JP2014201859A - Deodorant antibacterial fiber fabric excellent in durability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant fiber fabric obtained by mixing a cellulose fiber and a basic dye dyeable type fiber and excellent in deodorant performance to an aging odor, antibacterial performance, water absorption and diffusion performance, and wearing feeling.SOLUTION: There is provided a deodorant antibacterial fiber fabric obtained by mixing a cellulose fiber and a basic dye dyeable type fiber, having polyallylamine, 0.005 to 0.1 wt.% of metal particles having an average particle diameter of 5 to 100 nm, 0.3 to 0.8 wt.% of hydrophilic agent, an ammonia percentage reduction, isovaleric acid percentage reduction and nonenal percentage reduction of 70% or more, 85% or more and 75% or more respectively based on criteria authorized for deodorant processed fiber product after 50 times washing, and a bacteriostatic activity value of Staphylococcus aureus of 2.2 or more based on criteria authorized by a fiber product sanitation process council after 50 times washing.

Description

  The present invention relates to a mixed fabric of cellulose fiber and basic dye-dyeable fiber that is excellent in deodorant performance and antibacterial performance. More specifically, the present invention has excellent durability against deodorant performance and antibacterial performance, is excellent in washing durability of water absorption / diffusion performance, and is excellent in color development and dyeing fastness. The present invention relates to a mixed fabric with mold fibers.

  Cellulose fibers such as cotton are often used in clothing, but in recent years, deodorant performance and antibacterial performance have been used as functions to satisfy comfort when wearing clothes, especially comfort in daily life in summer. It has been demanded. To maintain comfort and comfort in the summer season when the temperature is above 25 ° C over the long term in the summer season and when it sweats with deodorant and antibacterial durability Immediate water absorption and diffusion are important for realizing good comfort.

Due to the progress of an aging society, a deodorizing function for an aging odor, which is a unique body odor emitted especially by middle-aged and elderly people, is required among deodorizing performance.
In general, the aging odor is considered to be caused by the odor components of ammonia, acetic acid, isovaleric acid, and nonenal. The deodorization of the aging odor requires a function of removing all these four components. Has been. In antibacterial properties, performance by S. aureus is typically required.

  Nonenal, which is one of the aging odors, is due to the reaction between lipid peroxide that was not decomposed due to the deterioration of the biological defense mechanism due to aging and palmitoleic acid that increases in secretion with age. Oxidative propagation by oxidized lipids turns valmitoleic acid into valmitooleic acid hydroperoxide, which is cleaved and decomposed into nonenal. As a method of inhibition, curen extract and ougon are used to block oxidative propagation by lipid peroxides. Although there is a method of applying an antioxidant such as an extract to the fiber surface, there is a problem that these antioxidants themselves do not have washing durability.

  The following Patent Document 1 discloses a fiber structure that is excellent in washing durability and effective in deodorizing Nonenal by attaching a specific amount of a polycation having a group that undergoes a Schiff reaction with Nonenal, a deodorant, and a photocatalyst to the fiber. Is disclosed. However, there is a problem that the water absorption diffusibility is poor and the antibacterial performance is also poor because the fiber structure is attached using a binder such as an acrylic resin.

  Further, in Patent Document 2 below, an antibacterial agent comprising a specific metal composition is applied to a woven or knitted fabric having a multilayer structure of two or more layers, so that it is excellent in sweat deodorization and antibacterial performance and has a high drying speed. It is disclosed that a woven or knitted fabric is obtained. However, since it is composed of a multilayer structure of two or more layers, there are restrictions on the fabric structure, the fabric is thick, and when worn as an inner fabric, there is a feeling of weight and thickness, and it feels hot and supple. There is a problem that it is uncomfortable because it is not present, and it is ineffective against the nonenal odor.

  In addition, in Patent Document 3 below, by providing an antibacterial metal component and an antibacterial inorganic oxide colloid solution, fine particles having an antibacterial property having an average particle size of 500 nm or less adhere firmly to the fiber, thereby improving antibacterial performance. It is disclosed that it is excellent. However, although antibacterial performance against Escherichia coli and staphylococci is good, there is a problem that there is no deodorizing effect against aging odors and poor water absorption diffusivity.

  Furthermore, Patent Document 4 below discloses that antibacterial, deodorant, water absorption and quick-drying performance are excellent by applying an aqueous solution of platinum nanocolloid or a mixed solution of this aqueous solution and an antibacterial deodorant or antibacterial deodorant. Has been. However, the fabric processed into cotton fiber has a deodorizing effect on aging odor after washing 10 times and antibacterial performance against Staphylococcus aureus, but especially in a mixed fabric of cellulose fiber and basic dyeable fiber, When processed into a long fiber composite fabric, there is a problem that there is no deodorizing effect on the aging odor after 50 washings and the water absorption diffusibility is also poor.

  Thus, at present, in dyed fabrics containing cellulose fibers and finished without using a binder, they are excellent in deodorizing performance and antibacterial performance against aging odors, and are excellent in washing durability of these performances, and in water-absorbing and diffusing performance. Dyeing products that are superior in color, have no stickiness to the skin, and have excellent color development and dyeing fastness performance have not been obtained.

