JP2009007736A - Method for producing bacteria, fungus and virus resisting fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing more-safety bacteria, fungus and virus resisting fiber that has a firm adsorption of the antimicrobial agent, a high microbial retention even after washing, further extremely small amount of the elution of the antimicrobial agent from the synthetic fibers. <P>SOLUTION: Synthetic fiber and an aqueous suspension including atomized pyridine antimicrobial agent of an inorganic value/organic value of 1.4 to 3.3 are allowed to flow under a tightly sealed, heated and pressurized condition, thereby the pyridine antimicrobial agent is adsorbed on the synthetic fiber. Then, the synthetic fiber is returned to the normal pressure condition and is treated with heat under a normal pressure. Thus, the bacteria, fungus and virus resisting fiber is produced. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing antibacterial / antifungal / antiviral fibers.

  Conventionally, a fiber structure imparted with antibacterial properties has been widely used in various clothing, bedding, interior products, and the like. In particular, nosocomial infections caused by methicillin-resistant Staphylococcus aureus (hereinafter referred to as “MRSA”) have become a problem, and the use of antibacterial fibers that impart antibacterial properties to lab coats and curtains is increasing.

  Among them, in recent years, low humidity conditions by the bacteria transfer method after industrial washing due to the problem of securing antibacterial efficacy with an evaluation method according to the actual use situation and safety of the antibacterial agent transfer from the fiber to the skin In the antibacterial activity test below, a fiber structure having high antibacterial activity and extremely little elution of the antibacterial agent from the fiber is required. Furthermore, in order to enhance hygiene, there is a need for fibers having not only antibacterial but also antifungal properties. In addition, virus problems such as SARS (Severe Acute Respiratory Syndrome) virus, avian influenza virus and human influenza virus are growing, and antiviral fibers are required.

  For example, an antibacterial fiber structure containing a pyridine antibacterial agent having a molecular weight of 200 to 700, an inorganic value / organic value = 0.3 to 1.4, and an average particle size of 2 μm or less is excellent in industrial washing durability. It is described in Patent Document 1 that it has antibacterial activity.

  Furthermore, Patent Document 2 describes that a product obtained by pressurizing a polyester fiber with pyrithione zinc and pyrithione copper is a good antibacterial fiber even after washing.

JP 2000-8275 A JP 2000-1119960 A

  However, in each of the above-mentioned documents, those having the required antibacterial property, antifungal property, washing resistance and the like have not been obtained. That is, the method described in Patent Document 1 describes that when the inorganic value / organic value exceeds 1.4, the antibacterial agent is poorly adsorbed on synthetic fibers such as polyester and the antibacterial efficacy is also poor. Moreover, it cannot be said that the synthetic fiber to which the antibacterial agent is attached by the method described in Patent Document 2 has sufficient antibacterial activity and antifungal properties by the bacteria transfer method in a low humidity state. Further, fibers having an antiviral effect have not been known so far.

  Therefore, the present invention has strong antibacterial agent adsorption power to fibers, high antibacterial and antifungal properties even after washing, and very little antibacterial agent elution from synthetic fibers. The purpose is to provide viral fibers.

  The present invention provides a hermetically heated aqueous suspension in which a synthetic fiber and a pyridine-based antibacterial agent having an inorganic value / organic value exceeding 1.4 and exceeding 3.3 are dispersed in the form of fine particles. By allowing the synthetic fiber to exhaust the pyridine antibacterial agent by flowing under pressure, the synthetic fiber is returned to normal pressure, and then the synthetic fiber is heat treated under normal pressure. -The above-mentioned problems have been solved by a method for producing mold and antiviral fibers.

  When the inorganic value / organic value exceeds 1.4, since it has moderate hydrophilicity, a high antibacterial effect can be obtained even in a low humidity state. On the other hand, the inorganic value / organic value is 3.3 or less, and has an appropriate hydrophobicity, and after returning to normal pressure after exhaustion, the molecular chain constituting the fiber is loosened. Since the antibacterial agent that entered the amorphous part is trapped inside the fiber due to abrupt contraction, the outflow from the fiber can be suppressed, and further, it was exhausted into the fiber by heat treatment under normal pressure Antibacterial agents bleed out near the surface, causing so-called bleed out, and can retain antibacterial, antifungal and antiviral properties even after washing.

Hereinafter, the present invention will be described in detail.
The present invention provides a hermetically heated aqueous suspension in which a synthetic fiber and a pyridine-based antibacterial agent having an inorganic value / organic value exceeding 1.4 and exceeding 3.3 are dispersed in the form of fine particles. By allowing the synthetic fiber to exhaust the pyridine antibacterial agent by flowing under pressure, the synthetic fiber is returned to normal pressure, and then the synthetic fiber is heat treated under normal pressure. -This is a method for producing mold-proof and anti-virus fibers.

