cotton, linen, silk, and wool; and composite fibers of these.

[0051] The antibacterial agent dispersion can be diluted with other liquid dispersion media as needed. For example, an antibacterial treatment solution can be prepared by adding another liquid dispersion medium to the antibacterial agent dispersion so that the concentration of the antibacterial agent is approximately 0.1% to 5% by weight. This antibacterial treatment solution can then be used to apply antibacterial treatment to various textile products.

[0052] For example, when using the padding method, the textile product is immersed in the antibacterial treatment solution described above, squeezed with a mangle to achieve a predetermined amount of adhesion, and then subjected to dry heat treatment for several seconds to several minutes at a temperature of approximately 100°C to 200°C, preferably 120°C to 190°C, to adhere the antibacterial agent to the textile product. At this time, a resin binder may be used in combination to prevent the antibacterial agent attached to the textile product from being washed off after processing.

[0053] Examples of resin binders include urethane resins, acrylic resins, polyester resins, vinyl acetate resins, silicone resins, and SBR resins. The type and amount of such resin binders can be arbitrarily selected within a range that allows the antibacterial agent of this embodiment to exert its full effect.

[0054] Furthermore, an adsorption processing method may be used to apply antibacterial treatment to textile products. For example, similar to conventional dyeing methods for textile products, an antibacterial treatment solution is placed in the dyeing apparatus along with the textile product, and then heated to a temperature of 70°C to 100°C to allow the antibacterial agent to adsorb onto the textile product. Alternatively, the antibacterial treatment solution may be placed in the dyeing apparatus at the same time as the dye, and dyeing and antibacterial treatment may be performed in the same bath under the same dyeing conditions.

[0055] In addition, in the antibacterial processed textile product of this embodiment, for example, the amount of surfactant attached may be set to be small in order to obtain a better texture, or no surfactant may be attached at all. For example, during or after the manufacturing of the antibacterial processed textile product by the method described above, the amount of surfactant attached can be reduced by immersing the antibacterial processed textile product to which the antibacterial agent and surfactant have been attached in a liquid solvent such as water, or by washing it with water or the like to remove at least a portion of the attached surfactant from the antibacterial processed textile product.

[0056] The antibacterial treated textiles of this embodiment may be washed regularly depending on their application. In this case, even if the antibacterial treated textiles contain an antibacterial agent and a surfactant at the start of use, the amount of surfactant adhering to them may decrease with repeated washing. Even in this case, the antibacterial agent is less likely to be washed off the antibacterial treated textiles, and the antibacterial treated textiles can exert their antibacterial effect over a long period of time.

[0057] Thus, antibacterial processed textiles with a small amount of surfactant attached, or those that do not contain surfactant, or those in which the amount of surfactant attached decreases after washing, or those that do not contain any surfactant, can be considered antibacterial processed textiles of this embodiment, as long as they are manufactured by the antibacterial processed textile manufacturing method of this embodiment.

[0058] (Other forms) The antibacterial agent dispersion of the first embodiment can be used for antibacterial treatment of various articles, not just textiles. For example, the antibacterial agent dispersion may be added to resins or paints to impart antibacterial properties, or the antibacterial agent dispersion may be diluted with a solvent such as water, and the diluted antibacterial agent dispersion may be sprayed onto the target article to apply antibacterial treatment to the article's surface. The antibacterial treatment may be applied not only to articles but also to the interiors of buildings, or to the interiors of vehicles such as automobiles, trains, aircraft, and ships.