Japanese Patent No. 4092554 JP 2010-163710 A Japanese Patent No. 3197126 Patent WO2012 / 086204

  The problem to be solved by the present invention is that the mixed fabric of cellulose fiber and basic dye-dyeable fiber is excellent in deodorizing performance, antibacterial performance and water-absorbing / diffusion performance, and has no stickiness on the skin surface. An object of the present invention is to provide a deodorant antibacterial fabric excellent in color development and dyeing fastness and a method for producing the same.

As a result of intensive studies to solve the above problems and repeated experiments, the present inventor gives polyallylamine, specific metal particles and a hydrophilic agent to a mixed fabric of cellulose fibers and basic dyeable fibers. As a result, it was found that deodorant performance, antibacterial performance and water absorption / diffusion performance were obtained, and the present invention was completed.
That is, the present invention is as follows.

[1] A deodorant antibacterial fiber fabric in which cellulose fibers and basic dye-dyeable fibers are mixed, containing polyallylamine, and metal particles having an average particle diameter of 5 to 100 nm are 0.005 to 0.005. Contains 1% by weight, contains 0.3-0.8% by weight of hydrophilic agent, and has an ammonia reduction rate, isovaleric acid reduction rate, and nonenal reduction rate of 70, respectively, in the deodorant processed fiber product certification standard after 50 washings. % Or more, 85% or more and 75% or more, and the bacteriostatic activity value of Staphylococcus aureus according to the recognition criteria of the textile product hygiene processing council after 50 washings is 2.2 or more Odor antibacterial fiber fabric.
[2] The deodorant antibacterial fiber fabric according to the above [1], wherein the polyallylamine has an average molecular weight of 1000 to 70000 and a content of 0.2 to 3.0% by weight.
[3] The deodorant antibacterial fiber according to [1] or [2], wherein the metal particles are made of at least one metal selected from gold, silver, platinum, rhodium, ruthenium and iridium. Fabric.
[4] The deodorant antibacterial fiber fabric according to any one of the above [1] to [3], wherein the hydrophilic agent is a cationic aromatic polyester polyether block copolymer.
[5] Deodorant antibacterial as described in any one of [1] to [4] above, wherein 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. Fiber fabric.
[6] When a mixed fabric of cellulose fiber and basic dyeable fiber is dyed with a cationic dye, polyallylamine and a hydrophilic agent are used in combination to give a polyallylamine and a hydrophilic agent, and then a metal colloid is applied and then heat treatment. The method for producing a deodorant and antibacterial fiber fabric according to any one of [1] to [5] above.
[7] The method for producing a deodorant and antibacterial fiber fabric according to the above [6], wherein the metal colloid is applied with an aqueous dispersion containing no binder resin.
[8] The above-mentioned [6] or [7], wherein the blended fabric is subjected to a 1.5 to 10% reduction treatment with a cellulolytic enzyme at a temperature of 65 ° C. or lower before cationic dyeing. A method for producing a deodorant antibacterial fiber fabric.

  The deodorant antibacterial fiber fabric of the present invention is a deodorant antibacterial fiber fabric composed of cellulose fibers and basic dye-dyeable fibers, and has excellent deodorant antibacterial performance. The fiber fabric is excellent in washing durability of performance and excellent in water-absorbing diffusibility, coloring property and dyeing fastness. In addition, the deodorant antibacterial fiber fabric of the present invention in which a streak-like groove having a specific size is formed on the surface of the cellulose fiber can be further improved by treating the cellulose fiber with a cellulolytic enzyme. .

Hereinafter, the present invention will be described in detail.
The deodorant antibacterial fiber fabric of the present invention is a mixed fabric composed of cellulose fibers and basic dye-dyeable fibers, and is excellent in deodorizing performance against aging odors, particularly isovaleric acid and nonenal, and Staphylococcus aureus It has excellent antibacterial performance against water, water absorption / diffusion performance, and improved washing durability.

  Cellulose fibers used in the present invention include natural cellulose fibers such as cotton and hemp, and regenerated cellulose fibers such as viscose rayon, copper ammonia rayon and polynosic, and regenerated cellulose fibers can be preferably used, and in particular, obtained by the copper ammonia method. It is preferable to use cupra (Asahi Kasei Fibers Co., Ltd. Bemberg) because the effect of the present invention is most noticeable.

  Conventionally, modified cellulose fibers obtained by graft copolymerization reaction of methacrylic acid to cellulosic fibers have been devised in order to impart deodorant performance. Such modified cellulose fibers are used as cellulose fibers in the present invention. Even if it is not used, the present invention exhibits a sufficient deodorizing performance. In consideration of cost and the like, the cellulose fiber is preferably a fiber that has not been subjected to such modification, specifically, a cellulose fiber that is not substantially imparted with a carboxyl group by post-treatment.

  In the fabric according to the present invention, it is preferable that the cellulose fiber is treated with a cellulolytic enzyme to form a streak-like groove having a specific size in the fiber axis direction. Thereby, the deodorizing effect with respect to basic gases, such as ammonia, and acidic gases, such as an acetic acid and isovaleric acid, increases. In particular, regenerated cellulose fibers (long fibers) are also preferable from the viewpoint of easy control of the width and length of the specific streak groove in the fiber axis direction when treated with a cellulolytic enzyme.