  The above “inorganic values” and “organic values” are values that treat the polarity of various organic compounds invented by Mr. Minoru Fujita in an organic concept [reform chemical chemistry-organic chemistry-Kawai Shobo ( 1971)], and then systematically compiled by Yoshio Koda [Organic Conceptual Diagram-Fundamentals and Applications-Sankyo Publishing (1984)]. This “inorganic value” represents a characteristic as an ionic bond, and “organic value” represents a characteristic as a covalent bond. Generally, as the “inorganic value” increases, hydrophilicity, When the “organic value” is high, it tends to be hydrophobic. These values are determined as shown in Table 1.

  Furthermore, the inorganic value of the metal in the chelate compound, which is considered to have an intermediate property between ionic bond and covalent bond, varies depending on the coordination state. In general, heavy metals such as copper have strong covalent bonds [see Yoshio Koda, Organic Conceptual Diagram-Fundamentals and Applications-Sankyo Publishing (1984), page 128], chelate compounds containing copper The inorganic value is considered to be the lowest value 400 for heavy metals. However, since the case where the ion binding property is increasing is also considered, the value of 500 further exceeding this is also considered. However, in general, only inorganic values of inorganic substances take a specific value [see the organic conceptual diagram on page 22]. However, considering that heavy metals do not affect the organic-inorganic balance of the entire compound molecule, the inorganic nature of the metal It is considered that the value may be 0. In this case, the inorganic value of the metal in the chelate compound is a hypothetical minimum value of 0. Similarly, zinc is also a heavy metal, and values from 0 to 500 are conceivable. In the present invention, the “inorganic value / organic value” is a value obtained by calculating “the sum of the inorganic values” and “the sum of the organic values” of the values defined above, and taking the ratio of the two. Say.

  In general, when an antibacterial agent is adsorbed to a fiber, the closer the inorganic value / organic value between the antibacterial agent and the fiber, the better the affinity and the better the adsorbability. For example, the polyester mentioned as the synthetic fiber is 0.7, and this value is said to have better affinity for the antibacterial agent closer to the fiber. However, when a pyridine antibacterial agent having an inorganic value / organic value of more than 1.4 and less than or equal to 3.3 is used, polyester or the like can be obtained by the method according to the present invention in spite of the general tendency described above. Thus, a fiber having excellent antibacterial, antifungal and antiviral properties can be obtained.

  The inorganic value / organic value of the pyridine antibacterial agent used in the method according to the present invention needs to be more than 1.4 and 3.3 or less. To exceed 1.4 means to be 1.401 or more, for example. 1.46 or more, 3.25 or less is desirable, 1.8 or more, and 2.9 or less is more desirable.

  When the inorganic value / organic value is 1.4 or less, for example, the polyester fiber having an inorganic value / organic value of 0.7 has a good affinity with the fiber, and further has a high hydrophobicity. In addition, water elution is also suppressed, and it is generally considered advantageous. However, when the efficacy in the bacteria transfer method under low humidity conditions is examined, if the inorganic value / organic value is 1.4 or less, it becomes too hydrophobic, and the effectiveness drops extremely. Furthermore, since it is too oleophilic, it is easily affected by detergents, and washing resistance is deteriorated, which is not preferable. Therefore, the inorganic value / organic value needs to exceed 1.4, and more preferably 1.8 or more. On the other hand, if the inorganic value / organic value exceeds 3.3, the hydrophilicity becomes too high, the adsorption to the fiber such as polyester is poor, the washing resistance is lowered because it is washed away with water, and the antibacterial from the fiber. Agent elution also increases, which is not preferable. Therefore, the inorganic value / organic value needs to be 3.3 or less, and more preferably 2.9 or less.

  As a pyridine type antibacterial agent satisfying the above conditions, for example, 2-pyridinethiol copper-1-oxide (hereinafter referred to as “pyrition copper”) in which M in the following chemical formula (1) is Cu, and M is Zn. 2-pyridinethiol zinc-1-oxide (hereinafter referred to as “pyrithione zinc”) is exemplified, and zinc pyrithione is particularly desirable.

  When the pyridine antibacterial agent is pyrithione zinc, the inorganic value is from Table 1, “bonds described in chemical formula (2) of pyrithione: 170 × 2 = 340”, “S bond: 20 × 2 = 40”. “Aromatic ring: 15 × 2 = 30”, and zinc can take a value of 0 to 500 as described above. Therefore, the sum of the inorganic values is in the range of 410-910. On the other hand, the organic value is “C: 20 × 10 = 200” and “S bond: 40 × 2 = 80”, which is 280 in total. Therefore, when this ratio is taken, the inorganic value / organic value = (410/280) to (910/280) = 1.46 to 3.25. If the inorganic value of zinc is the minimum value of 400 for heavy metals, the total inorganic value of pyrithione zinc is 810, and the inorganic value / organic value at that time is 2.9. These values are the same when the pyridine antibacterial agent is pyrithione copper.

  Therefore, the inorganic value / organic value of the pyridine antibacterial agent is 1.46 or more, preferably 3.25 or less, and more preferably 2.9 or less.