[0059] (Example 1) An antimicrobial agent dispersion was prepared and evaluated according to the above embodiment. Commercially available raw materials were used to prepare the antimicrobial agent dispersion. 1. Preparation of antibacterial agents Composition formula (Al 2 / 3An antimicrobial agent was prepared in which silver was supported on a sparingly soluble double phosphate salt of a metal represented by (Ca8·Zn(PO4)6). In this sparingly soluble double phosphate salt, the ratio of the equivalent weight of calcium metal to the total equivalent weight of the sparingly soluble double phosphate salt of the metal is 0.8. The raw materials were weighed so that the metal elements and phosphorus matched the proportions in the above compositional formula, and the antimicrobial agent was synthesized. First, 1000 g of a 40% aqueous phosphoric acid solution was heated to 50°C, and 55.3 g of zinc oxide, 406.9 g of calcium hydroxide, and 70.7 g of aluminum hydroxide were gradually added while stirring. After holding the mixture at 60°C for 5 hours, the resulting slurry was cooled to 30°C, transferred to a 2 L ball mill, and 10.6 g of silver nitrate was added and kneaded for 2 hours. The resulting slurry was washed with water, filtered, and the resulting cake was dried at 250°C for 12 hours to obtain an antimicrobial agent of double phosphate salt containing 0.95% by weight of silver. 2. Manufacturing of antimicrobial agent dispersion Using the prepared antimicrobial agent and the surfactants shown in Table 1, antimicrobial agent dispersions for samples 1 to 20, 22, and 23 were prepared. The phosphate esters shown in Table 1 are mixtures of monoesters and diesters. 25 parts by weight of antimicrobial agent, 2 parts by weight of surfactant, 0.1 parts by weight of silicone-based defoamer, and 35 parts by weight of water were weighed and mixed. The mixture was placed in a mill filled with 0.8 mm diameter glass beads and ground for 3 hours. After grinding, 0.15 parts by weight of xanthan gum was added to the mixture, and water was added to bring the total volume to 100 parts by weight to obtain an antimicrobial agent dispersion. Sample 21 was prepared similarly, except that no surfactant was added. 3. Evaluation of antimicrobial agent dispersions (1) Measurement of non-volatile content Each sample was held at 105°C for 40 minutes to evaporate the volatile components, and the weight of the remaining sample was measured to determine the concentration of non-volatile components in the antibacterial agent dispersion. The determined concentrations are shown in Table 1. (2) Evaluation of storage stability Samples 1 through 23 were left at 40°C for 30 days. The particle size distribution of each sample was measured immediately after preparation and after 30 days of storage. A Shimadzu Corporation SALD-2200 laser diffraction particle size analyzer was used to determine the 90% particle diameter based on volume. Samples with a 90% particle diameter of less than 1.5 μm were judged as passable (P), and samples with a 90% particle diameter of 1.5 μm or more were judged as failing (F). The determined 90% particle diameters are shown in Table 1. (3) Evaluation of changes in hue over time Each sample was observed immediately after manufacturing and after 30 days of storage. A sample was judged as passable (P) if there was no change in hue, i.e., if the hue was stable, and as failable (F) if a change in hue was observed. The results are shown in Table 1. 4. Results and Discussion As shown in Table 1, the antimicrobial agent dispersions of Samples 1 to 6 showed no change in hue after 30 days of storage, demonstrating excellent storage stability. This is thought to be because the surfactants in the antimicrobial agent dispersions are compounds having the structure shown by formula (I) or formula (II).

[0060] On the other hand, in the antimicrobial agent dispersions of samples 7 to 23, the surfactants do not have the structure shown by formula (I) or formula (II), resulting in insufficient color change after 30 days of storage and inadequate storage stability. Specifically, in the surfactants of samples 7 to 11, the number of moles of ethylene oxide added, n, in formula (I) or formula (II) is less than 4 or greater than 18. Also, in the surfactants of samples 12 and 13, the number of carbon atoms of R in formula (I) or formula (II) is less than 12. The surfactants of samples 14 to 20 are not phosphate esters shown by formula (I) or formula (II).

[0061] The antibacterial agent dispersion in sample 21 does not contain a surfactant. Therefore, its storage stability after 30 days is insufficient. The antibacterial agent dispersions in samples 22 and 23 contain polyacrylate as a surfactant, and exhibit excellent storage stability after 30 days. However, after 30 days of storage, the antibacterial agent dispersions began to change from brown to black. This is thought to be because silver that leached out during storage reacted with the polyacrylate, causing discoloration.

