JP2015190069A - Antibacterial and deodorant cloth having excellent durability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial and deodorant cloth that is treated with a metal chelate fine particle water dispersion having excellent antibacterial and deodorant performance, the cloth having excellent washing durability.SOLUTION: This invention provides an antibacterial and deodorant cloth that is a cloth on which metal chelate fine particles with an average particle diameter of 50 nm or less are deposited, wherein the number of metal chelate fine particles more than 50 nm in particle size are two or less per cloth surface area 500 nm.

Description

  The present invention relates to a fabric excellent in durability of antibacterial deodorizing performance. More specifically, the present invention is characterized in that the fabric is treated with an aqueous dispersion of metal chelate fine particles having antibacterial and deodorant performance, and the metal chelate fine particles are adhered to the surface of the fabric. In addition, the present invention relates to a fabric having excellent water absorption / diffusion performance, color development and dyeing fastness.

In recent years, antibacterial performance and deodorizing performance have been demanded as functions for satisfying comfort when wearing clothes, particularly comfort in daily life in summer. Especially in the summer season, long-term temperatures of 25 ° C or higher, such as in summer and midsummer environments, it has antibacterial and deodorant durability to maintain comfort and comfort, and sweat. Immediately absorbing water and diffusing when it is present is important to realize the comfort of wearing.
In order to achieve antibacterial and deodorant performance, textile products with metal fine particles such as zinc have been proposed, but many of them have low durability or a texture in environments where they are frequently washed in the summer season. There is a problem that it is bad and is not comfortable to wear.

In Patent Document 1 below, a fine zinc oxide is added to a polymer bath at the time of spinning to produce a polyamide fiber, a fabric is formed from the obtained fiber, and then chitosan is added to give ammonia deodorizing performance and antibacterial properties. It is disclosed that a fabric excellent in performance can be obtained. However, the deodorizing effect on the acidic odor is poor, there is a problem in durability of washing 50 times or more, and the water absorption / diffusion performance is poor, so that the comfort when sweating is poor.
Patent Document 2 below discloses that a fiber having antibacterial and deodorant performance can be obtained by applying zinc compound fine particles and zirconium compound fine particles together with a water-soluble binder resin to the fiber surface. However, since the metal fine particles are directly applied to the fiber surface together with the binder, there is no flexibility, the water absorption / diffusion performance is poor, and as a result, the comfort is not good, and the antibacterial deodorizing performance is not more than 50 times of washing. There is a problem.

Patent Document 3 below discloses that deodorization performance can be obtained by treating fibers with a treatment liquid containing chitosan, a carboxylic acid polymer, zinc oxide, and a binder resin. However, since the binder resin is used, there is a problem that it is not flexible, has poor water absorption and diffusion performance, is not comfortable to wear, and has no antibacterial effect.
Further, in Patent Document 4 below, a fabric excellent in antibacterial, deodorant, water absorption and quick-drying performance by applying an aqueous solution of platinum nanocolloid or a mixed solution of this aqueous solution and an antibacterial deodorant or antibacterial deodorant to the fabric. Is disclosed. However, although the antibacterial deodorizing effect on the fabric made of cotton fibers is good, when processed into a mixed fabric of cellulose fibers and synthetic fibers, especially a long fiber composite fabric, the deodorizing effect after 50 washings is poor and the water absorption There is a problem of poor diffusibility and poor comfort.

  In this way, at present, dyed fabrics that are finished without using a binder resin have excellent antibacterial and deodorant performances, and are excellent in washing durability and water absorption / diffusion performance of these performances. There is no dyed product that has a supple feel, is comfortable to wear, and has excellent color development and dyeing fastness performance.

Japanese Patent No. 3550816 Japanese Patent No. 3568613 Japanese Patent No. 3787675 International Publication No. 2012/086204 Pamphlet

  The problem to be solved by the present invention is that the metal chelate fine particles in the aqueous dispersion of metal chelate fine particles having excellent antibacterial and deodorant performance are directly and firmly attached to the fabric surface without using a resin binder, and thus the antibacterial performance and antibacterial properties are eliminated. An object of the present invention is to provide a fabric excellent in washing durability with odor performance.

