JP2013204205A - Deodorant regenerated cellulosic fiber, method for producing the same, and fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant regenerated cellulosic fiber in which a carboxyl group is introduced in cellulose without graft polymerization, and deodorant properties to ammonia is improved, a method for producing the same, and a fiber structure.SOLUTION: The deodorant regenerated cellulosic fiber is a regenerated cellulosic fiber including acrylate-based resin particles and a metal. The acrylate-based resin particles have an average particle diameter of 0.2 to 1.5 μm. The metal is present as a metal ion and/or metallic fine particles. In the regenerated cellulose fiber, the content of the metal is 300 mg/kg or more. The deodorant regenerated cellulosic fiber can be produced by spinning a viscose liquid for spinning prepared by blending acrylate-based resin particles having an average particle diameter of 0.2 to 1.5 μm in a viscose dope including cellulose, and treating the obtained viscose rayon yarn with a metal ion. The fiber structure includes the deodorant regenerated cellulosic fiber.

Description

  The present invention relates to a deodorant regenerated cellulose fiber, a method for producing the same, and a fiber structure, and particularly relates to a deodorant regenerated cellulose fiber having an improved deodorant property against ammonia, a method for producing the same, and a fiber structure.

  It is known that the regenerated cellulose fiber is produced by various methods such as a viscose method, a copper ammonia method, and a solvent spinning method. Since regenerated cellulose fibers such as rayon fibers have a substrate of cellulose, they themselves have properties that are gentle on the skin. Conventionally, it has been proposed to provide further functionality while utilizing the properties of such regenerated cellulose fibers.

Patent Document 1 proposes that copper ions are adsorbed on a rayon fiber kneaded with a vinyl acetate-maleic acid copolymer containing a carboxyl group to impart deodorizing properties. Patent Document 2 discloses a deodorizing sheet including a modified cellulose fiber in which a carboxyl group introduced by graft polymerization is substituted with a metal ion such as Zn ²⁺ .

  However, the rayon fiber proposed in Patent Document 1 has a problem that the deodorizing property against ammonia after washing is low. Further, in Cited Document 2, since a carboxyl group is graft-polymerized on cellulose, which is a linear polymer, steric hindrance of an amorphous part occurs, leading to a decrease in fiber strength, hygroscopicity and water absorption. There is a problem that the dyeing property is changed due to the influence of the dyeing and the way the dye is introduced.

Japanese Patent Publication No.8-13905 Japanese Patent No. 3304067

  In order to solve the above-mentioned conventional problems, the present invention introduces a deodorant regenerated cellulose fiber in which a carboxyl group is introduced into cellulose without graft polymerization and the deodorizing property against ammonia is improved, a method for producing the same, and a fiber structure. provide.

  The deodorant regenerated cellulose fiber of the present invention is a regenerated cellulose fiber containing acrylate resin particles and a metal, the acrylate resin particles have an average particle diameter of 0.2 to 1.5 μm, and the metal is It exists as metal ions and / or fine metal particles, and the regenerated cellulose fiber has a metal content of 300 mg / kg or more.

  The method for producing a deodorant regenerated cellulose fiber of the present invention is prepared by mixing viscose stock solution containing cellulose with acrylate resin particles having an average particle size of 0.2 to 1.5 μm to prepare a viscose solution for spinning. A step of extruding the spinning viscose liquid from a nozzle and coagulating and regenerating to obtain a viscose rayon yarn, and a step of treating the viscose rayon yarn with metal ions.

  The fiber structure of this invention contains the said deodorant reproduction | regeneration cellulose fiber.

  The present invention relates to a regenerated cellulose fiber having a high deodorizing property against ammonia, especially after repeated washing, and a fiber structure using the same, by containing acrylate resin particles and a metal in the regenerated cellulose fiber. Can be provided.

  The present inventor introduces carboxyl groups into cellulose by including acrylate resin particles in cellulose, and supports or adds a specific amount of metal to the carboxyl groups, thereby deodorizing regenerated cellulose fibers. Has been found to improve, leading to the present invention.

<Deodorized regenerated cellulose fiber>
In the deodorized regenerated cellulose fiber of the present invention, acrylate-based particles having a carboxyl group are contained in a base material having a semipermeable membrane called cellulose, and metal ions and / or metal fine particles are supported or added to the carboxyl groups. Therefore, metal ions and / or metal fine particles are contained in the cellulose (inside the fiber). In the deodorant regenerated cellulose fiber, there is little or no direct contact between the skin and metal ions or metal fine particles, but low molecules such as gas pass through cellulose, and if it is a water-soluble gas component, cellulose and It is considered that the deodorizing action by the metal works because it is adsorbed to the fiber due to hydrophilic properties such as water absorption and moisture absorption caused by the acrylate-based resin particles and comes into contact with metal ions or metal fine particles in the cellulose. In addition, the present invention provides a spinning viscose liquid prepared by mixing acrylate resin particles containing carboxyl groups with a viscose stock solution containing cellulose, compared to conventional methods of imparting carboxyl groups by crosslinking or graft polymerization. Since the carboxyl group is introduced into the cellulose by spinning, it does not affect the molecular structure of the cellulose as in the case of polymerization, so the cotton quality (fiber strength) is not greatly reduced, and the dyeability and color developability. It is thought that there is little influence on

  In the present invention, the acrylate-based resin particle is a particle mainly composed of an acrylonitrile-based polymer and having a carboxyl group modified, and a copolymer obtained by crosslinking and polymerizing acrylic acid, sodium acrylate, and acrylamide on the acrylonitrile-based polymer. The resin particle which consists of a long-chain synthetic polymer comprised from these.

The acrylate resin particles are not particularly limited. For example, a crosslinked structure is introduced into an acrylonitrile polymer containing 50% by mass or more of acrylonitrile by treatment with hydrazine, divinylbenzene or triallyl isocyanate, and the remaining nitrile groups are hydrolyzed. Acrylonitrile-based resin particles that are chemically converted into salt-type carboxyl groups by decomposition are preferred. Examples of the acrylonitrile particles include an acrylonitrile particle having a specific gravity of 1.1 to 1.4 g / cm ³ , a moisture absorption rate of 35 to 70% at 20 ° C. and 65% RH, and a carboxyl group modified. Resin particles are used. As such acrylonitrile-based resin particles, for example, an aqueous dispersion of acrylonitrile-based resin particles such as Tuftic (registered trademark) “HU-700E” manufactured by Toyobo Co., Ltd.) can be used.

  The acrylate resin particles have an average particle diameter of 0.2 to 1.5 μm, preferably 0.2 to 1.0 μm. In the present invention, the average particle diameter of the acrylate-based resin particles refers to a volume cumulative average particle diameter d50 measured by a laser diffraction light scattering particle size analysis measurement method. When the average particle diameter of the acrylate resin particles exceeds 1.5 μm, the productivity of the fibers is deteriorated and it is difficult to make the fibers finer. On the other hand, when the average particle diameter of the acrylate resin particles is less than 0.2 μm, aggregation of the acrylate resin particles easily occurs and the yield of the acrylate resin particles decreases. In the deodorant regenerated cellulose fiber of the present invention, as will be described later, by spinning a spinning viscose liquid prepared by mixing raw material viscose with acrylate resin particles, the acrylate resin particles are contained in the fiber. Therefore, the acrylate resin particles are present in the fiber in a state of being finely dispersed in the spinning viscose liquid or in a state close thereto. That is, the particle diameter of the raw acrylate resin particles and the particle diameter of the acrylate resin particles in the deodorized regenerated cellulose fiber are almost the same. In addition, the average particle diameter of the acrylate resin particles in the deodorant regenerated cellulose fiber of the present invention can be measured by using a microscope (VHX-500F, manufactured by Keyence) and performing side observation with transmitted light at a magnification of 3500 times. This can be confirmed by measuring the particle size at 30 points in the visual field and calculating the average value.

  In the deodorant regenerated cellulose fiber, the content of the acrylate resin particles is preferably 3 to 10% by mass, more preferably 4 to 9% by mass with respect to cellulose. In the deodorized regenerated cellulose fiber, if the content of the acrylate resin particles is less than 3% by mass with respect to cellulose, the deodorizing performance tends to be low, and if it exceeds 10% mass, the fiber strength is reduced. There is a possibility that it cannot be made fine. In the present invention, the content of the acrylate resin particles in the deodorized regenerated cellulose fiber can be confirmed by measuring the nitrogen content. The nitrogen content can be measured by dissolving the fiber by the Kjeldahl method and nitrogen as ammonia nitrogen. In the deodorant regenerated cellulose fiber, the nitrogen content is preferably 0.06 to 0.22% by mass, and more preferably 0.09 to 0.20% by mass.

  In this invention, a carboxyl group is introduce | transduced in a cellulose by making a regenerated cellulose fiber contain an acrylate-type resin particle. In the deodorant regenerated cellulose fiber, the total amount of carboxyl groups is preferably 0.4 to 1.0 mmol / g, more preferably 0.5 to 0.9 mmol / g. If the total amount of carboxyl groups is less than 0.4 mmol / g, the deodorizing property tends to be low, and if it exceeds 1.0 mmol / g, the amount of particles contained in the fiber is large and the fiber strength may be lowered. As the form of the carboxyl group, a salt form and an acid form are conceivable. In the salt form, more metal ions can be added to the carboxyl group.

  In the deodorant regenerated cellulose fiber, the metal content is 300 mg / kg or more, and is preferably 800 mg / kg or more from the viewpoint of better deodorization. Although the upper limit of metal content is not specifically limited, It is preferable that it is 15000 mg / kg from a viewpoint of exhibiting productivity and the other function which a carboxyl group has. If the metal content is less than 300 mg / kg, the desired deodorizing performance for ammonia cannot be obtained. In the present invention, the content of the metal in the deodorized regenerated cellulose fiber is as follows. The fiber is incinerated at 800 ° C., the incinerated product is dissolved in perchloric acid, the dissolved product is used as a sample, and the content in the waste water of JIS K 0102 Measured by a method using the spectrophotometric method for metals specified in the analytical method. In addition, when a metal is silver, content of the metal in the said deodorant reproduction | regeneration cellulose fiber is measured based on the ICP emission method.

  Although it does not specifically limit as said metal, Zinc, copper, magnesium, calcium, aluminum, silver, etc. are mentioned. Among these, zinc is preferably used from the viewpoint of not coloring the fiber. Zinc is also easy to handle and has the advantage of low cost. In the deodorized regenerated cellulose fiber, the metal may be present in any state of metal ions or metal fine particles. From the viewpoint of having an excellent deodorizing property against ammonia even after laundering, it is more preferable that it exists in the form of metal fine particles. Moreover, washing durability can be improved more by making the metal in the said deodorant reproduction | regeneration cellulose fiber exist in the state of a metal oxide.

  The above-mentioned deodorant regenerated cellulose fiber is a deodorant certification standard for ammonia as defined by the Japan Textile Evaluation Technology Council (JTETC) deodorant processed fiber product certification standard (revised on April 1, 2011) Meet. Specifically, the deodorized regenerated cellulose fiber has an ammonia reduction rate (ammonia deodorization rate) measured by a detector tube method stipulated by JTETC of 70% or more, preferably 75% or more. More preferably, it is 80% or more. The deodorant property of the deodorized regenerated cellulose fiber is preferably excellent in washing durability. For example, the ammonia deodorization rate is preferably 70% or more, more preferably 75% even after washing 10 times according to JIS L 0217 (103) using a neutral detergent (JAFET standard detergent). Or more, more preferably 80% or more.

  The deodorant regenerated cellulose fiber preferably has a fineness of 0.3 to 8.0 dtex (decitex). More preferably, it is 0.6-6.0 dtex, More preferably, it is 0.7-3.6 dtex. When the fineness is less than 0.3 dtex, the single fiber tends to be broken during stretching. If the fineness exceeds 8.0 dtex, the fiber regeneration state tends to be poor, and the hue of the fiber may deteriorate.

  The deodorant regenerated cellulose fiber is preferably provided in the form of a long fiber or a short fiber to form a fiber structure. Examples of the long fiber shape include tow, filament, and non-woven fabric, and examples of the short fiber shape include wet papermaking raw cotton, airlaid non-woven raw cotton, and card raw cotton. Examples of the fiber structure include tow, filament, spun yarn, batting (padded cotton), paper, nonwoven fabric, woven fabric, knitted fabric, and the like, which is a kind of fabric selected from the group consisting of knitted fabric, woven fabric, and nonwoven fabric. It is more preferable.

<Manufacture of deodorant regenerated cellulose fiber>
The deodorant regenerated cellulose fiber of the present invention is not particularly limited, but a spinning viscose liquid prepared by adding acrylate resin particles having an average particle diameter of 0.2 to 1.5 μm to raw material viscose is spun. And it is preferable to manufacture by treating the obtained viscose rayon yarn with metal ions.

  As the raw material viscose, a viscose stock solution containing 7 to 10% by mass of cellulose, 5 to 8% by mass of sodium hydroxide, and 2 to 3.5% by mass of carbon disulfide may be prepared and used. At this time, additives such as ethylenediaminetetraacetic acid (EDTA) and titanium dioxide can be used as necessary. The temperature of the raw material viscose is preferably maintained at 18 to 23 ° C. A viscose solution for spinning is prepared by mixing acrylate resin particles with a viscose stock solution containing cellulose. As the acrylate resin particles, those described above can be used. The acrylate resin particles are preferably used as an aqueous dispersion. As the aqueous dispersion of acrylate resin particles, for example, Tufic (registered trademark) “HU-700E” manufactured by Toyobo Co., Ltd.) may be used. The addition amount of the acrylate resin particles is preferably 3 to 10% by mass, more preferably 4 to 9% by mass with respect to cellulose. If the amount of the acrylate resin particles added is less than 3% by mass with respect to cellulose, the deodorizing performance tends to be low, and if it exceeds 10% by mass, the fiber strength is lowered and there is a possibility that it cannot be made fine. The acrylate resin particles have an average particle diameter of 0.2 to 1.5 μm, preferably 0.2 to 1.0 μm. In the present invention, the average particle diameter of the acrylate-based resin particles refers to a volume cumulative average particle diameter d50 measured by a laser diffraction light scattering particle size analysis measurement method. When the average particle diameter of the acrylate resin particles exceeds 1.5 μm, the productivity of the fibers is deteriorated and it is difficult to make the fibers finer. On the other hand, when the average particle diameter of the acrylate resin particles is less than 0.2 μm, aggregation of the acrylate resin particles easily occurs and the yield of the acrylate resin particles decreases.

  As the spinning bath (Mueller bath), it is preferable to use a strongly acidic bath containing 95 to 130 g / L of sulfuric acid, 10 to 17 g / L of zinc sulfate, and 290 to 370 g / L of sodium sulfate (sodium salt). A more preferable sulfuric acid concentration is 100 to 120 g / L. The spinning bath preferably has a temperature of 45 to 60 ° C.

  The said deodorant reproduction | regeneration cellulose fiber can be manufactured, for example using a normal circular nozzle. As the spinning nozzle, it is preferable to use a circular nozzle having a diameter of 0.05 to 0.12 mm and a number of holes of 1000 to 20000, depending on the target production amount. Using the spinning nozzle, the spinning viscose liquid is extruded into a spinning bath, spun, and coagulated and regenerated. The spinning speed is preferably in the range of 30 to 80 m / min. The stretching ratio is preferably 39 to 55%. Here, the stretching ratio indicates how much the sliver speed after stretching is increased when the sliver speed before stretching is 100. In terms of magnification, it is 1 before stretching and 1.39 to 1.55 times after stretching.

  The obtained rayon fiber yarn is cut into a predetermined length and scoured. The scouring step is preferably performed in the order of hot water treatment, hydrosulfurization treatment, bleaching, pickling, and oil application. Then, if necessary, excess oil agent and moisture are removed from the fiber by a method such as a compression roller or vacuum suction, and a drying treatment is performed.

  The treatment with metal ions may be performed during the scouring process or as post-processing after the scouring process. In order to satisfy the required quality, it is possible to perform treatment with metal ions at an appropriate timing. Fibers treated with metal ions are highly deodorant to ammonia. Further, when the metal is zinc, the color of the fiber becomes white, which is preferable.

  The treatment with metal ions can be performed using an aqueous solution of a metal compound in which a metal exists in an ionic state as a metal treatment solution. When the metal is zinc, it can be treated using an inorganic zinc compound that has an ionic bond with an acid compound such as zinc sulfate, zinc chloride, or zinc nitrate. From the viewpoint of easily attaching metal ions to the fiber, a sulfate compound is preferably a metal chloride or nitrate compound because the bond between sulfuric acid and metal ions is strong. In addition, when processing in a scouring process, a sulfuric acid compound may be sufficient. The method of treatment with metal ions is not particularly limited as long as the metal treatment liquid can be brought into contact with the fiber. For example, a method such as an immersion method, a spray method, or a shower method can be used.

  It is preferable that the density | concentration of the metal compound in the said metal processing liquid is 0.5-20.0 g / L in conversion of a metal, More preferably, it is 1.0-5.0 g / L. When the metal is zinc, the concentration of the zinc compound in the metal treatment liquid is preferably 0.5 to 20.0 g / L, more preferably 1.0 to 5.0 g / L in terms of zinc. . If the amount is less than 0.5 g / L, the amount of metal attached to the fiber decreases, and if it exceeds 20.0 g / L, the treatment of the waste liquid after the treatment and the cleaning of the excessively attached metal compound become troublesome. The processing temperature is satisfactory because the room temperature is sufficient.

In addition, due to the substitution reaction of the carboxyl group, it is more efficient to let a metal ion such as Zn ²⁺ act on a substance in which the H of the carboxyl group is substituted with Na, Ca or Mg. Metal ions can be introduced into the fiber in the form of metal salts or metal complexes. Specifically, in the case of zinc ions, in the scouring step, the zinc sulfate concentration is converted to zinc to 1.0 to 5.0 g / L in the sulfuric acid condition at the time of pickling after the water stream treatment. It is good to process so that it may become, and the circulating shower method.

  When treated with metal ions, carboxyl groups and metal ions are coordinated by ionic bonds, and further reduction treatment can reduce metal ions such as zinc ions to simple metals (metal particles). It is. The reduction treatment is not particularly limited, but can be performed using an aqueous solution containing a reducing agent. Examples of the reducing agent include sodium borohydride, hydrazine, formalin, an aldehyde group-containing compound, hydrazine sulfate, hydrocyanic acid and its salt, hyposulfite and its salt, thiosulfate, hydrogen peroxide, Rochelle salt, glucose, alcohol A compound containing a group, hypophosphorous acid and a salt thereof, and the like can be used. Specifically, it can be treated by a shower method (one pass) using a thiosulfate such as sodium thiosulfate.

  Alternatively, metal ions such as zinc ions can be fixed to the fiber as metal fine particles by electrical treatment. The electrical treatment is not particularly limited, but can be performed by energizing the metal treatment liquid.

  As described above, when metal ions such as zinc ions are fixed to the fiber as metal fine particles, the deodorant washing durability against ammonia is improved. Furthermore, it is technically possible to change a metal such as zinc into zinc oxide with higher safety by heating the fiber on which the metal is fixed with wet heat.

<Fiber structure>
The fiber structure of the present invention preferably has an ammonia deodorization rate of 70% or more, more preferably 75% or more, and further preferably 80% or more. The fiber structure preferably has an ammonia deodorization rate of 70% or more, more preferably 75% or more, and even more preferably 80% or more even after repeated washing, for example, 10 washings.

  Although the said fiber structure is not specifically limited, For example, it is preferable that they are a spun yarn, a nonwoven fabric, a woven fabric, or a knitted fabric, and it is more preferable that it is 1 type chosen from the group which consists of a knitted fabric, a woven fabric, and a nonwoven fabric.

  When the fiber structure is a spun yarn, it may be composed only of the deodorized regenerated cellulose fiber, or may be blended and compounded with other fibers. Examples of other fibers include other regenerated cellulose fibers other than the above deodorant regenerated cellulose fibers, cotton, hemp, wool, acrylic fibers, polyester fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers. Such spun yarn can be processed into a woven fabric or a knitted fabric and used for clothing or the like.

  When the said fiber structure is a textile fabric or a knitted fabric, it may be comprised only by the said deodorizing cellulose fiber and may contain another fiber. Examples of other fibers include other regenerated cellulose fibers other than the above deodorant regenerated cellulose fibers, cotton, hemp, wool, acrylic fibers, polyester fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers. The structure of the woven or knitted fabric is not particularly limited. For example, circular knitting, weft knitting, and warp knitting (tricot) are preferable for knitting, and plain weaving, twill weaving, and satin weaving are preferable forms of the fiber structure because the texture effect of the present invention can be exhibited well.

  When the said fiber structure is a nonwoven fabric, it may be comprised only with the said deodorant reproduction | regeneration cellulose fiber, and may be mixed with another fiber. Examples of other fibers include other regenerated cellulose fibers other than the above deodorant regenerated cellulose fibers, cotton, hemp, wool, acrylic fibers, polyester fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers. Examples of the form of the nonwoven fabric include a wet nonwoven fabric (wet papermaking), an airlaid nonwoven fabric, a hydroentangled nonwoven fabric, and a needle punched nonwoven fabric. Such a nonwoven fabric can be used, for example, for wet tissues, wet sheets such as interpersonal / objective wipers, hydrolytic sheets, and the like. Moreover, it can be used for sanitary sheets such as cosmetic puffs and absorbent bodies.

  For example, when the fiber structure is processed into a pile or the like, the fiber structure may be composed only of the deodorized regenerated cellulose fiber or may be mixed with other fibers. Examples of other fibers include other regenerated cellulose fibers other than the above deodorant regenerated cellulose fibers, cotton, hemp, wool, acrylic fibers, polyester fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers.

  In the said fiber structure, when mixing with another fiber, it is preferable to contain the said deodorant reproduction | regeneration cellulose fiber 10 mass% or more. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more. The upper limit of the content of the deodorant regenerated cellulose fiber when mixed is preferably 90% by mass. When the mixing ratio of the deodorant regenerated cellulose fiber is less than 10% by mass, it tends to be difficult to obtain high deodorant property and soft texture. In addition, when it exceeds 90% by mass, the ratio of the rayon fiber increases, so the hygroscopicity, moisture release, moisture absorption exothermic property and drapeability are high, but the rayon fiber inherently low strength, low drying property (hard to dry), It tends to be low stretchability and low stretchability, and in order to supplement such performance, it is preferably combined with other fibers.

  Other fibers to be mixed with the deodorant regenerated cellulose fiber can be appropriately selected according to the purpose, and are not particularly limited. For example, in order to improve strength, it is preferable to combine polyester fibers. For improving heat retention, polyacrylic fibers are preferred. For improving the low stretchability, polyurethane elastic fibers are preferred. Polyamide fibers are preferred for improving color development and improving flexural strength. In addition, it can improve the hard texture of cotton and add warmth of wool. It is preferable to appropriately combine the fibers according to the use and requirements of the fiber structure.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.

  As the acrylate resin particles, Tufic (registered trademark) “HU-700E” manufactured by Toyobo Co., Ltd. was used. Tuftic (registered trademark) “HU-700E” manufactured by Toyobo is an aqueous dispersion containing 20% of acrylate resin particles (main component), and the average particle diameter of the acrylate resin particles is 0.625 μm. The average particle diameter is a volume cumulative average particle diameter d50 measured by a laser diffraction light scattering particle size analysis measurement method using a particle size distribution measuring instrument (“FRA 9220” manufactured by Nikkiso Co., Ltd.). The nitrogen content in the acrylate resin particles is 2.2%.

Example 1
[Preparation of viscose liquid for spinning]
An aqueous dispersion of acrylate resin particles (Toughtic (registered trademark) “HU-700E” manufactured by Toyobo Co., Ltd., average particle diameter 0.625 μm) The mixture was added to the course and stirred and mixed in a mixer to prepare a viscose solution for spinning. The temperature was kept at 20 ° C. As the raw material viscose, a viscose stock solution containing 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.8% by mass of carbon disulfide was used.
[Spinning conditions]
The obtained viscose solution for spinning was spun at a spinning speed of 60 m / min and a draw rate of 50% by a two-bath tension spinning method to obtain a viscose rayon yarn having a fineness of 1.4 dtex. As the first bath (spinning bath), a Mueller bath (50 ° C.) containing 100 g / L of sulfuric acid, 15 g / L of zinc sulfate, and 350 g / L of sodium sulfate was used. A circular nozzle (hole diameter: 0.06 mm, number of holes: 4000) was used as a spinneret for discharging viscose. During spinning, there was no inconvenience such as single yarn breakage, and the spinnability of the mixed viscose was good.
[Scouring conditions]
The viscose rayon yarn obtained above was cut into a fiber length of 38 mm and scoured. In the scouring process, water washing was performed after the hot water treatment, and desulfurization was performed by showering sodium hydrosulfide. The obtained treated cotton is washed again with water, and treated with metal ions by a shower method using a metal treatment liquid having a zinc sulfate concentration of 1.0 g / L in terms of zinc and a sulfuric acid concentration of 1.0 g / L, Thereafter, an oil agent was applied in a shower, excess moisture and the oil agent were dropped from the fiber with a compression roller, and a drying treatment (60 ° C., 7 hours) was performed to obtain a fiber A.

(Example 2)
Fiber B was obtained in the same manner as in Example 1 except that a metal treatment solution having a zinc sulfate concentration of 0.5 g / L in terms of zinc and a sulfuric acid concentration of 1.0 g / L was used for the treatment with metal ions. .

(Comparative Example 1)
A fiber C was obtained in the same manner as in Example 1 except that a metal treatment solution having a zinc sulfate concentration of 0.1 g / L in terms of zinc and a sulfuric acid concentration of 1.0 g / L was used for the treatment with metal ions. .

(Comparative Example 2)
A fiber D was obtained in the same manner as in Example 1 except that a sulfuric acid solution having a concentration of 1.0 g / L was used instead of the metal treatment solution.

(Comparative Example 3)
Fiber E (ordinary rayon fiber) was produced in the same manner as in Example 1 except that raw material viscose was used as it was as a spinning viscose liquid and was not treated with metal ions.

(Example 3)
A fiber F was produced in the same manner as in Example 2 except that after treatment with metal ions, reduction treatment was further performed with a shower with an aqueous solution of sodium thiosulfate (concentration: 10.0 g / L).

  The total amount of carboxyl groups of the fibers A to F and the zinc content were measured as follows, and the results are shown in Table 1 below. Moreover, the deodorizing performance and the washing durability of the fibers A to F were measured and evaluated as follows, and the results are shown in Table 1 below.

(Measurement of carboxyl group)
(1) 1.2 g of the sample was immersed in 50 mL of 1 mol / L hydrochloric acid aqueous solution (pH 0.1), stirred and left for 5 minutes. Then, it stirred again and it adjusted so that pH of aqueous solution might be set to 2.5. Next, the sample was washed with water, dried at 105 ° C. for 2 hours with a constant temperature air dryer, and completely dried.
(2) 100 mL of ion exchange water, 0.4 g of sodium chloride, and 20 mL of a 0.1 mol / L sodium hydroxide aqueous solution were placed in a beaker.
(3) 1 g of the sample prepared in (1) is precisely weighed [W1 (g)], finely cut to a size that does not wrap around the stirrer, put in the beaker prepared in (2), and stirred for 15 minutes with a stirrer did. The stirred sample was suction filtered. 60 mL of the filtrate was taken, titrated with 0.1 mol / L hydrochloric acid aqueous solution using phenolphthalein as an indicator, and the titer was set to X1 (mL).
(4) The total amount Y (mmol / g) of carboxyl groups was calculated based on the following formula.
Total amount of carboxyl groups Y (mmol / g) = [{(0.1 × 20) − (0.1 × X1)} × (120/60)] / W1

(Measurement of zinc content)
The metal content in the fiber is as follows: the fiber is ashed at 800 ° C., the ashed product is dissolved in perchloric acid, the dissolved product is used as a sample, and the absorbance of zinc specified by the analysis method in waste water of JIS K 0102 It was measured by the method using the method.

(Deodorization performance)
The evaluation of the deodorizing performance was carried out by applying the method stipulated in the deodorant processed fiber product certification standard (revised on April 1, 2011) of the Japan Fiber Evaluation Technology Council (JTETC). Ammonia was used as the gas species. The deodorant certification standard for ammonia is a reduction rate of 70% or more.

Specifically, the evaluation was performed as follows according to the instrument analysis (detector tube method) stipulated by the Council for Textile Evaluation Technology. A 0.60 g sample was placed in a 5 L Tedlar bag and sealed. Next, 3 L of the odor component gas was injected into the Tedlar bag so as to have a prescribed initial concentration using a syringe. Two hours after injecting the odor component gas, the concentration of the odor component gas in the Tedlar bag was measured with a detector tube. A blank test was conducted in the same manner. And the reduction rate of the odor component was calculated | required by the following formula using the measured value in the case of using the measured value in a blank test, and a sample. The initial concentration of ammonia was 100 ppm.
Decrease rate (%) = [(measured value in blank test after 2 hours−measured value when using sample after 2 hours) / 2 measured value in blank test after 2 hours] × 100

(Washing durability)
(1) Laundry test sample: Raw cotton washing method: It was performed according to JIS L 0217 (103).
Detergent used: Neutral detergent (JAFET standard detergent)
Number of times of washing: 0, 10 times (2) Evaluation of deodorizing performance It was performed as described above.

  From the results shown in Table 1, the fibers of Examples containing acrylate resin particles and containing 300 mg / kg or more of zinc have high deodorizing properties against ammonia, and particularly high deodorizing properties against ammonia even after washing. It was found to have sex. In addition, as can be seen from the comparison between Example 2 and Example 3, by carrying out the reduction treatment, the zinc ions are fixed to the fiber as zinc fine particles, so that the zinc content in the fiber is increased and the washing durability is also improved. It has improved.

  On the other hand, although the fiber of the comparative example 3 (normal rayon fiber) and the acrylate resin particle which do not contain any acrylate resin particles and zinc are contained, the zinc content is less than 300 mg / kg. It was confirmed that the fiber of Example 1 and Comparative Example 2 containing acrylate resin particles but not treated with zinc ions significantly deteriorated in deodorizing performance against ammonia after 10 washings. In addition, although the fiber of the comparative example 2 contains about 10 mg / kg zinc, this adheres during the spinning process.

  The deodorant rayon fiber of the present invention can be used for fiber structures such as spun yarn, knitted fabric, woven fabric, non-woven fabric, tow, filament, batting (padded cotton), paper and the like. In addition, the fiber structure of the present invention can be used for clothes, cosmetic puffs, hygiene materials such as absorbent bodies, wet tissues, wet sheets such as interpersonal / objective wipers, water-degradable sheets, dry wipers, filters, and the like.

Claims (8)

Regenerated cellulose fiber containing acrylate resin particles and metal,
The acrylate resin particles have an average particle diameter of 0.2 to 1.5 μm,
The metal exists as metal ions and / or metal fine particles,
The regenerated cellulose fiber, wherein the metal content is 300 mg / kg or more.   The deodorized regenerated cellulose fiber according to claim 1, wherein the total amount of carboxyl groups in the regenerated cellulose fiber is 0.4 to 1.0 mmol / g.   The deodorized regenerated cellulose fiber according to claim 1 or 2, wherein the regenerated cellulose fiber contains 3 to 10 mass% of the acrylate resin particles with respect to cellulose.   The deodorant regenerated cellulose fiber according to any one of claims 1 to 3, wherein the metal is zinc. It is a manufacturing method of the deodorant reproduction | regeneration cellulose fiber of any one of Claims 1-4,
A step of preparing a viscose solution for spinning by mixing acrylate resin particles having an average particle size of 0.2 to 1.5 μm with a viscose stock solution containing cellulose;
A step of extruding the spinning viscose liquid from a nozzle and solidifying and regenerating to obtain a viscose rayon yarn;
A method for producing a deodorized regenerated cellulose fiber comprising a step of treating the viscose rayon yarn with metal ions.   The method for producing deodorized regenerated cellulose fibers according to claim 5, wherein the viscose rayon yarn treated with the metal ions is further reduced.   The method for producing a deodorant regenerated cellulose fiber according to claim 5 or 6, wherein the addition amount of the acrylate resin particles is 3 to 10% by mass with respect to cellulose.   The fiber structure containing the deodorant reproduction | regeneration cellulose fiber of any one of Claims 1-4.