TWI803493B - Particulate deodorant for fiber - Google Patents

Abstract

A deodorant for a fiber of the present invention includes an a-zirconium phosphate and/or an a-titanium phosphate having no greater than 5.0 µm of a maximum particle size, 0.2 µm to 0.7 µm of a median diameter, and 0.1 µm or greater of a D10 diameter, as particle sizies.

Description

Deodorant for fine particle fibers

field of invention

The invention relates to a deodorant for microparticle fibers, and belongs to the technical field of deodorants and fibers.

Background of the invention

In the pursuit of a more comfortable living environment in recent years, deodorant mats, deodorizing curtains, deodorizing filters, and clothes and bedding with deodorizing functions against sweat and old people have appeared on the market. products". In Patent Document 1, in order to obtain a deodorant that can deodorize both acid and alkali components, has high deodorization performance against malodors such as sweat odor, and is not easy to reduce the deodorization performance after repeated washing, and is used for fibers with water absorption, it is disclosed A deodorizing system using a liquid containing bentonite, aluminum silicate, binder resin, modified polysiloxane, zinc oxide and water.

In Patent Documents 2 and 3, as a method of directly adding an antibacterial agent or a deodorant to the fiber, an elastic yarn made of polyurethane starting from polymer diol and diisocyanate is disclosed. It is polyurethane elastic yarn containing metal phosphate and 4th grade ammonium salt antibacterial agent. Prior Art Documents Patent Documents

[Patent Document 1] Japanese Patent Laid-Open No. 2015-171449 [Patent Document 2] Japanese Patent No. 5413360 [Patent Document 3] Japanese Patent No. 5870928

Outline of the Invention Problems to be Solved by the Invention

However, the deodorant system disclosed in Patent Document 1 utilizes post-processing methods. Although products with temporary deodorant functions can be obtained, the binder used to attach the functional agent will cause damage to the texture or processing. There is a problem of lower productivity due to longer steps or lower washing durability. Also, the deodorants disclosed in Patent Documents 2 and 3 are mixed with fibers, and it is difficult to obtain a deodorizing effect in the buried part. In order to obtain a sufficient effect, it is necessary to increase the amount of addition. However, increasing the amount of addition will cause aggregation or large Particles are easy to mix in, and the thread is prone to breakage when spinning. The object of the present invention is to provide a deodorant with good spinnability and high deodorizing performance against basic gases such as trimethylamine and ammonia, especially excellent deodorizing performance against ammonia. means to solve problems

Specific means for solving the aforementioned problems are as follows. 1. A deodorant for fibers, comprising α-zirconium phosphate and/or α-titanium phosphate, having a median particle size of 0.2-0.7 μm, a maximum particle size of 5.0 μm or less, and a D10 diameter of 0.1 μm or more.

2. The deodorant agent for fibers according to the above 1., wherein the aforementioned α-zirconium phosphate is represented by the following formula (1): Zr _1-x Hf _x H _a (PO ₄ ) _b ·nH ₂ O (1) Formula (1) Among them, a and b are positive numbers satisfying 3b-a=4, b is 2.0<b≦2.1, x is a positive number of 0≦x≦0.2, and n is a positive number of 0≦n≦2.0.

3. The deodorant for fibers according to the above 1., wherein the α-titanium phosphate is represented by the following formula (2): TiH _a (PO ₄ ) _b・nH ₂ O (2) In the formula (2), a and b are A positive number satisfying 3b-a=4, b is a positive number of 2.0<b≦2.1, and n is a positive number of 0≦n≦2.0.

4. The deodorant for fibers according to any one of 1. to 3. above, wherein the moisture content of α-zirconium phosphate and α-titanium phosphate is 1.0% by weight or less.

5. The deodorant for fibers according to any one of 1. to 4. above, wherein α-zirconium phosphate and α-titanium phosphate are synthesized in an aqueous solution.