  The inorganic value / organic value of these pyridine antibacterial agents is slightly different from the inorganic value / organic value = 0.7 of polyester fiber having high organic property. Nevertheless, when these pyridine antibacterial agents are used on polyester fibers in water, the pyridine antibacterial agents are easily absorbed and exhausted by the polyester fibers. This is more stable when the pyridine antibacterial agent dispersed in the form of fine particles having an inorganic value / organic value of 3.3 or less is adsorbed on the surface of the polyester fiber rather than being independently present in water. This is probably because of this.

  Moreover, the water solubility of said pyridine type antibacterial agent is as low as 0.01-30 ppm, for example, 25 degreeC water solubility of pyrithione zinc which is said pyridine type antibacterial agent is 8 ppm, and in the case of pyrithione copper, it is 1 ppm or less. However, they are preferably used because they are adsorbed on synthetic fibers having a high organic property and are less leached into water.

  Furthermore, the organic solvent solubility of the pyridine antibacterial agent is 0.01 to 100 ppm as solubility at 25 ° C. in n-octanol, which is an organic solvent generally used for n-octanol / water partition coefficient. Is difficult to dissolve and has low affinity. For this reason, the antibacterial agent is not easily micelle by the detergent at the time of washing, and the antibacterial activity can be maintained high even after washing.

  The synthetic fiber is exhausted with the pyridine antibacterial agent. In general, a synthetic fiber made of a polymer is composed of a dense part (crystalline part) and a sparse part (non-crystalline part) where molecules are gathered, and has a glass transition temperature (hereinafter referred to as “Tg temperature”) or higher. Then, the molecular chain of the non-crystalline part is loosened and the fluidity is increased, so that molecules such as antibacterial agents can easily enter. Therefore, when exhausting while flowing the pyridine antibacterial agent and the synthetic fiber under a closed heating and pressurizing condition, the pyridine antibacterial agent is efficient in the fiber if the exhaustion is performed at the appropriate temperature above the Tg temperature. It is exhausted well and is in a good fixed state. In that case, it is necessary to make the pyridine antibacterial agent into the aqueous suspension. The aqueous suspension referred to here means that the state under normal temperature and normal pressure is the same, and more pyridine antibacterial agents may be dissolved under heating and pressurization. In the present invention, the aqueous suspension under normal temperature and normal pressure may be one in which all the pyridine antibacterial agents are dissolved under the heating and pressurization for exhaustion and are not suspended.

  The aqueous suspension is a suspension obtained by stirring or pulverizing the pyridine antibacterial agent in the presence of a dispersant such as a surfactant and water. The average particle size of the pyridine antibacterial agent in this aqueous suspension is preferably 0.1 to 2 μm, and more preferably 0.1 to 1 μm. If the average particle size exceeds 2 μm, precipitation may occur and the treatment agent may become unstable, and the particle size may be too large to cause exhaustion to the fibers during processing. Therefore, the pyridine antibacterial agent having a particle size of 2 μm or more is preferably 5% by weight or less, preferably 3% by weight or less, and preferably 1% by weight or less based on the total weight of the pyridine antibacterial agent. And more preferably 0.5% by weight or less.

  In addition, the average particle diameter of the particles of the pyridine antibacterial agent in the aqueous suspension is measured using a laser diffraction particle size distribution measuring device based on JIS R 1629, and the median diameter corresponding to a cumulative 50% is obtained. It is what I have sought.

  The dispersant is not particularly limited. For example, anionic surfactants such as lignin sulfonate, nonionic surfactants such as polyoxyethylene hydrogenated castor oil, and quaternary ammonium salt cationic surfactants. , PVA and the like. If necessary, a thickening agent, an antifreezing agent, and an antifoaming agent are added to these dispersants to form a slurry, and if necessary, a suspension is obtained using a ball mill, a ceramic mill or a pearl mill, and the above aqueous suspension is added. Use a suspension.

  The weight of the dispersant in the aqueous suspension is preferably 1/50 to 1/1 of the weight of the pyridine antibacterial agent, particularly preferably 1/25 to 1/2. When the amount of the dispersant is larger than this, the dispersant adheres to the fiber, the texture is impaired, and other dyeing auxiliary agents are adversely affected. On the other hand, if the amount is too small, the pyridine-based antibacterial agent settles and is not stable as a treatment agent, and there is a possibility that a problem may remain.

  When the synthetic fiber is exhausted with the pyridine antibacterial agent by the aqueous suspension, the aqueous suspension is preferably an aqueous solution containing 50 to 99.999% by weight of water. When the water content is 50% by weight or more, precipitation and aggregation are unlikely to occur, the stability is excellent, and handling becomes easy.

  The pH of the aqueous suspension is desirably 4 to 9, more desirably 5 to 8, and still more desirably 5.5 to 7. This is because, if the pH is less than 4 or more than 9, the pyridine antibacterial agent is decomposed, and the antibacterial / antifungal / antiviral properties are not maintained.