[0062] Figure 1 shows the relationship between the number of moles of ethylene oxide added (n) of the surfactant and the 90% particle size of the antibacterial agent after 30 days of storage for samples 1 to 11. As shown in Table 1, when the number of moles added (n) is less than 4, the 90% particle size of the antibacterial agent after 30 days of storage exceeds 1.5 μm. The 90% particle size is 1.5 μm or less for the number of moles added (n) from 4 to about 18, and when the number of moles added (n) is 20 or more, the 90% particle size exceeds 1.5 μm. In samples 1 to 11, the R of the surfactant shown in formula (I) or formula (II) is different, but regardless of the difference in R, if the number of moles added (n) is generally in the range of 4 to 18, the surfactant can suppress the aggregation of antibacterial agent particles and maintain the state of dispersion of antibacterial agent particles in the liquid solvent, even when the antibacterial agent dispersion is stored for about 30 days.

[0063] Thus, by including a surfactant represented by formula (I) or formula (II), an antimicrobial agent dispersion with excellent storage stability and suppressed color change can be realized.

[0064] [Table 1]

[0065] (Example 2) The antibacterial agent dispersion prepared in Example 1 was used to perform antibacterial treatment on textile products, thereby producing antibacterial treated textile products. The antibacterial properties of the obtained antibacterial treated textile products were evaluated. 1. Manufacturing of antibacterial treated textile products An antibacterial processed textile product was manufactured using the antibacterial agent dispersion of Sample 4. An antibacterial processing solution was prepared by adding 98.5 parts by weight of water to 1.5 parts by weight of the antibacterial agent dispersion of Sample 4. A commercially available polyester double pique (weight 240 g / m²) was used. 2 The fabric was immersed in the treatment solution and squeezed to ensure 100% wet pickup, allowing the treatment solution to adhere to the fabric. The resulting treated fabric was dried at 130°C for 5 minutes to obtain the polyester fabric for the antibacterial test of sample 31.

[0066] Similarly, commercially available cotton cloth (weight 100g / m 2 The fabric was immersed in the treatment solution and squeezed to ensure a wet pickup of 80% and to allow the treatment solution to adhere to the fabric. The resulting treated fabric was dried at 100°C for 5 minutes to obtain the cotton fabric for the antibacterial test of sample 32. 2. Preparation of reference textile products To investigate the antibacterial activity of the surfactant contained in the antibacterial agent dispersion of this disclosure, a reference fiber product with only the surfactant attached was prepared. The polyoxyethylene (7) oleyl ether sodium phosphate salt used in Sample 4 was prepared and diluted to a concentration of 0.15%. A commercially available polyester double pique (240 g / m²) was added to the aqueous solution of the resulting phosphate salt. 2 The fabric was immersed and squeezed to achieve a wet pickup of 110%, allowing the aqueous solution to adhere to the fabric. The resulting treated fabric was dried at 130°C for 5 minutes to obtain the polyester fabric for the antibacterial test of sample 41.

[0067] Similarly, commercially available cotton cloth (weight 100g / m 2 The fabric was immersed in an aqueous solution of phosphate ester salt, and squeezed to achieve a wet pickup of 110%, allowing the aqueous solution to adhere to the fabric. The resulting treated fabric was dried at 100°C for 5 minutes to obtain the cotton fabric for the antibacterial test of sample 42. 3. Antibacterial properties test of antibacterial treated textiles Antimicrobial activity tests were performed on the manufactured samples 31 and 32. Using the JIS L 1902 bacterial suspension absorption method, the polyester fabric used for the antimicrobial activity test of sample 31 was washed 10 times, and the antimicrobial activity values ​​against Staphylococcus aureus and Klebsiella pneumoniae after washing were determined. Similarly, the cotton fabric used for the antimicrobial activity test of sample 32 was washed 10 times, and the antimicrobial activity values ​​against Staphylococcus aureus after washing were determined. The results are shown in Table 2.

[0068] [Table 2]

[0069] Similarly, antimicrobial activity tests were performed on the prepared samples 41 and 42. Using the JIS L 1902 bacterial suspension absorption method, the antimicrobial activity values ​​against Staphylococcus aureus and Klebsiella pneumoniae of the polyester fabric used for the antimicrobial activity test of sample 41 before washing (0 washes) were first determined. Then, the polyester fabric used for the antimicrobial activity test of sample 41 was washed 10 times, and the antimicrobial activity values ​​against Staphylococcus aureus and Klebsiella pneumoniae after washing were determined. Similarly, the cotton fabric used for the antimicrobial activity test of sample 42 was washed 10 times, and the antimicrobial activity value against Staphylococcus aureus after washing was determined. The results are shown in Table 3.