  Although the cellulose fiber used by this invention is not specifically limited, It is preferable that a total fineness is 20-200 dtex and a single yarn fineness is 0.6-1.8 dtex. In addition, in the case of the L-shaped cross section, the cross-sectional shape is easy to obtain a supple texture and the specific surface area is large, so the efficiency of the weight loss treatment with cellulase is increased, and a streak groove is easily formed around the recess, This is preferable because the effects of the present invention are sufficiently achieved.

  Cellulose fibers may be used alone, or multiple types of cellulose fibers may be combined, or may be combined with other fibers. However, it is preferable that 50% or more of the regenerated cellulose fiber is contained, and 100% of the regenerated cellulose fiber is more preferable. The form of the fiber may be long fiber or short fiber, and may be uniform or thick in the length direction. And examples of the form of the yarn from which the fiber is processed include ring spun yarn, open-end spun yarn and air-jet fine spun yarn, sweet twisted yarn to strong twisted yarn, false twisted yarn, air-jet processed yarn, Examples thereof include indented yarn and knitted knitted yarn.

  Examples of yarn forms when cellulose fibers and other fibers are mixed include blends (blends, fleece blends, sliver blends, core yarns, silospans, silofils, hollow spindles, etc.), entangled blends, twists, designs Twisted yarn, covering (single, double), composite false twist (simultaneous false twist, first twist false twist), elongation difference false twist, phase difference, post-mixing after false twisting, and 2 feeds (simultaneous feed and feed difference) The mixed form by air injection processing etc. is mentioned.

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 dyeing seat component include alkali metal salts of sulfoisophthalic acid, 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 of the present invention 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 of the present invention contains a surfactant such as titanium oxide and alkylbenzene sulfonate, a conventionally known antioxidant, a coloring inhibitor, a light fastener, an antistatic agent, an alkali metal, and the like. Alternatively, it can be produced by a conventionally known method.
The basic dye dyeable fiber of 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. From the viewpoint of smooth texture and deodorizing performance, a fiber having an irregular cross section and a single yarn fineness of 0.6 to 1.8 dtex is preferable.

Further, the basic dye dyeable fiber used in the present invention may contain up to 30% 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 from 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 injection processed yarn, indentation processing Examples thereof include yarn and knitted knitted yarn.

  The deodorant antibacterial fiber fabric of the present invention contains cellulose fiber and basic dye-dyeable fiber, and the proportion of each fiber can be appropriately determined depending on the use, but from the aspect of fabric performance and deodorization performance. The cellulose fiber is preferably 20 to 60%, and the basic dyeable fiber is preferably 40 to 80%. In addition to both fibers, polyester, nylon, acrylic, silk, wool and the like may be mixed.

In the present invention, the form in which cellulose fibers and basic dyeable fibers are used in combination is a form in which the fibers are combined at the yarn-like stage to form mixed yarns, and the knitting and weaving using cellulose fibers and basic dyeable dyeable fibers. However, when it is made into a fabric, it is roughly classified into a form of a mixed fabric.
Examples of yarn forms when cellulose fibers and basic dye-dyeable fibers are mixed are blended (blended cotton, fleece blended, sliver blended, core yarn, silospan, silofil, hollow spindle, etc.), entangled blended fiber , 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, and there is a knitted fabric in which cellulose fibers and basic dyeable fibers are aligned or combined at the time of weaving and weaving.

In the deodorizing and antibacterial fiber fabric of the cellulose fiber and the basic dye-dyeable fiber in the present invention, before dyeing the above-mentioned mixed fabric, the weight of the fabric is 1.5 by cellulolytic enzyme treatment described later. It is preferable from the viewpoint of the deodorizing effect to reduce the amount by 10% to 10% and form a streak-like groove on the surface of the cellulose fiber.
When the weight loss rate is in the above range, 10 or more streak grooves having a width of 0.05 to 1.50 μm and a length of 3 to 25 μm exist on the surface of the cellulose fiber per 50 μm of the fiber axis length. In addition, the streak groove does not necessarily need to be substantially parallel to the fiber axis direction, and may be inclined up to 45 degrees.
By having such a streak-like groove, the specific surface area of the fiber is increased, the supplemental amount of each odor component of ammonia, acetic acid, isovaleric acid and nonenal is increased, and the mixed fabric with the basic dye-dyeable fiber is used. The deodorizing effect is enhanced, and a product having a high deodorizing effect for the aging odor referred to in the present invention is obtained, and the color sharpness is also increased.
Control of the width | variety and length of the above-mentioned streak-like groove | channel is easier in a regenerated cellulose fiber among cellulose fibers.

In addition, by having this streak groove, when sweating, the power to quickly absorb moisture and the power to diffuse moisture are demonstrated, so that it does not stick to the body, does not feel sticky, and dries quickly The effect is demonstrated, and the suppleness and flexibility are enhanced. In addition, the texture is good, the comfort is improved, the dehydration rate during washing is kept low, and the effect of quick drying after dehydration is also obtained. Will also last.
If the weight loss rate is 1.5% or more, the width of the streak groove is 0.05 μm or more, the length is 3 μm or more, the number is 10 or more, and the deodorizing effect can be enhanced. This is preferable because a color is obtained and the color becomes clear. On the other hand, when the weight loss rate exceeds 10%, there is a problem that the strength reduction of the cellulose fiber becomes large. A weight reduction treatment of 2.0 to 8.5% is more preferable because it can impart washing durability and color sharpness of the deodorizing effect of the mixed fabric. The weight loss process may be performed before or after or simultaneously with processes such as scouring and relaxing.