  When the pyridine antibacterial agent is exhausted to the synthetic fiber by the aqueous suspension, the concentration of the pyridine antibacterial agent in the aqueous solution is preferably 10 to 1600 ppm by weight, and 50 to 900% by weight. More desirably, it is ppm, and further desirably is 100 to 500 ppm by weight. When the content is 10 ppm by weight or less, exhaustion of the pyridine antibacterial agent to the synthetic fiber is not sufficient, and the antibacterial activity becomes too low. On the other hand, even if it is 1600 ppm by weight or more, a large amount of the pyridine antibacterial agent is consumed for its efficacy, which is not preferable.

  The aqueous suspension may be diluted with water and exhausted to the synthetic fiber so that the concentration of the pyridine antibacterial agent in the aqueous solution falls within this range. It is preferable to prepare a suspension and dilute it before use. For example, a 10 to 30% stock solution is prepared and diluted to a preferred concentration at the time of use. By doing so, the liquid can be stably stored for a long period of time, and the transportation cost to the site of use can be reduced.

  When the pyridine antibacterial agent is exhausted to the synthetic fiber by the aqueous suspension, the weight of the aqueous suspension is desirably 4 to 30 times that of the synthetic fiber, and 5 to 20 times. Is more desirable, and is more desirably 6 to 15 times. If it is less than 4 times, the amount of moisture is small, so the processing unevenness increases, and the quality may not be stable. On the other hand, even if it exceeds 30 times, there is a limit to the amount of medicine exhausted by the fiber, and many medicines are discarded without being used, resulting in waste.

  In addition, when exhausting the said aqueous suspension to the said synthetic fiber, you may add a dyeing agent and a dyeing auxiliary agent to the aqueous solution. For example, disperse dyes, acid dyes, cationic dyes, fluorescent whitening agents, water repellents, antifouling agents and the like generally used for fibers. Furthermore, if necessary, antibacterial agents such as zinc oxide and titanium oxide, insecticides, acaricides, flameproofing agents, antioxidants, fixing agents and the like may be added.

  The aqueous suspension is sealed together with the synthetic fiber and fluidized under heating and pressurizing conditions, thereby exhausting the pyridine antibacterial agent into the synthetic fiber. The gauge pressure at that time is preferably 0.5 to 4 kg / cm @ 2 (49 to 392 kPa), more preferably 1 to 3 kg / cm @ 2 (98 to 294 kPa). Further, the temperature is desirably 110 to 150 ° C, and more desirably 120 to 140 ° C. By being under this condition, the pyridine antibacterial agent is mainly selectively exhausted into the amorphous part of the synthetic fiber. When exhaustion is performed under such conditions, it is considered that the pyridine antibacterial agent is dissolved in an amount of about 50 to 200 ppm. If the temperature or pressure is lower than the above range, the amorphous part of the synthetic fiber does not swell and the pyridine antibacterial agent is hardly exhausted by the synthetic fiber. On the other hand, if the temperature or pressure is higher than the above range, the risk of mechanical explosion of the pressurizing device increases.

  The fluidizing time under the above heating and pressurizing condition is preferably 10 to 90 minutes, more preferably 15 to 80 minutes, and further preferably 20 to 60 minutes. If it is less than 10 minutes, the pyridine antibacterial agent is not sufficiently exhausted by the synthetic fiber, and the antibacterial / antifungal / antiviral properties may be insufficient. On the other hand, if the time is too long, the exhaustion of the pyridine antibacterial agent is almost finished, so that it takes only an extra time and the production efficiency is lowered.

  In the present invention, the device for sealing the aqueous suspension and the synthetic fiber needs to be able to withstand the temperature and pressure. In addition, it is necessary to have a function of allowing either or both of the aqueous suspension and the synthetic fiber to flow inside the apparatus. Examples of the fluidizing method include a method of rotating the synthetic fiber in a sealed apparatus and a method of circulating the aqueous solution.

  Further, when exhausting while flowing, it is desirable that the apparatus is not filled with the aqueous suspension but gas is present in the apparatus. This gas is desirably a gas that does not affect the aqueous suspension or the synthetic fiber, such as air, nitrogen, or argon. The volume ratio of the gas to the aqueous suspension in the apparatus is desirably 1/1 to 1/95, and more desirably 1/2 to 1/9. When the gas is contained in a volume ratio in the above range, the fluidity between the aqueous suspension and the synthetic fiber is good, the contact between the pyridine antibacterial agent and the synthetic fiber increases, and the absorption. Increases exhaust efficiency. Further, when gas is present, it functions as a pressure buffering material for the apparatus, and stable operation is performed. When the volume ratio of the gas to the aqueous suspension is more than 1/1, the contact between the synthetic fiber and the aqueous suspension is small, exhaustion efficiency is deteriorated, and processing unevenness is caused. It becomes easy to do. On the other hand, when there are more said aqueous suspensions than 1/95, the fluidity | liquidity of a liquid will worsen, exhaustion efficiency will worsen, and antibacterial, antifungal, and antiviral performance will become inadequate.