6. The deodorant for fibers according to any one of 1. to 5. above, which is for mixing with fibers.

7. A deodorant fiber comprising the deodorant for fiber according to any one of 1. to 6. above.

8. The deodorant fiber according to 7. above, wherein the fiber is at least one selected from the group consisting of polyester, polyurethane, nylon, rayon, acrylic resin, vinylon, and polypropylene . Invention effect

According to the present invention, it is possible to provide a deodorant having good spinnability, high deodorizing performance against basic gases such as trimethylamine and ammonia, especially excellent deodorizing performance against ammonia.

form for carrying out the invention

The present invention relates to a fiber-incorporating deodorant containing α-zirconium phosphate and/or α-titanium phosphate. In terms of particle size, the median particle size is 0.2 to 0.7 μm, the maximum particle size is 5.0 μm or less, and the D10 diameter is 0.1 μm or more. Hereinafter, embodiments of the present invention will be described in detail. In addition, unless otherwise stated, "%" means "% by weight", "part" means "part by weight", and "ppm" means "ppm by weight". In addition, in this embodiment, the description of "lower limit~upper limit" indicating the numerical range means "above the lower limit and below the upper limit", and the description of "upper limit~lower limit" means "below the upper limit and above the lower limit". That is, a numerical range including an upper limit and a lower limit is indicated. Moreover, in this embodiment, the combination of 2 or more of the preferable aspects mentioned later also belongs to a preferable aspect.

1. Particle size of deodorant The deodorant used in this embodiment is composed of α-zirconium phosphate and/or α-titanium phosphate, and its particle size is 0.2-0.7 μm in median size and 5.0 μm in maximum size µm or less, D10 diameter 0.1 µm or more.

The preparation method of the particle size of the deodorant used in this embodiment is not particularly limited, and it is preferable to synthesize it in an aqueous solution in order to obtain the target particle size distribution. If it is synthesized in an aqueous solution, it is easy to be uniform during the synthesis, and it is easy to obtain a particle size distribution with sharp peaks. On the other hand, if the particle size is adjusted by pulverization, the range of particle size distribution will be widened due to the mixing of fine powder and large particles, which will easily become the cause of thread breakage during spinning, so it is not good.

In addition, the particle diameter of this embodiment is a value obtained by measuring with a laser diffraction particle size distribution meter and analyzing the result on a volume basis.

The median particle size of the deodorant used in this embodiment is 0.2-0.7 μm. Preferably it is 0.2-0.6 μm. Even if the median particle size is around 1 μm, there is not much problem with the spinliness. However, when the same amount of deodorant is mixed into the fiber, the finer the particle size, the more the number of particles, and it is easy to show the deodorant effect. In addition, when the median diameter is 0.2 μm or more, the particles are less likely to aggregate, spinning becomes easier, and yarn breakage during spinning can be suppressed.

The deodorant used in this embodiment has a maximum particle size of 5.0 μm or less. Preferably it is 4.0 μm or less, more preferably 3.0 μm or less. When the maximum diameter is 5.0 μm or less, it is preferable because the yarn breakage during spinning can be suppressed. In addition, the lower limit value is preferably 0.7 μm or more.

The D10 diameter of the deodorant used in this embodiment is 0.1 μm or more. It is preferably at least 0.15 μm, more preferably at least 0.2 μm. When the D10 diameter is 0.1 μm or more, the particles are less likely to aggregate, spinning becomes easier, and yarn breakage can also be suppressed. Also, the preferable upper limit of the D10 diameter is 0.4 μm or less. When the D10 diameter is 0.4 μm or less, it is easy to obtain particles having a median diameter of 0.7 μm or less.

2. Types of deodorants This embodiment is a deodorant for fibers composed of α-zirconium phosphate and/or α-titanium phosphate having the aforementioned specific particle size. Hereinafter, α-zirconium phosphate and α-titanium phosphate will be described.

2-1. Alpha zirconium phosphate As the alpha zirconium phosphate used in this embodiment, as long as it has the particle size mentioned above, various compounds can be used. As the α-zirconium phosphate suitably used in this embodiment, the compound represented by the following formula (1) can be mentioned, and the theoretical cation exchange capacity per unit weight is 6.7meq/g. From the viewpoint of deodorizing performance, the cation exchange capacity of the compound represented by the following formula (1) is preferably 6.0 meq/g or more, more preferably 6.4 meq/g or more. Zr _1-x Hf _x H _a (PO ₄ ) _b・nH ₂ O (1) In formula (1), a and b are positive numbers satisfying 3b-a=4, b is 2.0<b≦2.1, and x is 0 A positive number of ≦x≦0.2, and n is a positive number of 0≦n≦2.0.