Cellulose-degrading enzyme as used in the present invention refers to cellulases such as exoglucanase, endoglucanase, serbiase, β-glucosidase, and cellobiase, and each can be used alone or in combination.
Examples of means for controlling the streak-like grooves on the surface of the cellulose fiber include enzyme (cellulase) concentration, pH, bath ratio, treatment temperature and time during the cellulolytic enzyme treatment. Treatment conditions include a bath ratio of 1: 0. In the case of acidic active cellulase, acetic acid and citric acid, in the case of neutral active cellulase, sodium phosphate and alkaline active cellulase so that the pH is about 5 to 1:50. In some cases, a buffering agent such as ammonia or sodium carbonate may be used alone or in combination for adjustment. The concentration of cellulase used varies depending on the activity of the cellulase and the target weight loss rate, but is generally 0.3 to 15% by weight, the treatment temperature is 40 to 65 ° C., and the treatment time is 30 to 300 minutes. .

After the treatment, the enzyme is deactivated, but it may be treated at a temperature at which the enzyme to be used is deactivated, and it is preferably 70 to 100 ° C. and 15 to 30 minutes. In addition, it is preferable to use an alkaline agent in the treatment bath in order to promote enzyme desorption.
In the treatment with cellulolytic enzymes, rotary dyeing machines such as rotary drum dyeing machines, paddle dyeing machines, Wins reel dyeing machines, jigger dyeing machines, liquid dyeing machines, and airflow dyeing machines can be used. It is preferable to use an apparatus capable of processing in an expanded state, such as a roll and pad-sig dyeing machine, because it is easy to control the formation of the streak groove of the present invention.

In the present invention, when metal particles are fixed to a fiber cloth, in order to obtain washing durability without using a binder resin and to obtain good deodorant antibacterial performance, the mixed cloth contains polyallylamine in advance. It is important to keep it.
The polyallylamine used in the present invention is a cationic polymer containing a primary amine as a main component, and is particularly excellent in affinity between cellulose fibers and basic dye-dyeable fibers, exhibits excellent adsorptivity, and is a polymer. Therefore, it is excellent in washing durability. For example, an allylamine hydrochloride polymer (CAS.NO.71550-12-4) composed of a primary amine alone, an allylamine amide sulfate polymer (CAS.NO.861901-41-9), CAS.NO.30551-89-4), allylamine hydrochloride / diallylamine hydrochloride copolymer (CAS.NO.97939-72-5) composed of primary amine and secondary amine, allylamine composed of primary amine and tertiary amine Hydrochloride / dimethylallylamine hydrochloride copolymer (CAS.NO.223474-45-1) and allyla Down-dimethyl allyl amine copolymer (CAS.NO.177606-24-5), and the like.

The average molecular weight of the polyallylamine is preferably 1000 to 70000, because it is uniformly adsorbed to the mixed fabric at the time of cationic dye dyeing, has no influence on the dyeability, and does not become hard. It can be used as an aqueous solution. More preferably, it is 5000-40000.
The content of polyallylamine in the present invention is preferably 0.2% by weight or more based on the mixed fabric of cellulose fiber and basic dyeable fiber. More preferably, it is 0.2-3.0 weight%, Most preferably, it is 0.4-2.0 weight%. If the content is less than 0.2% by weight, the content of metal particles to be treated later is also reduced, and good deodorant antibacterial performance cannot be obtained. Moreover, when polyallylamine is not provided at all, the washing durability performance of the metal particles deteriorates and the durable deodorant antibacterial performance of the present invention cannot be obtained. In particular, it is remarkable in a mixed fabric of cellulose fiber having a long fiber shape and dyeable fiber of basic dye. Moreover, when there is too much content, for example, exceeds 3.0 weight%, it exists in the tendency for a feel to become hard.

  In addition, any method such as exhaust processing, padding processing, spray processing, and dipping processing may be used for adding polyallylamine to the mixed fabric, but in order to uniformly and efficiently include the entire mixed fabric, basic dye dyeing is possible. It is preferable to treat the mold fiber in combination when dyeing with a cationic dye. The treatment temperature, treatment time, and pH of the treatment bath at that time may be any as long as they are conditions for dyeing with a cationic dye.

  In the present invention, the metal particles are preferably metal colloid-derived metal particles. Examples of the metal colloid used include metal colloids containing metal particles and water. Examples of the metal forming the colloidal particles include gold, silver, platinum, rhodium, ruthenium and iridium, noble metals are preferable, and platinum is particularly preferable. The metal particles are preferably not reactive, and the colloidal particles themselves are preferably not chemically changed.