  As described above, after the pyridine antibacterial agent is exhausted to the fiber, the inside of the apparatus is returned to normal pressure. When returning to normal pressure, it is desirable to return to normal pressure while cooling. More preferably, the pressure is lowered while cooling, and the pressure is released at a timing when the temperature becomes 110 ° C. or lower to obtain a normal pressure. By returning to normal pressure, the loosened molecular chain of the synthetic fiber closes, so that the pyridine antibacterial agent is immobilized in the synthetic fiber. Also, when cooling and returning to normal pressure, it is more desirable to continue the above flow because the uniformity of the pyridine antibacterial agent is increased and the adsorption exhaust unevenness can be reduced.

  Next, the synthetic fiber taken out from the apparatus after returning to normal pressure as described above is heat-treated in a normal pressure environment so that the pyridine-based antibacterial agent inside the synthetic fiber is oozed out. More can be present in the vicinity of the surface. This is because the inorganic value / organic value of the synthetic fiber and the inorganic value / organic value of the pyridine antibacterial agent are slightly separated, and the affinity between the fiber and the pyridine antibacterial agent is not so great. This is because it is not good and can be exuded. By performing this heat treatment, the resulting antibacterial / antifungal / antiviral fiber has more pyridine antibacterial agent present near the surface of the fiber, improving the antibacterial / antifungal / antiviral properties.

  Prior to the heat treatment, it is desirable to wash the synthetic fibers to wash away impurities, excess aqueous suspension, or simultaneously processed disperse dyes, other auxiliaries, and the like. The liquid used for washing is not particularly limited, but usually water or an alkaline liquid is used. The pyridine antibacterial agent necessary for exhibiting antibacterial / antifungal / antiviral properties is exhausted in the synthetic fiber, and even when washed, the antibacterial / antifungal / antiviral properties do not decrease.

  Specific methods for performing the heat treatment include methods of applying hot air or squeezing with a hot roller, but are not particularly limited to these methods. The appropriate temperature for carrying out this treatment is preferably a temperature range that is equal to or higher than the Tg temperature and that the synthetic fiber itself does not cause an undesirable alteration such as decomposition. The appropriate temperature and the appropriate treatment time vary depending on the type of the synthetic fiber.

  When the synthetic fiber is a polyester fiber, the pyridine antibacterial agent can be appropriately leached and fixed inside the synthetic fiber by heat treatment at (Tg + 40) to (Tg + 110) ° C. as the appropriate temperature. So desirable. Specifically, since Tg of many polyester fibers is 70 to 80 ° C, the appropriate temperature is preferably 110 to 190 ° C, and preferably 150 to 180 ° C. When the temperature is less than 110 ° C., the pyridine antibacterial agent hardly oozes out, the concentration of the pyridine antibacterial agent in the vicinity of the surface cannot be further increased, and no further increase in antibacterial activity is observed. On the other hand, when the temperature exceeds 190 ° C., the synthetic fiber itself may be deteriorated, and the pyridine antibacterial agent may be changed in color.

  The treatment time for the heat treatment is desirably 20 seconds to 3 minutes, and more desirably 30 seconds to 2 minutes. If it is too short, the pyridine antibacterial agent is difficult to ooze out, the concentration of the pyridine antibacterial agent in the vicinity of the surface cannot be further increased, and further improvement in antibacterial activity is not observed. On the other hand, if it is too long, it will take time, resulting in poor work efficiency and high cost.

  Furthermore, in the above heat treatment, a plurality of heat treatment steps in which the temperature rises stepwise, or the temperature continuously increases so that the temperature difference between the temperature at the start of heat treatment and the temperature of the maximum heat treatment is 20 ° C. or more. It is desirable to heat-treat the synthetic fiber by providing an ascending heat treatment step. Moreover, you may provide the heat treatment process provided as a step | paragraph, and the heat treatment process which raises temperature continuously. At first, heat treatment at a low temperature can prolong the moisture-rich state while heating, allowing the pyridine antibacterial agent to bleed out near the surface more efficiently. Viral nature can be improved. In addition, you may provide the heat processing process in which the temperature fell from the said maximum heat processing in steps or continuously after the heat processing process used as the said maximum heat processing.

  The above-mentioned plural stages are realistic from 2 to 10 stages, and if they are 11 stages or more, the work process becomes too complicated. The more preferable temperature difference is 20 to 80 ° C, and more preferably 30 to 70 ° C. The temperature at the start of the heat treatment is desirably 110 to 135 ° C, and more desirably 120 to 130 ° C. The maximum heat treatment temperature is desirably 150 to 190 ° C, and more desirably 160 to 185 ° C. When performing a multistage heat treatment process, the heat treatment time in each stage is preferably 30 seconds to 3 minutes, and more preferably 1 to 2 minutes. In addition, when raising temperature continuously, it is desirable that the temperature increase rate is 6-160 degreeC / min.