[0070] [Table 3]

[0071] 4. Results and Discussion According to JIS L 1902, an antibacterial activity value of 2.0 or higher indicates an antibacterial effect, and an antibacterial activity value of 3.0 or higher indicates a strong effect. Since the antibacterial activity values ​​of both samples 31 and 32 are sufficiently greater than 3.0, the antibacterial agent dispersion of this embodiment can impart a strong antibacterial effect to textile products, and the antibacterial processed textile products of this embodiment have excellent antibacterial properties.

[0072] Furthermore, the antibacterial activity value of sample 41 is less than 2.0 even before washing. The antibacterial activity values ​​of samples 41 and 42 after washing are even lower. In the surfactants used for samples 41 and 42, the number of moles of ethylene oxide added (n) is 7, but considering the similarity of the structures, it is thought that surfactants of formulas (I) and (II) would show a similar trend.

[0073] These results indicate that the surfactant used in the antibacterial agent dispersion of this embodiment, when used alone, does not possess the antibacterial properties required by JIS standards. On the other hand, the results for samples 31 and 32 suggest that in the antibacterial agent dispersion and antibacterial processed textile product of this embodiment, the surfactant hardly inhibits the antibacterial properties of the antibacterial agent. In other words, the antibacterial agent dispersion of this disclosure maintains the excellent antibacterial properties of the antibacterial agent, in which silver is supported on a poorly soluble double phosphate, while also providing excellent long-term storage stability.

[0074] The antimicrobial agent dispersion, antimicrobial processed textile product, and method for manufacturing the antimicrobial processed textile product described herein can also be described as follows.

[0075] The antibacterial agent dispersion relating to the first component is (A) An antibacterial agent comprising a sparingly soluble double phosphate of two or more metals selected from the group consisting of calcium, zinc, aluminum, magnesium, and copper, and silver supported on the double phosphate, (B) General formula (I)

[0076] [ka]

[0077] A phosphate monoester represented by the same and its salts, General formula (II)

[0078] [ka]

[0079] A surfactant comprising at least one selected from the group consisting of phosphate diesters represented by and their salts (in formulas (I) and (II), R 1 , R 2 , R 3Each of these is independently a linear or branched alkyl or alkenyl group having 12 to 18 carbon atoms, or a styrene-phenyl group; the salt is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an organic ammonium salt; and x, y, and z are each independently integers in the range of 4 to 18. (C) Liquid dispersion medium and Includes.

[0080] According to the first configuration, the antimicrobial agent dispersion contains a surfactant represented by formula (I) or formula (II), which suppresses aggregation and precipitation of antimicrobial agent particles even when stored for a long period of time, thus providing excellent storage stability.

[0081] The second configuration may include, in the first configuration, silver supported as an antibacterial agent in a proportion of 0.5% by weight or more and 5.0% by weight or less.

[0082] The third configuration may be that in the first or second configuration, the sparingly soluble phosphate double salt is a calcium, zinc, and aluminum phosphate double salt.

[0083] The fourth configuration may contain, in any one of the first to third configurations, a surfactant in a ratio of 0.1 parts by weight to 20 parts by weight per 100 parts by weight of the antibacterial agent.

[0084] The fifth composition may contain an antibacterial agent in any one of the first to fourth compositions in a proportion of 20% to 50% by weight.

[0085] The sixth configuration may further include a protective colloidal agent as a dispersing aid in any one of the first to fifth configurations.

[0086] The antibacterial processed textile product relating to the seventh configuration comprises a textile product and an antibacterial agent and surfactant contained in an antibacterial agent dispersion of any one of the first to sixth configurations, which are attached to the textile product.

[0087] The method for producing an antibacterial processed textile product according to the eighth composition involves treating the textile product with an antibacterial agent dispersion of any one of the first to sixth compositions to apply antibacterial treatment to the textile product and obtain an antibacterial processed textile product.