The average particle diameter of the metal particles is preferably in the range of 5 to 100 nm. More preferably, the range of 5-60 nm is illustrated. When the average particle size is less than 5 nm, there is a problem in that the dispersion stability when dispersed in water is poor and aggregation tends to occur. On the other hand, when it exceeds 100 nm, durability of various performances is deteriorated, which is not preferable.
The particle size of the metal particles contained in the metal colloid used in the present invention, that is, the metal particles contained in the mixed fabric of the present invention is represented by a circle equivalent, specifically, a photograph observed on an electron microscope. The projected area of the particle is calculated from the above and is expressed as the diameter of a circle having the same area. The average particle diameter is expressed as an average value of the above-mentioned equivalent circle.

  In the metal colloid used in the present invention, particles are obtained by dissolving a metal compound as a raw material in a solvent and reducing it to a metal. Examples of the metal compound used as a raw material include chloroauric acid, silver nitrate, chloroplatinic acid, rhodium (III) chloride, ruthenium (III) chloride, and iridium chloride. Examples of the reducing agent include citric acid, sodium citrate, tannic acid, hydrazine, and sodium borohydride. Although reaction temperature is not specifically limited, The temperature from room temperature to the boiling point of a solvent is preferable, More preferably, it is 25-100 degreeC, Most preferably, it is 40-100 degreeC. The reaction time is not particularly limited. Examples of the metal colloid dispersion solvent include water, ethanol, methanol and the like, preferably water.

The viscosity of the metal colloid is preferably in the range of 0.8 to 5.0 mPa · s at 25 ° C., more preferably in the range of 0.8 to 2.0 mPa · s. Furthermore, polyvinylpyrrolidone, polyacrylic acid, tetramethylammonium and the like may be contained as a protective agent in order to enhance storage stability. The pH of the metal colloid is preferably in the range of 2.5-5.
The content of the metal particles in the mixed fabric of the present invention is 0.005 to 0.1% by weight, more preferably 0.01 to 0.05% by weight. In addition, it is preferable to contain 0.01 to 0.03% by weight of metal colloid with respect to 1% by weight of polyallylamine in order to obtain good deodorant antibacterial performance. If the content of the metal colloid is less than 0.005% by weight, the deodorizing and antibacterial performance is poor, and if it exceeds 0.1% by weight, the cost increases, which is not preferable.

  In the present invention, by attaching polyallylamine, the metal particles can cover 80% or more of the fiber surface, and when applying the metal particles, no binder resin is used. And a decrease in water absorption performance can be suppressed. When metal particles are adsorbed on a mixed fabric with metal colloid using water as a dispersion solvent, it is preferable that the zeta potential of the metal colloid is in the range of −5 to −70 mV because the adsorbability and durability of the metal particles are increased.

In the present invention, the metal colloid, that is, the metal particles can be adsorbed to the mixed fabric by any method such as exhaust processing, padding processing, spray processing, dipping processing, and ink jetting. Padding or spraying that can be applied without increasing the viscosity is preferred. In the padding process, the above-mentioned polyallylamine is adsorbed at the time of dyeing the cationic dye, and then the metal colloid is adsorbed. At this time, the processing temperature can be carried out at room temperature, and the pH of the processing liquid is 3.5 to 5.5. In order to improve the dispersibility and adsorptivity of the metal colloid, it is preferable to carry out with the acidity of. After applying the metal colloid by the padding method, it is preferable to carry out a heat treatment at 110 to 170 ° C. in order to increase the durability. The spray processing uses a spray nozzle device in which the water diameter of the metal colloid is 1 to 30 μm after the polyallylamine is adsorbed on the mixed fabric during dyeing of the cationic dye, and the coating amount is 20 to 60 g / m ² . In order to improve durability, it is preferable to apply the heat treatment at a temperature of 110 to 170 ° C.
In the present invention, since a hydrophilic agent to be post-treated at the time of cationic dyeing is provided, the metal colloid penetrates uniformly in padding processing or spray processing.

  In the present invention, since the metal particles are strongly adsorbed to the polyallylamine contained in the mixed fabric, the washing durability of the metal particles is increased without using a binder resin. In particular, a basic dye-dyeable fiber having a higher ζ-potential on the fiber surface is superior in washing durability because the amount of metal colloid adsorbed, that is, the amount of metal particles adsorbed is large. Furthermore, in the present invention, when the above-mentioned polyallylamine and metal particles are adsorbed after reducing the cellulose with a cellulolytic enzyme, the polyallylamine and the metal are formed in the recesses of the streak groove formed in the fiber axis direction on the surface of the cellulose fiber. Since the particles are adsorbed, the washing durability becomes even higher.

  The dyeing of the mixed fabric of the cellulose fiber and the basic dyeable fiber according to the present invention is performed after the treatment with the cellulolytic enzyme when the treatment with the cellulolytic enzyme is performed. Any condition can be applied to the dyeing of the cellulose fiber as long as the cellulose fiber is normally used. The dyeing procedure may be performed before dyeing the basic dye-dyeable fiber. It is preferable for maintaining the finished dough pH on the weakly acidic side.

  In addition, dyeing of the basic dyeable fiber is performed using a cationic dye. Cationic dyes are water-soluble dyes that are soluble in water and have basic groups. Di- and triacrylmethane-based, quinoneimine (azine, oxazine, thiazine) -based, xanthene-based, methine-based (polymethine, azamethine) Examples thereof include dyes such as heterocyclic azo series (thiazole azo, triazole azo, benzothiazole azo) and anthraquinone series. In addition, as a dispersion type cationic dye that is made water-dispersible by blocking a basic group, Kayacryl ED (manufactured by Nippon Kayaku Co., Ltd.), KIWA CDP (manufactured by Kiwa Chemical Industry Co., Ltd.), Nicilon CDPN (Nissei Kasei Co., Ltd.) It is preferable to dye using Aizen Cathilone DP (made by Hodogaya Chemical Co., Ltd.) or the like because it is easy to give an aromatic polyester polyether block copolymer described later at the time of dyeing.

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, by reducing the surface of the cellulose fiber with a cellulose-degrading enzyme, a streak groove can be formed in the yarn length direction. This streak groove promotes the ability to absorb moisture and imparts a hydrophilic agent. Exhibits the ability to quickly diffuse the absorbed water. In order to obtain comfort, two forces are required, and these two forces can be expressed by a water drop disappearance time and a 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 Has been found to be excellent in the wearing comfort of the mixed fabric product when it is 12 cm ² or more. Further, it has been found that the rate of change of the water absorption diffusion area after 50 washings is more preferably 50% or less of the water absorption diffusion area when not washed.

  Moreover, in order to obtain said water absorption diffusion area in the mixed fabric of this invention, it is necessary to make a hydrophilic agent adsorb | suck. The adsorption amount of the hydrophilic agent is preferably 0.3 to 0.8% by weight, more preferably 0.4 to 0.6% by weight in terms of solid content with respect to the weight of the mixed fabric. If the adsorbed amount is less than 0.3% by weight, the water absorption diffusion performance and durability cannot be sufficiently improved. This is not preferable because the decrease is apparent. As the hydrophilic agent, known hydrophilic agents can be used without any limitation, and examples thereof include polyamide resin, polyurethane, water-absorbing silicone, water-absorbing urethane, and aromatic polyester polyether block copolymer. Adsorption to the mixed fabric may be carried out by any method such as exhaustion method or dipping method at the same time as dyeing or after dyeing. It is preferable to use in combination and adsorb.

In addition, the deodorizing performance is further enhanced by adding a cationic aromatic polyester polyether block copolymer to the basic dyeable fiber among the hydrophilic agents.
The cationic aromatic polyester polyether block copolymer used in the present invention is preferably a block copolymer comprising terephthalic acid and / or isophthalic acid and alkylene glycol and / or polyalkylene glycol. As a commercial product of the copolymer, SR-C1800 produced by cation emulsification manufactured by Takamatsu Oils and Fats Co., Ltd. can be mentioned, and it can be preferably used for enhancing water diffusibility.

In addition, the finishing method of the dyed fabric can be applied as long as cellulose fibers are usually used, and may be set as appropriate according to the characteristics of the mixed 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 mixed dyed fabric comprising cellulose fibers and basic dye-dyeable fibers thus obtained is a deodorant processed fiber product certification standard (April 1, 2010 edition) established by the Japan Fiber Evaluation Technology Council. Excellent deodorizing performance against the aging odor specified in 1. Specifically, in the JTETC deodorant classification “aged odor” deodorization test, which will be described later, the ammonia reduction rate according to the deodorant processed fiber product certification standard established by JTETC is 70% or more, preferably 75% or more. The reduction rate is 80% or more, preferably 85% or more, the reduction rate of isovaleric acid is 85% or more, preferably 90% or more, and the reduction rate of nonenal is 75% or more, preferably 85% or more. Moreover, it is excellent in the antibacterial performance prescribed | regulated to the authentication standard which a textile product hygiene processing council (SEK) establishes. Specifically, the bacteriostatic activity value in Staphylococcus aureus described later is 2.2 or more, preferably 2.5 or more.
The deodorant fiber fabric of the present invention is excellent in water absorption performance in addition to the above deodorization antibacterial 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) JTETC deodorant classification “Aging odor” deodorization test Deodorization test using four components of ammonia, acetic acid, isovaleric acid and nonenal (2-nonenal; CAS No. 463-53-8) as odor components The deodorant performance was evaluated by the following method.
<Deodorization performance evaluation>
1. Instrument analysis test: Instrument analysis was conducted on the above four components in accordance with the certification standards for deodorized textile products determined 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 and nonenal were measured by a gas chromatography method.
Judgment is a pass “○” when all the conditions of ammonia reduction rate of 70% or more, isovaleric acid reduction rate of 85% or more and nonenal reduction rate of 75% or more are satisfied, and other cases are rejected as “X”. Judged.
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 it is equivalent or weaker than the judgment odor gas Note that the judgment odor is ammonia, acetic acid, isovaleric acid, nonenal with odor intensity 2.0 Gas was used.