  As the synthetic fiber for exhausting the pyridine antibacterial agent by the above process, the polyester fiber is desirable because of its excellent industrial washing durability. Polyester fibers include not only petroleum-derived fibers such as polyethylene terephthalate, but also natural fibers such as polylactic acid. Furthermore, natural fibers such as cotton, wool, silk, and semi-synthetic fibers such as rayon may be used in combination with the above synthetic fibers. The form of the synthetic fiber to be used is not particularly limited, such as yarn, woven fabric, and non-woven fabric.

  The synthetic fiber exhausted with the antibacterial agent by the production method according to the present invention has an inorganic value / organic value of the antibacterial agent of 3.3 or less, a low water solubility of 30 ppm or less, and heating and pressurization. Since the antibacterial agent is strongly fixed near the surface by exhausting while flowing under conditions, and then returning to normal pressure and heat-treating, the above pyridine antibacterial agent is almost dissolved even after water treatment such as washing Therefore, the antibacterial activity is maintained at a high level, and the antibacterial / antifungal / antiviral fiber is safe and excellent. Furthermore, since the inorganic value / organic value of the antibacterial agent exceeds 1.4 and is moderately hydrophilic, the effect is sufficiently exerted even under low humidity conditions such as experimental conditions in the bacterial transfer method, Antibacterial, antifungal and antiviral fiber with high antibacterial efficacy.

Furthermore, DNA viruses such as SARS virus, Lassa fever virus, Ebola hemorrhagic fever virus, AIDS virus, West Nile virus, Dengue virus, Japanese encephalitis virus, bird flu virus, human influenza virus, smallpox virus, herpes virus, etc. It also becomes an antibacterial, antifungal and antiviral fiber having antiviral properties. In addition, it is considered that the antiviral effect is exerted on the fiber obtained by the production method according to the present invention due to the denaturing action of the antibacterial agent on the viral coat protein, and obtained by this production method. Antibacterial, antifungal, and antiviral fibers have antibacterial agents efficiently adhered to the fibers even after washing.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the following text, “%” means “% by weight”. First, each test method and washing method will be described.

(Method for measuring the amount adsorbed on fibers)
The amount of adsorption to the fiber was estimated by measuring the difference in the pyridine antibacterial agent contained in the aqueous suspension before and after exhaustion under heating and pressure. That is, the amount of zinc or copper contained in the aqueous suspension before exhaustion treatment and the amount of zinc or copper remaining in the liquid after exhaustion treatment were measured using an atomic absorption photometer. From the difference, the amount of pyridine antibacterial agent adsorbed in the fiber was calculated.

(Test bacteria and evaluation methods for antibacterial tests)
Antibacterial properties were evaluated using two types of Staphylococcus aureus (Staphylococcus aureus and MRSA) and Klebsiella pneumocniae. As evaluation objects, processed fabrics before and after washing were used (represented as “front” and “rear” in the table, respectively).

  First, as a first evaluation method, a fungus transfer method described in an antibacterial test method for textiles defined in JIS L 1902 (2002) (denoted as “fungus transfer method” in the table) was performed. Judgment is made by comparing the decrease in the number of bacteria after 4 hours of culturing under low humidity with the number of bacteria recovered from each test cloth. The case where it was made effective ((circle)) and the case where it is less than 0.5 was made invalid (x).

  Further, as a second evaluation method, a bacterial liquid absorption method (indicated as “bacterial liquid test” in the table) defined in JIS L 1902 (2002) was carried out. The determination was made effective (◯) when the bacteriostatic activity value of each test cloth was 2.2 or more, and invalid (x) when less than 2.2.

(Test fungus for antifungal test and evaluation method)
The antifungal property was evaluated using four types of fungi (Aspergillus niger, Penicillium citrinum, Chaetmium globosum, and Myrothecium verrucaria). As an evaluation method, a wet method defined in JIS Z 2911 (2000) was performed. Judgment is effective (○) when the display method 0 of the antifungal test results (no growth of the hyphae is not observed in the inoculated part of the sample or test piece), and 1 (the hyphae recognized in the inoculated part of the sample or test piece) The area of the growth part is not more than 1/3 of the total area) and 2 (the area of the growth part of the mycelium found in the inoculated part of the sample or test piece is more than 1/3 of the total area) is invalid (X).

(Antiviral test and evaluation method)
Conducted at the Virus Testing Center, the Center for Disease Control and Control of the People's Republic of China. Inactivation against SARS virus outside the body of processed fabric 50 times after industrial washing using virus CPE (cytopathogenic effect) method in culture system of African green monkey kidney passage cells (VERO E6: provided by Virus Test Center) The effect was evaluated by comparing with the virus control group.