In the aforementioned formula (1) of α-zirconium phosphate, hafnium (Hf) is derived from a raw material zirconium compound. x in formula (1) is a positive number of 0<x<1. In this embodiment, 0<x≦0.2 is preferable, more preferably 0.005≦x≦0.1, more preferably 0.005≦x<0.03. In this embodiment, if the content of hafnium increases, the ion exchange performance will be improved. However, hafnium has radioactive isotopes, so when used in electronic parts, it is better to suppress the value of x. n in formula (1) is preferably at most 0.2, more preferably at most 0.1, more preferably at most 0.05. By setting the value of n to 2.0 or less, when the resin is melted during yarn spinning, water of crystallization is easily desorbed, and foaming and yarn breakage can be prevented.

With regard to the production method of the α-zirconium phosphate used in this embodiment, known techniques can be applied, and there is no limitation on raw materials or equipment. For example, the methods described in Japanese Patent No. 5545328 and Japanese Patent No. 5821258, etc. are mentioned. As a method for producing α-zirconium phosphate, a method of reacting raw material compounds in an aqueous solution is preferable because uniform particles can be easily obtained. For example, a method of mixing an aqueous solution of a zirconium compound with an aqueous solution containing phosphoric acid and/or its salt (hereinafter referred to as "phosphoric acid (salt)") to form a precipitate, followed by aging to crystallize it, etc.

Zirconium compounds as raw materials for production include zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconyl sulfate, and zirconium oxychloride, etc., preferably zirconium nitrate, zirconium acetate, zirconium sulfate, Zirconium carbonate, zirconium basic sulfate, zirconyl sulfate, and zirconium oxychloride are more preferably zirconium oxychloride in consideration of reactivity and economy.

Phosphoric acid (salt) as a raw material for production includes phosphoric acid, sodium phosphate, potassium phosphate, ammonium phosphate, etc. Phosphoric acid is preferred, preferably high-concentration phosphoric acid with a weight concentration of about 75% to 85%. The reaction ratio of phosphoric acid (salt) is calculated as a molar ratio relative to the charge of the zirconium compound, and is 2 or more, preferably 2.05 or more, more preferably 2.1 or more. The reaction ratio of phosphoric acid (salt) may be a large excess relative to the zirconium compound. However, considering the conductivity of the supernatant, the above-mentioned molar ratio is 3 or less, preferably 2.9 or less, more preferably 2.6 the following.

In the production of α-zirconium phosphate, by adding the oxalic acid compound, the production of the compound will be faster, the waste of raw materials can be reduced and the production can be efficiently produced, so it is preferable. Examples of the oxalic acid compound in this case include oxalic acid dihydrate, ammonium oxalate, and ammonium hydrogen oxalate, and oxalic acid dihydrate is preferred. The reaction ratio of oxalic acid is calculated based on the molar ratio relative to the zirconium compound, and is 2.5-3.5, preferably 2.7-3.2, more preferably 2.8-3.0. In this embodiment, if it is this ratio, since the manufacture of alpha zirconium phosphate becomes easy, it is preferable.

After mixing the aqueous solution of zirconium compound and the aqueous solution containing phosphoric acid (salt), aging is carried out. The aging can be carried out at normal temperature. However, in order to speed up the aging, it is better to carry out under wet normal pressure above 90°C. In addition, in A pressure environment higher than normal pressure and a condition exceeding 100°C are called hydrothermal conditions, and synthesis is also possible under these conditions. When producing α-zirconium phosphate under hydrothermal conditions, it is preferable to perform the synthesis at 130° C. or lower from the viewpoint of production cost.

The production time of α-zirconium phosphate may be any time as long as α-zirconium phosphate can be synthesized. For example, alpha zirconium phosphate can be obtained by aging after mixing phosphoric acid (salt) with a zirconium compound and forming a precipitate. The aging time will vary depending on the aging temperature. For example, aging at 90°C is preferably more than 4 hours. In addition, even if aging is performed for 24 hours or longer, the content of α-zirconium phosphate tends to reach a limit and cannot be further increased. The synthesized α-zirconium phosphate is separated by filtration, carefully washed with water, and then dried to obtain α-zirconium phosphate.

2-2. α-Titanium Phosphate As the α-titanium phosphate used in this embodiment, as long as it has the aforementioned particle size, various compounds can be used. As the α-titanium phosphate suitably used in this embodiment, the compound represented by the following formula (2) can be mentioned, and the theoretical cation exchange capacity per unit weight is 7.7meq/g. From the viewpoint of deodorizing performance, the cation exchange capacity of the compound represented by the following formula (2) is preferably 6.2 meq/g or more, more preferably 6.7 meq/g or more. TiH _a (PO _4)b ·nH ₂ O (2) Among formula (2), a and b are positive numbers satisfying 3b-a=4, b is 2.0<b≦2.1, n is a positive number of 0≦n≦2.0 .

n in the aforementioned formula (2) of α-titanium phosphate is preferably 0.2 or less, more preferably 0.1 or less, more preferably 0.05 or less. By setting the value of n to 2.0 or less, when the resin is melted during yarn spinning, water of crystallization is desorbed, and foaming and yarn breakage can be prevented.

The production method of α-titanium phosphate can be applied to conventional techniques, and there is no limitation on raw materials or equipment. As a method for producing α-titanium phosphate, a method of reacting raw material compounds in an aqueous solution is preferable because uniform particles can be easily obtained. For example, it can be produced by adding phosphoric acid to an aqueous solution of a titanium compound to form a precipitate and crystallize it. For example, a method of mixing an aqueous solution of a titanium compound and an aqueous solution containing phosphoric acid (salt) to form a precipitate, followed by aging to crystallize it, and the like.

Titanium sulfate etc. are mentioned as a titanium compound of a manufacturing raw material. Examples of the phosphoric acid (salt) as the raw material for production include the same compounds as those described above.

3. Moisture content in deodorant The moisture content of the deodorant used in this embodiment is preferably 1.0% by weight or less. More preferably, it is 0.7 weight% or less. By setting the moisture content to 1.0% by weight or less, foaming or hydrolysis of the resin can be prevented when making a master batch, which is preferable.

4. Deodorant fiber This embodiment is a deodorant for fiber, and as a method of producing deodorant fiber using this deodorant, it is sufficient to follow a conventional method. For example, the method of mixing the deodorant of this embodiment into a fiber and spinning it, or the method of coating a deodorant solution on the fiber after spinning, etc. are mentioned.

Any known chemical fiber can be used as the usable fiber resin. Preferred specific examples include polyester, polyurethane, nylon, rayon, acrylic, vinylon, and polypropylene. These resins may be single polymers or copolymers. In the case of a copolymer, there is no particular limitation on the polymerization ratio of each copolymerization component.

The deodorant of this embodiment is preferably used as a deodorant for fiber mixing. In this case, as a specific production method of the deodorant fiber, there is a method in which the deodorant of this embodiment is mixed with molten liquid fiber resin or dissolved fiber resin solution, and the method is spun.

The ratio of the deodorant of this embodiment contained in resin for fibers is not specifically limited. Generally speaking, if the content is increased, the deodorant effect can be strongly exerted and lasted for a long time. However, even if the content exceeds a certain level, the deodorizing effect will not be much different, or the resin strength will decrease. It is better to use There are 0.1-3.0 parts by weight per 100 parts by weight of the resin, more preferably 0.5-2.0 parts by weight.

The deodorant fiber using the deodorant of this embodiment can be used in various fields where deodorization is necessary, such as underwear, stockings, socks, quilts, quilt covers, seat cushions, quilt blankets, and carpets , curtains, sofas, car seat cushions, air filters and nursing clothes and many other fiber products. [Example]

Next, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the following examples. The physical properties and deodorizing performance of the deodorant were measured in accordance with the following methods.

(1) Particle size: Median particle size, maximum particle size, and D10 diameter The particle size measurement of deodorants is carried out by the laser diffraction particle size distribution measuring device "LA-950" manufactured by Horiba Seisakusho Co., Ltd. The results are parsed on a volumetric basis. The measurement conditions were such that a deodorant dispersion liquid in which 1.0% by weight of a deodorant was added to 100% by weight of water was dispersed with ultrasonic waves, and the measurement was performed at a refractive index of 2.4.

(2) Spinning linearity test A master batch in which 10% by weight of a deodorant was added to 100% by weight of a polyester resin (MA2101M manufactured by Unitika) was produced. Next, this master batch was mixed with polyester resin pellets not containing a deodorant, and each addition amount (% by weight) was adjusted. Using a multifilament spinning machine, it was spun at a spinning temperature of 275°C and a spinning speed of 500m/min for 2 hours, and stretched at 120°C so that the elongation became 280-320%, and a deodorant-containing product was obtained. Polyester. At this time, as the oil agent, a water-soluble oil agent (DELION 6033 manufactured by Takemoto Oil & Fat Co., Ltd. was diluted 10 times with water) that is generally used for polyester fiber spinning was used. Continuous spinning was carried out for 2 hours, and the spinning property was evaluated according to the following determination method. The smaller the thread breakage rate, the better the spinnability. ○○: wire breakage rate is less than 3.0% ○: wire breakage rate is more than 3.0% and less than 6.0% △: wire breakage rate is more than 6.0% and less than 10.0% ╳: wire breakage rate is more than 10.0% ─: cannot be evaluated

(3) Deodorization test 1 The deodorization test is based on the certification standard for deodorized processed fiber products (developer: Product Certification Department of Japan Association for Fiber Evaluation Technology Association, date of formulation: September 2002 1 day), as follows, the deodorization evaluation of odor components was carried out by machine test. In addition, the fiber evaluation technology association of the corporate juridical person judges the reduction rate of each odor component as "having a deodorizing effect" based on the machine analysis test, and marks it in Table 1. ○Detection tube method 1. Adjustment of the product obtained by cylindrically braiding the extension thread produced in (2) above and performing alkali weight reduction treatment (boiling in 4% by weight sodium hydroxide aqueous solution for 1 hour, bath ratio = 1/40) into 10cm×10cm and put into a Tedlar Bag. 2. Inject a specific amount of test gas shown in Table 1, measure the residual gas concentration (ppm) after 2 hours with a component-corresponding detection tube (manufactured by Gastec), calculate the reduction rate of the residual gas concentration and record it as deodorization Rate. The determination is obtained by the average value of n=3. In addition, the gas filling volume is 3L, and the dilution gas uses dry air or nitrogen gas.

(4) Deodorization test 2 (durability test) After washing the cylindrical braided fibers subjected to the alkali weight reduction treatment in the above (3) 1 for 10 times, it was measured by the detection tube method described in the above (3) 2 .

(5) Moisture content The moisture content was calculated by [(weight after heating-weight before heating)/weight before heating] by heating the deodorants obtained in Examples and Comparative Examples at 150°C for 2 hours. As a result, it was 0.3 weight% in Examples 1-4, 0.4 weight% in Examples 5-12, 0.3 weight% in Comparative Examples 1-10, and 0.4 weight% in Comparative Examples 11-14.

[Table 1]

<Examples 1 and 2> Add 1160mL of deionized water and 173.4g of 35% hydrochloric acid to a 2L round bottom flask, and add 288.4g of 20% aqueous solution of zirconium oxychloride hexahydrate containing 0.18% of hafnium, and dihydrate the oxalic acid dihydrate 119.2 g dissolved therein. While carefully stirring this solution, 134.4 g of 75% phosphoric acid was added. It was heated to 98°C over 2 hours, and stirred and refluxed for 12 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain zirconium phosphate. This was pulverized with a rotor high-speed pulverizer (manufactured by FRITSCH, P-14 (manufactured in 1997): 16000 rpm, mesh 80 μm). As a result of measuring the obtained zirconium phosphate, it was confirmed that it was α-zirconium phosphate. The compositional formula of the α-zirconium phosphate was measured, and the compositional formula was: Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01 ·0.05H ₂ O with a median particle size of 0.51 μm, a maximum particle size of 2.5 μm, and a D10 diameter of 0.22 μm. Details are indicated in Table 2.

<Example 3, 4> Add 1056mL of deionized water and 185.2g of 35% hydrochloric acid to a 2L round bottom flask, and add 322.7g of 20% aqueous solution of zirconium oxychloride hexahydrate containing 0.18% of hafnium, and dihydrate oxalic acid 109.2 g were dissolved therein. While carefully stirring this solution, 160.8 g of 75% phosphoric acid was added. It was heated to 98°C over 2 hours, and stirred and refluxed for 12 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain zirconium phosphate. As a result of measuring the obtained zirconium phosphate, it was confirmed that it was α-zirconium phosphate. The compositional formula of the α-zirconium phosphate was measured, and the compositional formula was: Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01・0.05H ₂ O with a median particle size of 0.22 μm, a maximum particle size of 2.2 μm, and a D10 diameter of 0.15 μm. Details are indicated in Table 2.

<Examples 5 and 6> 228.75 mL of deionized water and 202.7 g of 75% phosphoric acid were added to a 500 mL round bottom flask. While carefully stirring, 68.55 g of titanium sulfate was added, and stirring was continued for 10 minutes. Thereafter, it was heated up to 100° C. over 1 hour, and stirred and refluxed for 44 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain titanium phosphate. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The compositional formula of the α-titanium phosphate was measured, and the compositional formula was: TiH _2.02 (PO ₄ ) _2.01 ·0.05H ₂ O with a median particle size of 0.56 μm, a maximum particle size of 2.6 μm, and a D10 size of 0.25 μm. Details are indicated in Table 2.

<Examples 7 and 8> 228.75 mL of deionized water and 202.7 g of 75% phosphoric acid were added to a 500 mL round bottom flask. While carefully stirring, 68.55 g of titanium sulfate was added, and stirring was continued for 10 minutes. Thereafter, it was heated up to 85° C. over 1 hour, and stirred and refluxed for 20 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain titanium phosphate. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The compositional formula of the α-titanium phosphate was measured, and the compositional formula was: TiH _2.02 (PO ₄ ) _2.01 ·0.05H ₂ O with a median particle size of 0.21 μm, a maximum particle size of 2.2 μm, and a D10 size of 0.14 μm. Details are indicated in Table 2.

<Examples 9 and 10> The α-zirconium phosphate synthesized in Example 1 and the α-titanium phosphate synthesized in Example 5 were mixed at a ratio of 1:1 and used as a deodorant. The median diameter, maximum particle diameter, and D10 diameter of the mixture are shown in Table 2.

<Examples 11 and 12> The α-zirconium phosphate synthesized in Example 3 and the α-titanium phosphate synthesized in Example 7 were mixed at a ratio of 1:1 and used as a deodorant. The median diameter, maximum particle diameter, and D10 diameter of the mixture are shown in Table 2.

<Comparative Examples 1 and 2> A zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. was used. Details of the preparation are shown in Table 3.

<Comparative examples 3 and 4> 95 mL of deionized water and 1800 g of 75% phosphoric acid were added to a 500 mL round bottom flask. After adding 360 g of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium while carefully stirring, the temperature was raised to 98° C. over 1 hour, and stirred and refluxed for 12 hours. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The median particle size is 0.11 μm, the maximum particle size is 1.4 μm, and the D10 diameter is 0.05 μm. Details are indicated in Table 3.

<Comparative Examples 5 and 6> 1500 mL of deionized water was added to a 2L round bottom flask, and 210 g of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% of hafnium was added, and 240 g of oxalic acid dihydrate was dissolved therein. While carefully stirring this solution, 90 g of 75% phosphoric acid was added. It was heated to 98°C over 2 hours and refluxed with stirring for 24 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain zirconium phosphate. As a result of measuring the obtained zirconium phosphate, it was confirmed that it was α-zirconium phosphate. The compositional formula of the α-zirconium phosphate was measured, and the compositional formula was: Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01・0.05H ₂ O with a median particle size of 2.1 μm, a maximum particle size of 10.0 μm, and a D10 diameter of 0.81 μm. Details are indicated in Table 3.

<Comparative Examples 7 and 8> Disperse 10% of the zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. in water, add 50% by weight of 30 μm zirconia particles, and use Disper (special A Homodisper, model L (manufactured in 1994) manufactured by Kikka Kogyo Co., Ltd. (currently PRIMIX Co., Ltd.) was subjected to wet pulverization at a rotation speed of 3000 rpm for 2 hours. The median particle size is 0.52 μm, the maximum particle size is 5.1 μm, and the D10 diameter is 0.07 μm. Details are indicated in Table 3.