The present inventor has intensively studied to solve the above-mentioned problems and repeated experiments, and when the metal compound is subjected to ultrasonic irradiation treatment in the presence of a chelating agent, metal chelate fine particles having excellent antibacterial and deodorant performance can be obtained. It has been found that by applying fine particles to a fabric without using a resin binder, a fabric having excellent antibacterial and deodorant washing durability and high water absorption and diffusion performance can be obtained, and the present invention has been completed.
That is, the present invention is as follows.

[1] Antibacterial deodorizing property characterized in that it is a fabric to which metal chelate fine particles having an average particle size of 50 nm or less are adhered, and has 2 or less metal chelate fine particles having a particle size of more than 50 nm per 500 nm ^{2 of} fabric surface area. Fabric.
[2] The above, wherein the fabric is immersed in a dispersion obtained by dispersing metal chelate fine particles in an acidic solution having a pH of 3.5 to 5.0 and treated at a temperature of 100 to 135 ° C. for 15 to 45 minutes. The method for producing an antibacterial and deodorant fabric according to 1).

  The metal chelate fine particle aqueous dispersion used in the present invention has an excellent antibacterial deodorizing performance, and by treating the fabric with this aqueous dispersion, it has an excellent antibacterial deodorizing performance. A fabric excellent in washing durability, having a supple feel, excellent in water diffusibility and comfort, and excellent in color development and dyeing fastness can be obtained.

Hereinafter, the present invention will be described in detail.
The metal chelate fine particle aqueous dispersion used in the present invention is a fine particle aqueous dispersion having a structure in which a metal is chelated with a chelating agent. The metal chelate fine particle water dispersion can be obtained by irradiating a solution of a metal compound, a chelating agent and water dissolved in alcohol with ultrasonic irradiation to chelate the metal and make it fine, and then disperse in water. it can.

  In general, when the particle size of the metal oxide is reduced, there is a problem that the interaction between particles appears and the particles tend to aggregate. In the present invention, the metal compound is irradiated with ultrasonic waves in the presence of a chelating agent and water. Since the metal is chelated and finely divided, the metal chelate fine particle aqueous dispersion having excellent dispersibility can be easily obtained without aggregation when further dispersed in water.

  The chelating agent referred to in the present invention is a diketone such as 2,4-pentanediol and ethyl acetoacetate, a polyhydric alcohol such as 1,2-propanediol and diethylene glycol, N, N-dimethylethanolamine, and triethanolamine. Alkanolamines such as glycolic acid, lactic acid, citric acid, malic acid, etc., each of which can be used alone or in combination, and among them, oxycarboxylic acid is a metal It is preferable because variation in the particle size of the chelate fine particles can be reduced, and when dispersed in water, it is easy to obtain a dispersion free of aggregation and is easily adsorbed to the fabric by a non-binder. The chelating agent is preferably dissolved in water and then added to the alcohol for dissolution.

  The metal used in the present invention may be at least one selected from silver, copper, zinc, gold, and platinum. The metal compound used in the present invention may be selected from inorganic salts such as metal nitrates, chlorides, sulfates and carbonates, or hydrophilic organic acid salts such as acetates and citrates. It is preferable because the salt is easily soluble in alcohol, and when the chelated metal chelate fine particles are dispersed in water, a dispersion free from aggregation is easily obtained.

  The alcohol used in the present invention may be selected from aliphatic alcohols such as ethanol and methanol. Among them, the use of methanol has a small variation in the particle size of the metal chelate fine particles obtained by ultrasonic treatment, and the average particle size. Is preferable because it is easy to obtain fine particles of 50 nm or less, preferably 20 nm or less.

  In the present invention, an average particle size of 50 nm or less, preferably 20 nm or less is obtained by adding a chelating agent dissolved in water to an alcohol, dissolving the solution, and further irradiating the solution in which the metal compound is dissolved with an ultrasonic wave. Metal chelate fine particles can be obtained. At this time, the molar ratio of the chelating agent to be dissolved in water and water is preferably 1: 1. Moreover, when the chelating agent dissolved in water is added to the alcohol and dissolved, it is preferably added to and dissolved in approximately 10 to 50 times the volume of alcohol. The concentration of the metal compound dissolved in the alcohol solution in which the chelating agent is dissolved is preferably 0.001 mol / L or more.

  In the present invention, in order to directly attach the metal chelate fine particles to the fabric surface without using a binder resin, the metal chelate fine particles must have an average particle size of 50 nm or less, preferably 20 nm or less. This can be achieved by sonication.

  The frequency of ultrasonic waves in the ultrasonic treatment is preferably 10 to 200 kHz, and metal chelate fine particles having an average particle diameter of 1.5 to 20 nm are obtained within this range. If the frequency is less than 10 kHz, the cavitation strength is too strong and the particle size variation is large, which is not preferable, and if it exceeds 200 kHz, the cavitation effect is small, so that the chelation of the metal is insufficient and the average particle size is too small. It becomes larger than 50 nm and is not preferable. The ultrasonic treatment can be performed using an ultrasonic homogenizer, an ultrasonic disperser, an ultrasonic cleaner, or the like.

In addition, means for controlling the degree of metal chelation and the particle size of metal chelate fine particles in ultrasonic irradiation treatment include the alcohol concentration, the ratio of the chelating agent and metal compound dissolved in alcohol, the treatment temperature and time, The alcohol concentration is about 5 to 20 times the weight of the metal compound, the ratio of the chelating agent to the metal compound is about 1: 1 to 1: 4, the treatment temperature is 35 to 65 ° C., and the treatment time Is 30 to 300 minutes.
In addition, when ultrasonic treatment is performed, it is preferable to perform the treatment in a closed system because the metal chelate fine particles have a stable average particle size of 50 nm or less.

Moreover, in this invention, it can be confirmed by analyzing the solution after ultrasonication by FT-IR whether the metal was chelated by ultrasonication. Judgment of chelation can be judged by whether the peak of the IR chart is shifted according to the compound used for the chelating agent. For example, when zinc acetate is used as the metal compound and lactic acid is used as the chelating agent, 1420 cm ^{− 1,} 1580 cm can peak at out-of-plane deformation vibration of OH carboxymethyl ions determined to be chelated by moving in ^-1, the moving distance of the peak at this time is 5 cm ^-1 or more If it is, it can be judged that it is chelated.

  Next, the sonicated solution is diluted with water to obtain an aqueous dispersion of metal chelate fine particles. In this case, the concentration of the metal chelate fine particles is preferably 0.01 to 2.0% by weight, 1.5% by weight is more preferred. If this concentration is less than 0.01% by weight, the antibacterial deodorizing performance is insufficient when the fabric is treated. On the other hand, when the content exceeds 2.0% by weight, the dispersion stability is poor, and aggregation occurs and particles having a particle diameter of 50 nm or less cannot be obtained. To disperse in water, stirring the water with a magnetic stirrer, etc., throwing the metal chelate fine particles into this water and stirring for about 10 to 20 minutes. Since a body is easy to obtain, it is preferable. At this time, when the pH of the aqueous solution is in the range of 3.5 to 5.0, the dispersibility is stable without aggregation.

  In the present invention, since the metal is chelated, an aqueous dispersion of metal chelate fine particles having an average particle diameter of 4 to 50 nm is obtained without causing aggregation, and when oxycarboxylic acid is used as a chelating agent, there is no aggregation. A colorless and transparent aqueous dispersion is easily obtained, and the zeta potential of the metal chelate fine particle aqueous dispersion can be easily controlled in the range of −5 to −70 mV, which is preferable because the adsorptivity to the fabric is increased. The metal chelate fine particle aqueous dispersion thus obtained can be used as an antibacterial deodorant for fabrics.

  In the present invention, in order to attach the metal chelate fine particles to the fabric, the method of treating the fabric with the metal chelate fine particle aqueous dispersion may be any method such as dipping, padding, spraying, and inkjet processing. Dipping processing that facilitates efficient adsorption and high adsorption efficiency is preferred.

  The fibers constituting the fabric of the present invention are preferably natural fibers such as cotton, hemp, silk and wool, regenerated cellulose fibers such as viscose rayon, copper ammonia rayon and polynosic, and synthetic fibers such as polyester, acrylic and polyamide. A basic dye-dyeable fiber obtained by modifying a polyester fiber with an acidic group is particularly preferable because it has high adsorptivity to metal chelate fine particles and excellent washing durability.

  In the present invention, the basic dye-dyeable fiber is a fiber made of polyester in which a polyethylene terephthalate, polybutylene terephthalate or polypyropylene terephthalate unit is a main constituent component and a basic dye-dyed seating component is copolymerized.

  Examples of the basic dye-dyed seating component include alkali metal salts of sulfoisophthalic acid and phosphonium salts of sulfoisophthalic acid, and ester-forming derivatives derived therefrom. Specific examples include alkali metal salts of sulfoisophthalic acid such as 5-sodium sulfoisophthalic acid and 5-lithium sulfoisophthalic acid, and 5- (tetraalkyl) phosphonium sulfoisophthalic acid and ester-forming derivatives derived therefrom. It is done. Of these, 5-sodium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 5- (tetrabutyl) phosphonium sulfoisophthalic acid and 5- (tetraethyl) phosphonium sulfoisophthalic acid are preferred from the viewpoint of deodorizing performance.

The copolymerization amount of the basic dye-dyed seat component is preferably 0.1 to 5 mol%, more preferably 0.5 to 3.5 mol%, based on the total acid component, from the viewpoint of deodorizing performance. It is. If the copolymerization amount is less than 0.1 mol%, the deodorizing performance cannot be obtained. On the other hand, if it exceeds 5 mol%, a decrease in the yarn strength and light resistance becomes apparent, which is not preferable.
The basic dye-dyeable fiber used in the present invention contains a surfactant such as an alkylbenzene sulfonate, a conventionally known antioxidant, a coloring inhibitor, a light-proofing agent and an antistatic agent, titanium oxide and an alkali metal. And can be produced by a conventionally known method.

  The basic dyeable fiber used in the present invention is not particularly limited, but the total fineness is preferably 20 to 200 dtex. Further, the cross-sectional shape may be flat, constricted flat, triangular, quadrilateral, three or more multi-leaf shape, C-type, H-type, W-type, X-type or hollow cross-section in addition to the round shape. An irregular cross section is preferable from the viewpoint of smooth texture and deodorizing performance, and the single yarn fineness is preferably 0.6 to 1.8 dtex.

Further, the basic dye-dyeable fiber used in the present invention may contain up to 70% of other fibers such as silk, wool, polyester, polyamide and polyacrylic fibers.
The form of the fibers may be long fibers or short fibers, and may be uniform or thick in the length direction. Examples of the form of the yarn in which the fiber is processed include ring spun yarn, open-end spun yarn and air-jet fine spun yarn, sweet-twisted yarn to high-twisted yarn, false twisted yarn, air-jet processed yarn, indentation processing Examples thereof include yarn and knitted knitted yarn.

  In addition, the basic dye-dyeable fiber and other fibers can be mixed in the form of a composite yarn mixed at the yarn stage, and the basic dye-dyeable fiber and other fibers are used for knitting and weaving. In the case of making a fabric, it is roughly classified into a mixed fabric.

  Examples of yarn forms when using basic dye dyeable fibers and other fibers are blended (mixed cotton, fleece blended, sliver blended, core yarn, silospan, silofil, hollow spindle, etc.), entangled blended fibers , Cross twist, design twist yarn, covering (single, double), composite false twist (simultaneous false twist, pre-twist false false twist), elongation difference false twist, phase difference, post-mixing after false twisting, and 2 feeds (simultaneous Feed and feed difference) Mixed use forms such as air injection processing.

  Examples of the form of the cloth to be mixed when making the cloth include a knitted fabric, a woven fabric, a non-woven fabric, and a composite fabric thereof (for example, a laminated fabric). As a specific example, there is a so-called on-machine mixed article, which includes a knitted fabric in which basic dye-dyeable fibers and other fibers are mixed together by knitting or weaving.

  In the present invention, the metal chelate fine particles are preferably attached to the fabric by a dipping method that facilitates efficient adsorption in industrial production. The dipping process can be performed simultaneously with the dyeing of the fabric or after the dyeing. The metal chelate fine particle aqueous dispersion is added to a bath in which the pH of the processing liquid is adjusted to an acidity of 3.5 to 5.0. It is preferable that the ratio is 1:10 to 30, the processing temperature is 100 to 135 ° C., and the processing time is 15 to 45 minutes, because the metal chelate fine particles are easily adsorbed stably and the washing durability is high. At this time, when the treatment temperature is less than 100 ° C., the adsorptivity of the metal chelate fine particles is poor and the washing durability is also poor. On the other hand, if the processing temperature exceeds 135 ° C., the equipment becomes large and the cost is high, which is not preferable. When the pH of the processing liquid is less than 3.5 or exceeds 5.0, the adsorptivity of the metal chelate fine particles deteriorates, which is not preferable.

  In the present invention, since the metal chelate fine particles are directly adsorbed on the fabric surface, the washing durability of the metal chelate fine particles is enhanced without using a binder resin. In particular, when a basic dye-dyeable fiber modified with an acidic group is used, it is more strongly adsorbed and has a higher adsorption rate, so it has excellent durability over 50 washings, and metal chelate fine particles after 50 washings The dropout rate is 10% or less. Moreover, since the metal chelate fine particles are adhered without using a binder resin, a supple texture can be obtained and a decrease in water absorption performance can be suppressed.

  The amount of metal chelate fine particles attached to the fabric is preferably 0.01 to 0.5% by weight, more preferably 0.05 to 0.3% by weight. If the adhesion amount of the metal chelate fine particles is less than 0.01% by weight, the antibacterial deodorizing performance after 50 washings is poor, and if it exceeds 0.5% by weight, the cost is increased, which is not preferable.

In the present invention, for example, when zinc acetate fine particles chelated with lactic acid are adsorbed on the fabric surface using zinc acetate as the metal compound, the particle size of the fine particles is observed with an electron microscope, and per 500 nm ^{2 of} the fabric surface area, The number of particles having a particle diameter exceeding 50 nm is 2 or less, and it can be observed that fine particles having a particle diameter of 50 nm or less are adhered. In particular, when a basic dye dyeable fiber is used as the fiber, it can be observed that the surface of the fabric is coated with zinc chelate fine particles having a particle diameter of 20 nm or less. This state is the same even after repeated washing 50 times, and the durability is high.

Any condition can be applied to the dyeing of the fabric of the present invention as long as it is a commonly practiced condition.
In addition, when metal chelate fine particles are attached to the fabric simultaneously with the dyeing of the fabric composed of the basic dye-dyeable fiber with the cationic dye, the metal chelate fine particle adsorption efficiency is high and the washing durability is high. A product with high color developability is obtained.

In order to feel comfortable when sweating while wearing clothes, it is necessary for the fabric to have the ability to absorb moisture. Remains uncomfortable without being resolved. In order to eliminate the sticky feeling, it is necessary to quickly diffuse the absorbed water. In the present invention, since the metal chelate fine particles are directly adsorbed on the fabric surface, ultra fine undulations can be formed on the fabric surface, and the ability to quickly diffuse moisture by increasing the undulations and surface area is exhibited. The comfort when sweating when worn can be expressed by the water drop disappearance time and the water absorption diffusion area. In applications where the number of times of washing is large, such as underwear or sports clothing worn in the summer, at least 50 times of durability is required. In the present invention, as a result of examining the relationship between the water drop disappearance time, the water absorption diffusion area, and the comfort, the water drop disappearance time after 50 washings is 2 seconds or less, preferably 1 second or less, and the water absorption diffusion area is 10 cm ² or more, preferably When it is 12 cm ² or more, the wearing comfort of the fabric product is excellent. Moreover, it is more preferable that the rate of change of the water absorption and diffusion area after 50 washings is 50% or less of the water absorption and diffusion area when not washed.

  Moreover, as long as it is the conditions currently normally implemented, all can be applied for the finishing method of a dyed fabric, and what is necessary is just to set suitably according to the characteristic of a fabric. Moreover, since the deodorizing performance is stably obtained when the fabric pH of the finished fabric is weakly acidic, it is preferable to add and adjust a non-volatile organic acid in the finish agent bath.

  The fabric thus obtained is excellent in antibacterial performance as defined in the certification standard established by the Textile Products Sanitary Processing Council (SEK). Specifically, the bacteriostatic activity value in Staphylococcus aureus described later is 2.2 or more, preferably 2.5 or more. Moreover, it is excellent in the deodorizing performance with respect to the sweat odor prescribed | regulated by the deodorant processed textile product certification standard (April 1, 2010 edition) which a corporation | organization corporation fiber evaluation technology meeting establishes. Specifically, in the JTETC deodorant classification “sweat odor” deodorization test, which will be described later, the reduction rate of ammonia is 70% or more, preferably 75% or more, and the decrease in acetic acid according to the deodorant processed fiber product certification standard established by JTETC. The rate is 80% or more, preferably 85% or more, and the reduction rate of isovaleric acid is 85% or more, preferably 90% or more.