Specifically, it is as follows.
<Process cloth and virus pretreatment>
Two strains of SARS virus (SARS-COV-P5: Coronavirus isolate, provided by the Virus Resource Center (Certificates of the People's Republic of China Pharmaceuticals and Biological Products Certificate: SH200400011), and SARS-COV-P11: Coronavirus isolate, Diluted with pure water so that the virus dilution concentration is 100 TCID50 (TCID50 = half tissue culture infectious dose) provided by the Virus Resource Center (certified by the People's Republic of China Pharmaceuticals and Biological Products Test Certificate: SH200400017). Was poured into a processed cloth after 50 times of industrial washing to fully infiltrate the cloth. This was left at room temperature for 10, 15, 30, 45 minutes, 1, 2, 3 hours, and then the virus diluted solution in the processed cloth was pushed out with aseptic tweezers to obtain a solution (hereinafter referred to as “treatment solution”). Obtained).

<Confirmation of inactivation effect by viral CPE method in VERO E6 cell culture system>
VERO E6 cells were inoculated at a concentration of 400,000 cells / ml into 96-well culture plates (provided by Beijing Takashiba Forest Biotechnology Co., Ltd.) and cultured at 37 ° C. for 24-48 hours to monolayer the cells. To this, 100 μl of each of the above-mentioned treatment liquids in each time course was put in 4 holes. This was cultured for 6 days in an environment of 5% CO2, and virus CPE was observed with an inverted microscope, and the results were recorded.

  The criteria at that time are as follows. “-” Indicates no change in viral cell CPE and 100% virus was inactivated, “+” indicates 25% or less CPE change and 75% virus inactivated, “++” indicates 26 50% inactivation with ~ 50% CPE change, "++++" not inactivated with 51-75% CPE change, 25% inactivation, "++++" not inactivated with 76-100% CPE change It shows that.

(Dissolution test method)
Measure the amount of pyridine antibacterial agent eluted from the processed fabric before washing into water ((1) in the table), 20% ethanol aqueous solution ((2) in the table), and 4% acetic acid ((3) in the table). did. Specifically, 20 g of the solution was immersed in 1 g of fiber in 20 ml of a solution at 40 ° C. for 10 days, the impure organic matter in the eluate was decomposed by hydrochloric acid treatment, and the remaining metal was measured with an atomic absorption photometer. The initial amount of the pyridine antibacterial agent attached to the fiber was measured by the above-described method for measuring the amount of adsorption onto the fiber.

(Washing method)
Industrial washing was carried out by a washing method in accordance with Ordinance No. 13 of the Ministry of Health, Labor and Welfare established by the Japan Textile Evaluation Technology Council (JTETC). Specifically, it was carried out 50 times under conditions of 80 ° C. (industrial laundry) using a JAFET standard detergent.

(Production of aqueous suspension)
Next, the manufacturing method of aqueous suspension is demonstrated.
As a pyridine-based antibacterial agent, pyrithione zinc (manufactured by Arch Chemical Co., Ltd., abbreviated as “ZPT” in the table, where the inorganic value / organic value is calculated as 2.9 when the inorganic value of zinc and copper is 400). ), Pyrithione copper (manufactured by Arch Chemical Co., Ltd., abbreviated as “CuPT” in the table), and sodium pyrithione where the inorganic value / organic value is calculated as 5.0 when the inorganic value of sodium is 500 (Manufactured by Arch Chemical Co., Ltd., abbreviated as “NaPT” in the table). Each physical property is as follows.
(Physical properties of zinc pyrithione)
Inorganic value / organic value: 2.9
・ Water solubility: 8ppm (25 ℃)
Organic solvent solubility (octanol): 5ppm
・ Average particle size: 0.5μm
-Ratio of particles of 2 μm or more: 0%
・ PH: 6.6
(Pyrithione copper properties)
Inorganic value / organic value: 2.9
・ Water solubility: 0.5ppm (25 ℃)
Organic solvent solubility (octanol): 0.3 ppm
・ Average particle size: 0.5μm
-Ratio of particles of 2 μm or more: 0.5%
・ PH: 7.1
(Physiology of pyrithione sodium)
Inorganic value / organic value: 5.0 (value calculation is described in Table 2. In the table, “I / O value” is abbreviated.)
Water solubility: 53% (25 ° C)
Organic solvent solubility (octanol): 0.1 ppm
・ Average particle size: Water-soluble (complete dissolution)
-Ratio of particles of 2 μm or more: Water-soluble (complete dissolution)
-PH: 8.3

The above pyridine antibacterial agents were mixed in the following component ratios.
-Pyrithione zinc, pyrithione copper or pyrithione sodium: 20 parts by weight-Polyoxyethylene alkyl ether sulfate ester salt (dispersing agent, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Hightenol 08E): 3 parts by weight-Glycerin (freezing agent Wako Jun) Yaku Kogyo Co., Ltd.): 2 parts by weight / purified water: 75 parts by weight was mixed into a paste, and then pyrithione zinc and pyrithione copper were made into a suspension having an average particle diameter of 0.5 μm using a ceramic mill. Sodium pyrithione was stirred to form a transparent uniform liquid. The obtained aqueous suspension or transparent liquid was diluted with water so that the respective pyridine antibacterial agents would be 0.8% to obtain an aqueous suspension (aqueous transparent liquid for sodium pyrithione). The pH of the obtained aqueous suspension is 6.8 using pyrithione zinc, 7.1 using pyrithione copper, and 7.4 using sodium pyrithione, respectively.