(2) Evaluation of antibacterial properties The antibacterial property evaluation was conducted in accordance with the unified testing method of the Textile Products Hygiene 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, a standard cloth (a cloth specified in the processing effect evaluation test manual for antibacterial and deodorant processed products) and a test cloth. As test bacteria, Staphylococcus aurcus ATCC 6538P is used. The bacteriostatic activity value, which is an antibacterial index, was calculated by the method, and those having a bacteriostatic activity value of 2.2 or more were judged to be antibacterial.
Bacteriostatic activity value = LogB-LogC
A: Average number of bacteria collected immediately after inoculation with standard cloth
B: Average number of bacteria after 18 hours culture of standard cloth
C: Average number of bacteria after 18 hours of culturing of test cloth However, satisfying (LogB-LogA)> 1.5 was set as a test establishment condition.

(3) Average particle diameter of metal particles The projected area of the metal particles was calculated from a photograph of the sample fabric observed on an electron microscope, and the diameter of a circle having the same area was obtained to obtain the particle diameter of the metal particles. Any five locations on the sample fabric were measured and averaged.
(4) State of streak-like groove on cellulose fiber surface Using a scanning electron microscope (manufactured by Hitachi, Ltd., model S-3500N), the cellulose fiber surface of the sample was magnified 1800 times, and five photographs were taken as appropriate. Compared with the scale gauge, the width and length of the streak groove were measured, and the average value was obtained. Moreover, the number was measured, the number per fiber length 50 micrometers was calculated, and the average value was calculated | required.

(5) Washing condition 50 times according to JIS L-0217 103 method. The detergent used was Kao Attack 1 g / L.
(6) 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.

(7) Water-absorbing diffusion area The fabric was attached to a round frame for embroidery with a diameter of 15 cm, and 0.1 ml of a water-soluble blue dye (containing 0.005 wt% of CI Acid Blue 62) was 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.
(8) 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

(9) Texture evaluation Relative evaluation of the mixed dyed product was performed according to the following criteria based on the feel of the inspector (30 people), and the criteria obtained with the feel of 21 people or more were shown.
○: Soft, soft and comfortable to wear
△: Slightly inferior in softness and touch
X: Hard and unpleasant to the touch (10) 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.

(11) Content of polyallylamine, metal particles, and hydrophilic agent 1) Polyallylamine: The treatment fabric was measured using an elemental analyzer (manufactured by Horiba, Model EMGA-930) at any five locations, and the concentration of nitrogen ( g / g-treated fabric) was calculated and converted to the polyallylamine concentration (g / g-treated fabric), and the average value was multiplied by 100 to obtain the polyallylamine content (% by weight) of the treated fabric.
2) Metal particles: Using a fluorescent X-ray analyzer (type RIX-3100, manufactured by Rigaku) for the treated fabric, any five locations were measured, quantitative analysis of the amount of metal was performed, and the average value was obtained as the content. .
3) Hydrophilic agent: Using an X-ray photoelectron spectroscopic analyzer (manufactured by Shimadzu, model ESCA-3400) for the treated fabric, five arbitrary positions were measured to obtain the carboxylic acid concentration (g / g treated fabric). Converted to a concentration (g / g treated fabric), the average value was multiplied by 100 to obtain the hydrophilic agent content (% by weight) of the treated fabric.

[Examples 1 to 3]
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, The remaining 56dtex / 45f cupra (Asahi Kasei Fibers Co., Ltd. Bemberg) was inserted during the processing step and interlaced to obtain a composite yarn of 106dtex / 93f.
Next, using the obtained composite yarn, a milled circular knitted fabric was produced by a conventional method at 24 gauge. The mixing ratio of the cellulose fiber in this knitted fabric was 53%, and the mixing ratio of the basic dye-dyeable fiber was 47%.
Then, after pre-wetting at 60 ° C. in a spread form, pre-setting at 185 ° C., using the enzyme treatment conditions shown below, treatment time so that the weight loss rate is 2.4% using a liquid flow dyeing machine The weight loss was adjusted.
<Enzyme treatment conditions>
Enzyme solution: Cellulase T (manufactured by Amano Enzyme, End + Exo-type Cellulase) 8% omf
pH: 4.5 (adjusted with acetic acid and sodium acetate)
Auxiliary agent: Immacol C2GL: 4 g / L
Bath ratio: 1:30
Processing temperature: 45 ° C

After the treatment, a deactivation treatment was carried out at 80 ° C. for 15 minutes, followed by washing with water and dyeing of cellulose fibers under the following conditions.
<Dyeing condition 1>
Reactive dye: Sumifix HF Blue BG: 0.9% omf
Sodium sulfate: 20 g / L
Sodium carbonate: 10 g / L
Auxiliary agent: Immacol C-2GL: 4 g / L
Bath ratio: 1:20
Dyeing temperature: 60 ° C
Dyeing time: 60 minutes

After dyeing, hot water washing and water washing were repeated at 90 ° C., and after dehydration, the basic dye-dyed fiber was dyed under the following conditions. At this time, polyallylamine PAA-D41-HCL (average molecular weight 20000, pure content 40%) manufactured by Nitto Bo Medical as polyallylamine and SR-C1800 manufactured by Takamatsu Oils and Fats as a hydrophilic agent were added to the dyeing bath. The amount added was adjusted so that the content in the fabric would be the value shown in Table 1.
<Dyeing condition 2>
Dispersion type cationic dye: Kayacrill Blue 2RL-ED: 1.5% omf
Sodium sulfate: 4 g / liter pH: 4.3
Bath ratio: 1:20
Dyeing temperature: 105 ° C
Dyeing time: 45 minutes