<Comparative Examples 9 and 10> Disperse 10% of the zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. in water, add 50% by weight of 10μm zirconia particles, and use Disper to turn Wet pulverization was carried out at 3000 rpm for 2 hours. The median particle size is 0.2 μm, the maximum particle size is 4.5 μm, and the D10 diameter is 0.05 μm. Details are indicated in Table 3.

<Comparative examples 11 and 12> 228.75 mL of deionized water and 202.7 g of 75% phosphoric acid were added to a 500 mL round bottom flask. While carefully stirring, 68.55 g of titanium sulfate was added, and stirring was continued for 10 minutes. Thereafter, the temperature was raised to 100° C. over 1 hour, and stirred and refluxed for 100 hours. After cooling, the obtained precipitate was carefully washed with water, and then dried at 105° C. to obtain titanium phosphate. As a result of measuring the obtained titanium phosphate, it was confirmed that it was α-titanium phosphate. The compositional formula of the α-titanium phosphate was measured, and the compositional formula was: TiH _2.02 (PO ₄ ) _2.01 ·0.05H ₂ O with a median particle size of 1.05 μm, a maximum particle size of 5.8 μm, and a D10 size of 0.51 μm. Details are indicated in Table 3.

<Comparative Examples 13 and 14> Disperse 10% of α-titanium phosphate synthesized in Comparative Example 6 in water, add 50wt% of 30 μm zirconia particles, and perform wet pulverization for 2 hours at 3000 rpm using Disper. The median particle size is 0.49 μm, the maximum particle size is 5.2 μm, and the D10 diameter is 0.06 μm. Details are indicated in Table 3.

<Comparative examples 15 and 16> Aluminum dihydrogen tripolyphosphate deodorant "K-FRESH 100P" manufactured by TAYCA Co., Ltd. was used. The median particle size is 1.1 μm, the maximum particle size is 5.9 μm, and the D10 diameter is 0.55 μm. Details are indicated in Table 3.

<Reference example> The deodorant evaluation was carried out without adding a deodorant, and directly spinning and cylindrical knitting.

The deodorants used in the examples have excellent spinnability without fear of thread breakage. The fiber added with the deodorant of the example has excellent deodorizing performance and maintains deodorizing performance after washing. On the other hand, the deodorants used in the comparative examples were not good in spinnability, deodorant performance, or both. The weight loss rate caused by alkali treatment was 13-18% by weight in all samples.

[Table 2]

[table 3]

Industrial Applicability The deodorant of the present invention is fine particles and has a narrow particle size distribution, so it has excellent spinnability. In addition, especially those mixed with fibers have excellent deodorizing performance against ammonia and have high washing resistance.

(none)

Claims (8)

A deodorant for fibers, characterized by comprising α-zirconium phosphate and/or α-titanium phosphate, with a particle size of 0.2-0.6 μm in median, 3.0 μm or less in maximum particle size, and 0.1-0.4 μm in D10 diameter. The deodorant for fibers as claimed in claim 1, wherein the aforementioned alpha zirconium phosphate is represented by the following formula (1): Zr _1-x Hf _x H _a (PO ₄ ) _b ‧nH ₂ O (1) In the formula (1), a and b are positive numbers satisfying 3b-a=4, b is 2.0<b≦2.1, x is a positive number 0≦x≦0.2, n is a positive number 0≦n≦2.0. The deodorant for fibers as claimed in claim 1, wherein the aforementioned α-titanium phosphate is represented by the following formula (2): TiH _a (PO ₄ ) _b ‧nH ₂ O (2) In the formula (2), a and b satisfy 3b -a=4 is a positive number, b is 2.0<b≦2.1, n is 0≦n≦2.0. The deodorant for fibers according to claim 1, wherein the water content of the aforementioned α-zirconium phosphate and α-titanium phosphate is 1.0% by weight or less. The deodorant for fibers according to claim 1, wherein the aforementioned α-zirconium phosphate and α-titanium phosphate are synthesized in an aqueous solution. The deodorant for fibers as claimed in claim 1, which is for mixing fibers. A deodorant fiber, comprising the deodorant for fiber according to any one of Claims 1 to 6. Such as the deodorant fiber of claim 7, wherein the aforementioned fiber is selected from polyester, polyurethane, nylon, rayon, acrylic At least one of the group consisting of resin, vinylon and polypropylene.