The antibacterial deodorant fabric of the present invention is excellent in water absorption performance in addition to the above antibacterial deodorization performance. Specifically, the water drop disappearance time after 50 washings is 2 seconds or less, and the water absorption diffusion area is 10 cm ² or more. The fastness performance is also good, and specifically, it is a dyed product with high commercial value in which the fastness to sweat alkali in the JIS-L-0848 A method is grade 3 or higher.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited only to these examples.
The characteristic value measurement method used in the examples and the like will be described below.
(1) Confirmation of chelation of metal chelate fine particles Using an FT-IR apparatus (manufactured by Nicolet, Magna 760), measure the solution before and after sonication under the following measurement conditions, and confirm the peak top variation degree. When it fluctuated by 5 cm ⁻¹ or more, it was judged that chelation was performed.
Measurement method: single reflection ATR method (DuraScope diamond ATR crystal manufactured by STJapan)
Measurement area: 700 to 4000 cm ⁻¹
Resolution: 4cm ^-1
Integration count: 32 times

(2) Particle size of metal chelate fine particles in dispersion The particle size of metal chelate fine particles in a solution after ultrasonic treatment and in a solution diluted and dispersed in water is measured five times with a Zetasizer Nano ZS device manufactured by MALVERN. The average value was obtained.
(3) Particle size of metal chelate fine particles on fabric surface The projected area of metal chelate fine particles is calculated from a photograph of a sample fabric observed with an electron microscope, and the diameter of a circle having the same area is obtained. The diameter. The particle diameters of all the metal chelate fine particles existing in a surface area of 500 nm ² were measured at any five locations on the sample fabric and averaged.

(4) Durability of washing with metal chelate fine particles Before and after washing of a fabric to which metal chelate fine particles are adhered, elemental analysis is performed with a fluorescent X-ray apparatus (Rigaku, RIX3001), and the metal element strength is measured. The dropout rate was calculated. In addition, arbitrary 5 places were measured and averaged.
Dropping rate of metal chelate fine particles (%) = ((element strength before washing−element strength after washing) / element strength before washing) × 100

(5) Evaluation of antibacterial properties The antibacterial properties were evaluated in accordance with the unified testing method of the Textile Products Sanitary Processing Council (SEK). After sterilization, dry specimens in a clean bench (square test piece 0.4 g with a side of about 18 mm) were sterilized with high-pressure steam in advance and then cooled with water. Inoculate 0.2 ml of the test bacteria suspension adjusted to (1 ± 0.3) × 10 ⁵ cells / ml so that the entire specimen is uniformly immersed, and tighten the sterilized cap. This was cultured at 37 ± 1 ° C. for 18 hours, and the number of viable bacteria after the culture was measured.
There are two types of specimens: standard cloth (cloth specified in the processing effect evaluation test manual for antibacterial and deodorant processed products) and test cloth. Staphylococcus aurcus ATCC 6538P is used as the test bacteria, and the following formula: The bacteriostatic activity value, which is an index of antibacterial activity, was calculated, and those having a bacteriostatic activity value of 2.2 or more were judged to have antibacterial activity. However, the condition for satisfying the test was to satisfy (LogB-LogA)> 1.5.
Bacteriostatic activity value = LogB-LogC
Here, A is the average number of bacteria collected immediately after inoculation with the standard cloth, B is the average number of bacteria after 18 hours of culture of the standard cloth, and C is the average number of bacteria after 18 hours of culture of the test cloth. Value.

(6) JTETC deodorant classification “sweat odor” deodorization test Deodorization performance was evaluated using three components of ammonia, acetic acid and isovaleric acid as odor components, and the deodorization performance was evaluated by the following method.
<Deodorization performance evaluation>
1. Instrument analysis test: Instrument analysis was conducted on the above three components in accordance with the deodorant processed fiber product certification standard defined by JTETC. That is, the odor component and the sample were put in a container, and the residual concentration of the odor component after being left for 2 hours (sample test concentration after 2 hours) was measured. The reduction rate of the odor component was calculated by the following formula using the residual concentration of the container containing only the odor component as the blank test concentration.
Decrease rate (%) = (Blank test concentration after 2 hours−Sample test concentration after 2 hours) / (After 2 hours)
Empty test concentration) x 100
Ammonia and acetic acid were measured by a detector tube method, and isovaleric acid was measured by a gas chromatography method. In the judgment, a case where the conditions of ammonia reduction rate of 70% or more, acetic acid reduction rate of 80% or more and isovaleric acid reduction rate of 85% or more are satisfied is judged as “good”, and other cases are judged as “good”. .

2. Sensory test: Put odor component and sample into flask, compare sample odor and odor in flask after standing for 2 hours with judgment odor. The case where it judged was set as the pass.
Odor “strong”: When stronger than the judgment odor gas Odor “weak”: When equal or weaker than the judgment odor gas Note that the judgment odor includes ammonia, acetic acid, and isovaleric acid gas with an odor intensity of 2.0. Using.

(7) pH of dyed fabric
The pH of the extract according to JIS L-1096 was measured by the B method (ISO method) to determine the pH of the fabric.
(8) Washing condition 50 times according to JIS L-0217 103 method. The detergent used was Kao Attack (1 g / L).
(9) Water drop disappearance time The water drop disappearance time was evaluated according to JIS L-1097 dropping method. Measurement was performed five times for each sample, and the average water droplet disappearance time was determined. At this time, the average amount of one water droplet was 0.039 ml.

(10) Water-absorbing diffusion area The fabric is attached to a round frame for embroidery with a diameter of 15 cm, and 0.1 ml of water-soluble blue dye (containing 0.005 wt% of CI Acid Blue 62) is dropped on the fabric surface for 3 minutes. The water-absorbing and diffusing area that was later wetted and spread is determined by the following equation.
Water absorption diffusion area (cm ² ) = [vertical diameter (cm) × horizontal diameter (cm)] × π ÷ 4
Measurement was performed 5 times for each sample, and the average water absorption and diffusion area was determined.

(11) Evaluation of color development The spectral reflectance R of the fabric was measured for the dyed product, and was determined from the Kubelka-Munk equation shown below. Larger values indicate higher color developability (higher surface concentration), that is, better color development. The value at 610 nm, which is the maximum absorption wavelength of the dye, was adopted.
K / S = (1-R) ² / 2R

(12) Texture evaluation Relative evaluation of the dyed finished product was performed according to the following criteria based on the feeling of 30 inspectors, and the criteria obtained with the feeling of 21 or more were shown.
○: supple, soft and comfortable to wear
Δ: Slightly inferior and soft to the touch
×: Hard and unpleasant to the touch

(13) Fastness to sweat alkali The dyed product was evaluated using a sweat alkali artificial sweat according to the JIS-L-0848-A method. The degree of contamination of the test piece and the attached white cloth piece were judged by comparing with the gray scale for color change and the gray scale for contamination, respectively.

[Examples 1 to 3]
<Preparation of metal chelate fine particle aqueous dispersion>
A solution in which 5.4 g of lactic acid was dissolved in 1.08 g of water was added to 100 ml of methanol and mixed uniformly, and 13.2 g of zinc acetate (dihydrate) was dissolved in the resulting solution with stirring.
Next, while heating this solution to 50 ° C., ultrasonic irradiation was performed in a sealed state for 2 hours at a high frequency output of 80 W and a transmission frequency of 40 kHz using an ultrasonic device.

Where before and after the ultrasonic treatment solution was confirmed out-of-plane deformation vibration of the OH of the carboxyl ion in the chart analysis by FT-IR, to 1450cm ^-1 is 1420cm ^-1, 1570cm ^-1 is varied to 1580cm ^-1 Therefore, it was determined that zinc was chelated and zinc chelate fine particles were generated. Next, when the particle diameter of the generated fine particles was measured with Zetasizer Nano ZS, it was confirmed that the average particle diameter was 4.1 nm.

  Next, 14.8 g of the obtained zinc chelate fine particle dispersion was added to 1000 g of water and stirred for 10 minutes with a magnetic stirrer to obtain a 0.2 wt% aqueous dispersion of zinc chelate fine particles. The obtained aqueous dispersion had a pH of 4.7, was colorless and transparent and had no aggregates, and the average particle size of the zinc chelate fine particles was 7.8 nm.

<Applying metal chelate fine particles to fabric>
Mitsubishi Rayon Co., Ltd. basic dye-dyeable polyester fiber (trade name: AHY) 70 dtex / 48 f of POY is false twisted at 185 ° C. by a conventional method to obtain a 76 dtex / 48 f composite I got a thread. Next, using the obtained composite yarn, a milled circular knitted fabric was produced by a conventional method at 24 gauge. Then, after pre-wetting at 60 ° C. in a spread form, pre-setting at 185 ° C., and then treatment with an aqueous dispersion of zinc chelate fine particles simultaneously with dyeing under the conditions shown below.

<Dyeing conditions>
Dispersion type cationic dye: Kayacrill Blue 2RL-ED: 1.5% omf
pH: 4.3 (adjusted with lactic acid)
Zinc chelate fine particle concentration: adjusted so that the amount of adhesion to the fabric is the amount shown in Table 1. Bath ratio: 1:20
Temperature: 120 ° C
Time: 40 minutes After dyeing, hot water washing and water washing are repeated twice in this order at 80 ° C., then a sewing improver and a softening agent are added to the water bath and applied to the fabric by the padding method. Finished by heat treatment at 140 ° C.

The resulting dyed fabric had a pH of 5.9, a basis weight of 147 g / m ² , a coarse density of 55 / inch, a well density of 33 / inch, and a thickness of 0.52 mm. When the obtained dyed fabric was observed with an electron microscope at a magnification of 100,000 times, no zinc chelate fine particles having a particle diameter exceeding 50 nm per 500 nm ^{2 of} the fiber surface area, and the particle diameter was 20 nm or less. It was confirmed that it was covered with zinc chelate fine particles. This state was the same after washing 50 times.

  Table 1 shows the evaluation results of the antibacterial performance, deodorization performance, water absorption / diffusion performance, color development, sweat alkali fastness, and texture of the obtained dyed fabric. From the results shown in Table 1, the fabrics obtained in Examples 1 to 3 have excellent antibacterial performance, deodorization performance, water absorption and diffusion performance, color development, and sweat alkali fastness performance, and have a supple texture and commercial value. It turns out that it is a high dyeing fabric.

[Comparative Example 1]
A dyed fabric was obtained in the same manner as in Example except that zinc chelate fine particles were not added in the dyeing of the fabric. The obtained dyed fabric was subjected to a heat treatment at 140 ° C. by applying zinc oxide by a pad method under the conditions shown below in combination with a resin binder.
<Finish preparation formulation>
Zinc oxide fine particle water dispersion (Sumitomo Osaka Cement ZW-230B; average particle size 67
nm): 10 parts by weight Silicone binder (Pinetex S-200L, manufactured by Yamato Chemical): 3 parts by weight The antibacterial performance, deodorization performance, water absorption / diffusion performance, color development, fastness to sweat alkali, and texture of the obtained dyed fabric The evaluation results are shown in Table 1.

  From the results in Table 1, the dyed fabrics obtained in Examples 1 to 3 of the present invention are superior in antibacterial performance, deodorant performance, and water absorption / diffusion performance durability compared to the fabric obtained in Comparative Example 1, and color development. It can be seen that this is a dyed fabric having high properties, excellent texture, and high commercial value.

  The fabric treated with the metal chelate fine particle aqueous dispersion of the present invention is excellent in antibacterial performance, deodorization performance and water absorption / diffusion performance, excellent in color developability and fastness performance, has a supple feel, and is comfortable to wear. Since it is an excellent antibacterial and deodorant fabric, it can be suitably used in the inner field, sports clothing field, and nursing clothing field.

Claims (2)

An antibacterial deodorant fabric characterized in that it is a fabric to which metal chelate fine particles having an average particle size of 50 nm or less are adhered, and has 2 or less metal chelate fine particles having a particle size exceeding 50 nm per 500 nm ^{2 of the} surface area of the fabric.   The fabric is immersed in a dispersion in which metal chelate fine particles are dispersed in an acidic solution having a pH of 3.5 to 5.0, and is treated at a temperature of 100 to 135 ° C for 15 to 45 minutes. Of producing antibacterial and deodorant fabrics.