After dyeing, hot water washing and water washing were repeated twice in this order at 80 ° C., and then the treatment with metal colloid was performed by the padding method under the following conditions.
<Metal colloid treatment>
Metal colloid: Platinum colloid (average particle diameter of platinum is 7 nm, solvent is water, and polyvinylpyrrolidone is contained as 1% of protective agent). The amount added to the padding bath was adjusted so that the content in the fabric would be the value shown in Table 1. In addition, the zeta potential of the platinum colloid was −19.8 mV (measured by Malvern Zeta Sizer ZS).
Padding bath: The pH was adjusted to 3.8, and a sewing improver and a softening agent were added.
After the metal colloid treatment, it was finished by heat treatment at 140 ° C.

The obtained dyed fabric had a pH of 5.9, a basis weight of 145 g / m ² , a coarse density of 54 / inch, a well density of 33 / inch, and a thickness of 0.50 mm. When the obtained dyed fabric was observed with an electron microscope at a magnification of 1800, twelve streaks having a width of 0.4 μm and a length of 7.9 μm per fiber length of 50 μm were present on the surface of the cellulose fiber. It was.
Table 2 below shows the evaluation results of the deodorant performance, antibacterial performance, water absorption / diffusion performance, color developability and fastness to sweat alkali of the obtained dyed fabric. From the results of Table 2, it can be seen that the fabrics obtained in Examples 1 to 3 are dyed fabrics having excellent deodorizing performance, antibacterial performance, water absorption and diffusion performance, color developability, and fastness to sweat alkali, and high commercial value. .

[Comparative Example 1]
A dyed fabric was obtained in the same manner as in Example 2 except that the hydrophilic agent was not added in the dyeing of the basic dyeable fiber. Table 2 shows the evaluation results of the deodorized performance, antibacterial performance, water absorption / diffusion performance, color development, and sweat alkali fastness of the obtained dyed fabric.
[Comparative Example 2]
A dyed fabric was obtained in the same manner as in Example 2 except that the metal colloid treatment was not performed. Table 2 shows the evaluation results of the deodorized performance, antibacterial performance, water absorption / diffusion performance, color development, and sweat alkali fastness of the obtained dyed fabric.
From the results in Table 2, the dyed fabrics obtained in Examples 1 to 3 of the present invention are superior in the deodorizing performance, antibacterial performance, and water absorption / diffusion performance durability compared to the fabrics obtained in Comparative Examples 1 and 2. It can be seen that this is a dyed fabric having high color developability, excellent texture and high commercial value.

  The deodorant antibacterial fiber fabric of the present invention is a deodorant antibacterial fiber fabric excellent in deodorant performance, antibacterial performance and water absorption / diffusion performance, excellent in color development and fastness performance, and excellent in wearing feeling. It can be suitably used in the inner field and sports clothing field.

Claims (8)

  A deodorizing and antibacterial fiber fabric in which cellulose fiber and basic dyeable fiber are mixed, and contains 0.005 to 0.1% by weight of metal particles containing polyallylamine and having an average particle diameter of 5 to 100 nm. Containing, 0.3 to 0.8% by weight of a hydrophilic agent, the ammonia reduction rate, the isovaleric acid reduction rate and the nonenal reduction rate in the deodorant processed fiber product certification standard after 50 washings are each 70% or more, Deodorant and antibacterial properties, characterized in that the bacteriostatic activity value of Staphylococcus aureus is not less than 2.2 and not less than 85% and not less than 75%, and the criteria for recognition by the Council for Textile Hygiene Processing after 50 washings Fiber fabric.   The number average molecular weight of polyallylamine is 1000-70000, and content is 0.2-3.0 weight%, The deodorizing antibacterial fiber fabric of Claim 1 characterized by the above-mentioned.   The deodorant antibacterial fiber fabric according to claim 1 or 2, wherein the metal particles are made of at least one metal selected from gold, silver, platinum, rhodium, ruthenium and iridium.   The deodorizing and antibacterial fiber fabric according to any one of claims 1 to 3, wherein the hydrophilic agent is a cationic aromatic polyester polyether block copolymer. The deodorant antibacterial fiber fabric according to any one of claims 1 to 4, wherein a water drop disappearance time after 50 washings is 2 seconds or less and a water absorption diffusion area is 10 cm ² or more.   When dyeing a mixed fabric of cellulose fiber and basic dyeable fiber with a cationic dye, polyallylamine and a hydrophilic agent are used in combination to add a polyallylamine and a hydrophilic agent, and then a metal colloid is added and then heat-treated. The manufacturing method of the deodorizing antibacterial fiber fabric as described in any one of Claims 1-5 characterized by the above-mentioned.   7. The method for producing a deodorant antibacterial fiber fabric according to claim 6, wherein the metal colloid is applied with an aqueous dispersion containing no binder resin.   The deodorant antibacterial fiber fabric according to claim 6 or 7, wherein the mixed fabric is subjected to a 1.5 to 10% reduction treatment with a cellulose-degrading enzyme at a temperature of 65 ° C or lower before dyeing with a cationic dye. Manufacturing method.