[0088] The ninth configuration is that, in the eighth configuration, the treatment using the antimicrobial agent dispersion may involve attaching at least the antimicrobial agent to the textile product.

[0089] In the tenth configuration, the surfactant may be further attached to the textile product by treatment with an antimicrobial agent dispersion, as in the ninth configuration.

[0090] The 11th configuration is that, in the 8th configuration, the treatment using the antibacterial agent dispersion may involve immersing the textile product in the antibacterial agent dispersion, allowing a predetermined amount of antibacterial agent to be retained in the textile product, and then heating to adhere the antibacterial agent to the textile product.

[0091] In the 12th configuration, the treatment using the antimicrobial agent dispersion may involve placing the textile product into an apparatus containing the antimicrobial agent dispersion, followed by heating to allow the antimicrobial agent to be adsorbed onto the textile product. [Industrial applicability]

[0092] The antimicrobial agent dispersion of this disclosure is suitably used for antimicrobial processing of various articles and other items. Furthermore, the antimicrobial processed textile product and the method for producing the antimicrobial processed textile product of this disclosure are suitably used for textile products for various applications.

Claims

1. (A) An antibacterial agent comprising a sparingly soluble double phosphate of two or more metals selected from the group consisting of calcium, zinc, aluminum, magnesium, and copper, and silver supported on the double phosphate, (B) General formula (I) 【Chemistry 1】 A phosphate monoester represented by the same and its salts, General formula (II) 【Chemistry 2】 A surfactant comprising at least one selected from the group consisting of phosphate diesters represented by and their salts (in formulas (I) and (II), R １ , R ２ , R ３ Each of these is independently a linear or branched alkyl or alkenyl group having 12 to 18 carbon atoms, or a styrene-phenyl group; the salt is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an organic ammonium salt; and x, y, and z are each independently integers in the range of 4 to 18. (C) Liquid dispersion medium and An antibacterial agent dispersion containing an antibacterial agent.

2. The antibacterial agent dispersion according to claim 1, wherein the antibacterial agent contains the supported silver in a proportion of 0.5% by weight or more and 5.0% by weight or less.

3. The antibacterial agent dispersion according to claim 1, wherein the poorly soluble double phosphate is a double phosphate of calcium, zinc, and aluminum.

4. The antibacterial agent dispersion according to claim 1, comprising the surfactant in a ratio of 0.1 parts by weight to 20 parts by weight per 100 parts by weight of the antibacterial agent.

5. The antibacterial agent dispersion according to claim 1, comprising the antibacterial agent in a proportion of 20% by weight or more and 50% by weight or less.

6. The antibacterial agent dispersion according to claim 1, further comprising a protective colloidal agent as a dispersion aid.

7. The antibacterial agent dispersion according to claim 1, wherein the 90% particle size of the antibacterial agent by volume is 0.1 μm or more and 1.0 μm or less.

8. Textile products, An antibacterial agent and surfactant contained in the antibacterial agent dispersion according to any one of claims 1 to 7, wherein the antibacterial agent and surfactant attached to the textile product, Antibacterial treated textile products.

9. A method for producing an antibacterial processed textile product, comprising treating a textile product with an antibacterial agent dispersion according to any one of claims 1 to 7 to provide antibacterial processing to the textile product and obtain an antibacterial processed textile product.

10. The method for producing an antibacterial processed textile product according to claim 9, wherein the treatment using the antibacterial agent dispersion causes at least the antibacterial agent to adhere to the textile product.

11. A method for producing an antibacterial processed textile product according to claim 10, further comprising applying the surfactant to the textile product by treatment with the antibacterial agent dispersion.

12. The method for producing an antibacterial processed textile product according to claim 9, wherein the treatment using the antibacterial agent dispersion involves immersing the textile product in the antibacterial agent dispersion, allowing a predetermined amount of antibacterial agent to be retained in the textile product, and then heating to adhere the antibacterial agent to the textile product.

13. The method for producing an antibacterial processed textile product according to claim 9, wherein the treatment using the antibacterial agent dispersion involves placing the textile product into an apparatus containing the antibacterial agent dispersion, and then heating it to adsorb the antibacterial agent onto the textile product.

Images