(Synthetic fibers)
As synthetic fibers, polyester fibers (Fiber Tropical for Color Dyeing Company: 150 denier x 48 filaments manufactured by Toray Industries, Inc., abbreviated as “PET” in the table) were used.

( Reference Example 1)
The aqueous suspension of pyrithione zinc was diluted with water so that the concentration of pyrithione zinc was 400 ppm to obtain an aqueous solution. A ratio of 10 g of polyester fiber to 150 ml of this aqueous solution was placed in a sealed container having an internal volume of 180 ml, and air as a gas was sealed in a high-temperature and high-pressure machine with a gas / liquid ratio of 2/15. . The hermetic container was rotated in a high-temperature and high-pressure machine and subjected to high-temperature and high-pressure treatment for 1 hour at a temperature of 130 ° C. and a gauge pressure of 1.9 kg / cm 2 (186 kPa) while flowing inside. After that, the pressure was reduced while cooling while continuing the flow in a sealed state, and the flow was stopped after confirming that the internal temperature was 100 ° C. or less and the internal pressure was 0 kg / cm 2 (0 kPa) as a gauge pressure. The polyester fiber was taken out. The fiber thus taken out was washed with water and then heat treated at 130 ° C. for 1 minute and then at 170 ° C. for 1 minute with an atmospheric pressure heat dryer to obtain a processed cloth which was an antibacterial / antifungal / antiviral fiber. Table 3 shows the results of elution and antibacterial / antifungal evaluation of the processed fabric before and after industrial washing. In addition, since processing unevenness may occur, the evaluation was performed three times under the same conditions while changing the sampling location. In addition, the inorganic value / organic value is expressed as “I / O value” in the table, and 100% of the pyridine antibacterial agent used is adsorbed out of the adsorption concentration of the pyridine antibacterial agent on the polyester fiber. The adsorption concentration of the pyridine antibacterial agent measured by the adsorption amount measuring method is expressed as “expected concentration”.

( Reference Example 2)
A processed cloth which is an antibacterial / antifungal / antiviral fiber was obtained in the same manner except that pyrithione copper was used instead of pyrithione zinc in Reference Example 1. Table 3 shows the evaluation results of this work cloth.

( Reference Example 3)
A processed cloth which is an antibacterial / antifungal / antiviral fiber was obtained in the same manner except that the heat treatment for 1 minute at 130 ° C. in Reference Example 1 was not performed. Table 3 shows the evaluation results of this work cloth.

(Comparative Example 1)
A processed cloth was obtained in the same manner except that sodium pyrithione was used in place of pyrithione zinc in Reference Example 1. Table 3 shows the evaluation results of this work cloth.

(Comparative Example 2)
A processed cloth was obtained in the same manner as in Reference Example 1 except that the inside was not flowed during heating and pressurization. Table 3 shows the evaluation results of this work cloth.

(result)
Antibacterial fibers produced by flowing pyridine-based antibacterial agents with inorganic / organic values exceeding 1.4 and not more than 3.3 under heated and pressurized conditions show a stable antibacterial effect. Also, no elution occurred. On the other hand, those using a pyridine antibacterial agent whose inorganic value / organic value exceeds 3.3, or those that are not allowed to flow during heating and pressurization, the antibacterial effect is not stable and elution occurs. I have.

(Example 1 )
In Reference Example 1, a processed cloth that was antibacterial / antifungal / antiviral fiber was obtained in the same manner as in Reference Example 1 except that an aqueous solution diluted with water so that the concentration of pyrithione zinc was 267 ppm was used. The expected adsorption concentration at that time was 0.4%, and the actually measured concentration was 0.38%. Moreover, industrial washing was similarly performed 50 times at 80 degreeC. An antiviral test was performed using this processed cloth. The results are shown in Table 4. An inactivation effect on the virus appeared in 1 hour or more, and a 100% inactivation effect was obtained in 3 hours.
(Comparative Example 3: Control)
An antiviral test was performed using the above virus diluted solution that had not been treated with a processed cloth. The results are shown in Table 4.

Claims (2)

  The antiviral agent containing 2-pyridinethiol zinc-1-oxide, 2-pyridinethiol copper-1-oxide, or both represented by the following chemical formula (1).

  Antiviral effect on at least one of SARS virus, Lassa virus, Ebola virus, AIDS virus, West Nile virus, Dengue virus, Japanese encephalitis virus, avian influenza virus, human influenza virus, smallpox virus, and herpes virus The antiviral agent according to claim 1, comprising: