JP6965553B2 - Deodorant for fine particle fibers - Google Patents

Description

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

In recent years, with the demand for a more comfortable living environment, "deodorant" for clothes, bedding, etc., which has a deodorant sheet, deodorant curtain, deodorant filter, and deodorant function against sweat odor, aging odor, etc. "Sex products" are also becoming available.
In Patent Document 1, both acid and base components can be deodorized, the deodorant property against bad odors such as sweat odor is high, the deodorant property does not easily decrease even after repeated washing, and a deodorant that gives fibers having water absorption. Disclosed is a deodorant system using a liquid containing smectite, aluminum silicate, binder resin, modified silicone compound, zinc oxide and water.

In Patent Documents 2 and 3, as a method of directly incorporating an antibacterial agent or a deodorant into a fiber, it is an elastic thread made of polyurethane using a polymer diol and diisocyanate as starting materials, and is a metal phosphate and a quaternary ammonium. A polyurethane elastic yarn containing a salt-based antibacterial agent is disclosed.

Japanese Unexamined Patent Publication No. 2015-171449 Japanese Patent No. 5413360 Japanese Patent No. 5870928

However, in the deodorizing system disclosed in Patent Document 1, although it is a post-processing method and a product having a deodorizing function can be obtained temporarily, the texture is impaired by the binder for adhering the functional agent. In addition, there are problems such as a decrease in productivity and a decrease in washing durability due to a long processing process.
Further, when the deodorants described in Patent Documents 2 and 3 are kneaded into fibers, it is difficult to obtain a deodorizing effect on the buried portion, and it is necessary to increase the addition amount in order to obtain a sufficient effect. If the amount is increased, agglomeration occurs and large particles are likely to be mixed, so that there is a drawback that yarn breakage during spinning is likely to occur.
An object of the present invention is to provide a deodorant having good spinnability, high deodorizing performance against basic gases such as trimethylamine and ammonia, and particularly excellent deodorizing performance of ammonia.

Specific means for solving the above problems are as follows.
1. 1. Fibers containing zirconium α-phosphate and / or titanium α-titanium phosphate having a median diameter of 0.2 to 0.7 μm, a maximum particle size of 5.0 μm or less, and a D10 diameter of 0.1 μm or more. Deodorant for.

2. The deodorant for fibers according to 1 above, wherein the zirconium α-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, and x is a positive number of 0 ≦ x ≦ 0.2. , N is a positive number of 0 ≦ n ≦ 2.0.

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

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

5. The deodorant for fibers according to any one of 1 to 4 above, wherein zirconium α-phosphate and titanium 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 used for kneading fibers.

7. A deodorant fiber containing at least one of the fiber deodorants according to 1 to 6 above.

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

According to the present invention, a deodorant having good spinnability because it does not cause aggregation even when added to fibers, has high deodorizing performance against basic gases such as trimethylamine and ammonia, and is particularly excellent in ammonia deodorizing performance. Can be provided.

The present invention has zirconium α-phosphate and / or α-phosphoric acid having a median diameter of 0.2 to 0.7 μm, a maximum particle size of 5.0 μm or less, and a D10 diameter of 0.1 μm or more. Regarding deodorant for kneading fibers containing titanium.
Hereinafter, the present invention will be described in detail.
Unless otherwise specified, "%" means "% by weight", "parts" means "parts by weight", and "ppm" means "ppm by weight". Further, in the present invention, the description of "lower limit to upper limit" representing the numerical range represents "lower limit or higher and lower limit or lower", and the description of "upper limit to lower limit" represents "lower limit or lower limit and higher limit or higher". That is, it represents a numerical range including an upper limit and a lower limit. Furthermore, in the present invention, a combination of two or more of the preferred embodiments described below is also a preferred embodiment.

1. 1. Deodorant for use in the particle size present invention deodorant consists α zirconium phosphate and / or α titanium phosphate, the particle size is the median diameter 0.2 to 0.7 [mu] m, and maximum particle size of 5 It is 0.0 μm or less and the D10 diameter is 0.1 μm or more.

The method for preparing the particle size of the deodorant used in the present invention is not limited, but it is preferable to synthesize it in an aqueous solution in order to obtain the desired particle size distribution. When synthesized in an aqueous solution, it is easy to make it uniform during synthesis, and it is easy to obtain a sharp particle size distribution. On the other hand, if the particle size is adjusted by pulverization, fine powder and large particles are mixed and the width of the particle size distribution is widened, which tends to cause yarn breakage during spinning, which is not preferable.

The particle size in the present invention indicates a value measured by a laser diffraction particle size distribution meter and the result analyzed on a volume basis.

The median diameter of the deodorant used in the present invention is 0.2 to 0.7 μm. It is preferably 0.2 to 0.6 μ. Even if the median diameter is around 1 μm, there is little problem with spinnability, but when kneaded into the fiber, the number of fine particles is larger and the deodorizing effect is more likely to occur, so the median diameter is 0.2 to 0.7 μm. Fine particles are preferred. Further, if the median diameter is smaller than 0.2 μm, it tends to aggregate and cause yarn breakage during spinning, which is not preferable.

The maximum particle size of the deodorant used in the present invention is 5.0 μm or less. It is preferably 4.0 μm or less, and more preferably 3.0 μm or less. If the maximum diameter is larger than 5.0 μm, it may cause yarn breakage during spinning, which is not preferable.

The D10 diameter of the deodorant used in the present invention is 0.1 μm or more. It is preferably 0.15 μm or more, and more preferably 0.2 μm or more. If the D10 diameter is smaller than 0.1 μm, it is not preferable because it tends to agglomerate, it becomes difficult to spin, and it tends to cause yarn breakage. The preferred upper limit of the D10 diameter is 0.4 μm. If the D10 diameter exceeds 0.4 μm, it becomes difficult to obtain particles having a median diameter of 0.7 μm or less.

2. Types of Deodorant The present invention is a deodorant for fibers made of zirconium α-phosphate and / or titanium α-phosphate having the above-mentioned specific particle size.
Hereinafter, zirconium α-phosphate and titanium α-titanium phosphate will be described.

2-1. α-Zirconium Phosphate As the α-zirconium phosphate used in the present invention, various compounds can be used as long as they have the above-mentioned particle size.
The zirconium α-phosphate used in the present invention is preferably a compound represented by the following formula (1) and having a cation exchange capacity of 6.7 meq / g per unit weight.
_{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, and x is a positive number of 0 ≦ x ≦ 0.2. , N is a positive number of 0 ≦ n ≦ 2.0.

In the above formula (1) of α-zirconium phosphate, hafnium (Hf) is derived from the raw material zirconium compound. X in equation (1) is a positive number with 0 <x <1. In the present invention, it is preferably 0 <x ≦ 0.2, more preferably 0.005 ≦ x ≦ 0.1, and even more preferably 0.005 ≦ x <0.03. In the present invention, the ion exchange performance is improved when the hafnium content is high, but since hafnium has radioactive isotopes, when it is used for electronic components, if it is too high, it may have an adverse effect.
N in the formula (1) is preferably 0.2 or less, more preferably 0.1 or less, and further preferably 0.05 or less. When the value of n is 2.0 or less, water of crystallization is desorbed when the resin is melted during spinning, and foaming and yarn breakage can be prevented.

As the method for producing zirconium α-phosphate used in the present invention, conventional techniques can be applied, and there are no restrictions on raw materials, equipment, or the like. For example, the methods described in Japanese Patent No. 5545328 and Japanese Patent No. 5821258 can be mentioned.
As a method for producing zirconium α-phosphate, a method of reacting the raw material compound 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 a salt thereof [hereinafter referred to as "phosphoric acid (salt)"] to form a precipitate, which is aged and crystallized. Can be mentioned.

Examples of the zirconium compound used as a manufacturing raw material include zirconium nitrate, zirconium acetate, zirconium sulfate, zirconium carbonate, basic zirconium sulfate, zirconium oxysulfate, and zirconium oxychloride. Basic zirconium sulfate, zirconium oxysulfate and zirconium oxychloride are preferable, and zirconium oxychloride is more preferable in consideration of reactivity and economy.

Examples of the phosphoric acid (salt) of the production raw material include phosphoric acid, sodium phosphate, potassium phosphate, ammonium phosphate and the like, and phosphoric acid is preferable, and more preferably a high concentration of about 75% to 85% by weight. Phosphate.
The reaction ratio of phosphoric acid (salt) is the molar ratio of the charge to the zirconium compound, which is 2 or more, preferably 2.05 or more, and more preferably 2.1 or more.
The reaction ratio of phosphoric acid (salt) may be large or excessive with respect to the zirconium compound, but considering the conductivity of the supernatant, the above molar ratio is 3 or less, preferably 2.9 or less, and 2.6. The following is more preferable.

In the production of α-zirconium phosphate, it is preferable to add an oxalic acid compound because the production of the compound becomes faster, the raw material is less wasted, and the compound can be produced efficiently.
Examples of the oxalic acid compound in this case include oxalic acid dihydrate, ammonium oxalate and ammonium hydrogen oxalate, and oxalic acid dihydrate is preferable.
The reaction ratio of oxalic acid is a molar ratio to the zirconium compound of 2.5 to 3.5, more preferably 2.7 to 3.2, and even more preferably 2.8 to 3.0. In the present invention, this ratio is preferable because it facilitates the production of α-zirconium phosphate.

An aqueous solution of a zirconium compound and an aqueous solution containing a phosphoric acid (salt) are mixed and then aged. The aging may be carried out at room temperature, but in order to accelerate the aging, a wet normal pressure of 90 ° C. or higher is used. The condition of exceeding 100 ° C. in a pressure atmosphere higher than the normal pressure is called a hydrothermal condition, and the synthesis may be carried out under this condition. When zirconium α-phosphate is produced under hydrothermal conditions, it is preferable to synthesize it 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 the α-zirconium phosphate can be synthesized. For example, α-zirconium phosphate can be obtained by mixing phosphoric acid (salt) and a zirconium compound to cause precipitation, and then aging. The aging time depends on the aging temperature.
For example, aging at 90 ° C. is preferably 4 hours or more. Even if the aging is carried out for 24 hours or more, the content of zirconium α-phosphate tends to reach a plateau.
The zirconium α-phosphate after synthesis can be obtained by further filtering, washing well with water, and drying to obtain zirconium α-phosphate.

2-2. As the α-titanium α-phosphate used in the present invention, various compounds can be used as long as they have the above-mentioned particle size.
As the titanium α-phosphate used in the present invention, a compound represented by the following formula (2) and having a cation exchange capacity per unit weight of 6.7 meq / g is preferable.
TiH _a (PO ₄ ) _b · nH ₂ O (2)
In equation (2), a and b are positive numbers satisfying 3b−a = 4, b is 2.0 <b ≦ 2.1, and n is a positive number 0 ≦ n ≦ 2.0. ..

The n of α-titanium phosphate in the above formula (2) is preferably 0.2 or less, more preferably 0.1 or less, and further preferably 0.05 or less. By setting the value of n to 2.0 or less, it is possible to prevent water of crystallization from desorbing when the resin is melted during spinning, resulting in foaming and yarn breakage.

Conventional techniques can be applied to the method for producing α-titanium phosphate, and there are no restrictions on raw materials or equipment.
As a method for producing α-titanium phosphate, a method of reacting the raw material compound 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 crystallizing 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, which is aged and crystallized can be mentioned.

Examples of the titanium compound as a raw material for production include titanyl sulfate and the like.
Examples of the phosphoric acid (salt) as a raw material for production include the same compounds as described above.

3. 3. Moisture content in deodorant The water content of the deodorant used in the present invention is preferably 1.0% by weight or less. More preferably, it is 0.7% by weight or less. By setting the water content to 1.0% by weight or less, foaming and hydrolysis of the resin can be prevented during the production of the masterbatch, which is preferable.

4. Deodorant Fiber The present invention is a deodorant for fibers, and as a method for producing a deodorant fiber using the deodorant, a conventional method may be followed.
For example, a method of kneading the deodorant of the present invention into fibers and spinning, a method of applying a deodorant solution to the spun fibers, and the like can be mentioned.

As the resin for fibers that can be used, any known chemical fiber can be used. Preferred specific examples thereof include polyester, polyurethane, nylon, rayon, acrylic, vinylon, polypropylene and the like. These resins may be homopolymers or copolymers. In the case of a copolymer, the polymerization ratio of each copolymer component is not particularly limited.

The deodorant of the present invention can be preferably used as a deodorant for kneading fibers.
Specific examples of the method for producing the deodorant fiber in this case include a method in which the deodorant of the present invention is kneaded into a molten liquid fiber resin or a dissolved fiber resin solution and spun.

The proportion of the deodorant of the present invention contained in the fiber resin is not particularly limited.
Generally, if the content is increased, the deodorizing property can be exerted strongly and can be maintained for a long period of time, but even if the content is increased to a certain extent or more, the deodorizing effect does not make a big difference, or the strength of the resin decreases. Therefore, it is preferably 0.1 to 3.0 parts by weight, and more preferably 0.5 to 2.0 parts by weight per 100 parts by weight of the resin.

Deodorant fibers using the deodorant of the present invention can be used in various fields requiring deodorant properties, such as underwear, stockings, socks, duvets, duvet covers, cushions, blankets, carpets, and curtains. , Sofas, car seats, air filters and nursing clothing, etc., can be used for many textile products.

Next, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. The physical characteristics and deodorizing performance of the deodorant of the present invention were measured by the following methods.

(1) Particle size: Mediane size, maximum particle size, D10 size The particle size of the deodorant was measured with a laser diffraction type particle size distribution measuring device "LA-950" manufactured by Horiba, and the results were analyzed on a volume basis.
As for the measurement conditions, a deodorant dispersion liquid to which 1.0% of deodorant was added to 100% of water was dispersed by ultrasonic waves, and the measurement was performed at a refractive index of 2.4.

(2) Spinnability Test A masterbatch in which 10% of a deodorant was blended with 100% of polyester resin (MA2101M manufactured by Unitika Ltd.) was prepared. Then, this masterbatch was mixed with polyester resin pellets containing no deodorant, and adjusted so as to have each addition amount (% by weight). This was spun using a multifilament spinning machine at a spinning temperature of 275 ° C. and a spinning speed of 500 m / min for 2 hours, and stretched at 120 ° C. so that the elongation was 280 to 320%, and deodorant-containing polyester. Obtained fiber.
At this time, a normal water-soluble oil agent for polyester fiber spinning (Delion 6033 manufactured by Takemoto Oil & Fat Co., Ltd. diluted 10-fold with water) was used as the oil agent.
Spinning was carried out continuously for 2 hours, and the spinnability was evaluated according to the following determination method.
○ ○: Thread break rate is less than 3.0% ○: Thread break rate is 3.0% or more and less than 6.0% Δ: Thread break rate is 6.0% or more and less than 10.0% ×: Thread break rate is 10.0% or more-: Cannot be evaluated

(3) Deodorant test 1
The deodorant test conforms to the deodorant processed textile product certification standard (establisher: Product Certification Department of the Textile Evaluation Technology Council, establishment date: September 1, 2002), and is subjected to the following equipment test. The deodorant property of the odorous component was evaluated. Table 1 shows the acceptance criteria for the reduction rate of each odor component in the instrumental analysis test by the Japan Textile Evaluation Technology Council as "having a deodorizing effect".
〇Detection tube method 1. The drawn yarn produced in (2) above was knitted into a cylinder and subjected to an alkali weight loss treatment (boiling in a 4% sodium hydroxide aqueous solution for 1 hour, bath ratio = 1/40), adjusted to 10 cm x 10 cm, and a tedler bag. I put it in.
2. A predetermined amount of test gas shown in Table 1 is injected, the residual gas concentration (ppm) after 2 hours is measured with a component-compatible detector tube (manufactured by Gastec), the reduction rate of the residual gas concentration is calculated, and deodorization is performed. Notated as a rate. The measurement was performed with an average value of n = 3. The gas filling amount was 3 L, and dry air or nitrogen gas was used as the diluting gas.

(4) Deodorant test 2 (durability test)
After washing the tubular knitted fiber that had been subjected to the alkali weight loss treatment in 1 of (3) above 10 times, the measurement was performed by the detector tube method according to 2 of (3) above.

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

<Examples 1 and 2>
1160 mL of deionized water and 173.4 g of 35% hydrochloric acid were placed in a 2 L round-bottom flask, and 288.4 g of a 20% aqueous solution of zirconium oxychloride containing 0.18% hafnium was added. 2 g was dissolved. 134.4 g of 75% phosphoric acid was added with good stirring of this solution. The temperature was raised to 98 ° C. in 2 hours, and the mixture was stirred and refluxed for 12 hours. After cooling, the obtained precipitate was thoroughly washed with water and then dried at 105 ° C. to obtain zirconium phosphate. This was crushed with a rotor speed mill (16000 rpm, sieve mesh 80 μm). As a result of measuring the obtained zirconium phosphate, it was confirmed that it was α-zirconium phosphate.
When the composition formula of this α-zirconium phosphate was measured, the composition formula was
Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01・ 0.05H ₂ O
The median diameter was 0.51 μm, the maximum particle size was 2.5 μm, and the D10 diameter was 0.22 μm. Details are shown in Table 2.

<Examples 3 and 4>
1056 mL of deionized water and 185.2 g of 35% hydrochloric acid were placed in a 2 L round-bottom flask, 322.7 g of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, and then oxalic acid dihydrate 109. 2 g was dissolved. While stirring the solution well, 160.8 g of 75% phosphoric acid was added. The temperature was raised to 98 ° C. in 2 hours, and the mixture was stirred and refluxed for 12 hours. After cooling, the obtained precipitate was thoroughly 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.
When the composition formula of this α-zirconium phosphate was measured, the composition formula was
Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01・ 0.05H ₂ O
The median diameter was 0.22 μm, the maximum particle size was 2.2 μm, and the D10 diameter was 0.15 μm. Details are shown in Table 2.

<Examples 5 and 6>
228.75 mL of deionized water was placed in a 500 mL round bottom flask, and 202.7 g of 75% phosphoric acid was added. 68.55 g of titanyl sulfate was added while stirring well, and stirring was continued for 10 minutes. Then, the temperature was raised to 100 ° C. in 1 hour, and the mixture was stirred and refluxed for 44 hours. After cooling, the obtained precipitate was thoroughly 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.
When the composition formula of this α-titanium phosphate was measured, the composition formula was
TiH _2.02 (PO ₄ ) _2.01・ 0.05H ₂ O
The median diameter was 0.56 μm, the maximum particle size was 2.6 μm, and the D10 diameter was 0.25 μm. Details are shown in Table 2.

<Examples 7 and 8>
228.75 mL of deionized water was placed in a 500 mL round bottom flask, 202.7 g of 75% phosphoric acid was added, 68.55 g of titanyl sulfate was added with good stirring, and stirring was continued for 10 minutes. Then, the temperature was raised to 85 ° C. in 1 hour, and the mixture was stirred and refluxed for 20 hours. After cooling, the obtained precipitate was thoroughly 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.
When the composition formula of this α-titanium phosphate was measured, the composition formula was
TiH _2.02 (PO ₄ ) _2.01・ 0.05H ₂ O
The median diameter was 0.21 μm, the maximum particle size was 2.2 μm, and the D10 diameter was 0.14 μm. Details are shown in Table 2.

<Examples 9 and 10>
A 1: 1 mixture of zirconium α-phosphate synthesized in Example 1 and titanium α-titanium phosphate synthesized in Example 5 was used as a deodorant.
Table 2 shows the median diameter, maximum particle diameter, and D10 diameter of this mixture.

<Examples 11 and 12>
A 1: 1 mixture of zirconium α-phosphate synthesized in Example 3 and titanium α-titanium phosphate synthesized in Example 7 was used as a deodorant.
Table 2 shows the median diameter, maximum particle diameter, and D10 diameter of this mixture.

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

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

<Comparative Examples 5 and 6>
To 1500 mL of deionized water in a 2 L round bottom flask, 210 g of a 20% aqueous solution of zirconium oxychloride containing 0.18% hafnium was added, and then 240 g of oxalic acid dihydrate was dissolved. 90 g of 75% phosphoric acid was added while stirring the solution well with. This was heated to 98 ° C. in 2 hours and stirred and refluxed for 24 hours. After cooling, the obtained precipitate was thoroughly 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.
When the composition formula of this α-zirconium phosphate was measured, the composition formula was
Zr _0.99 Hf _0.01 H _2.03 (PO ₄ ) _2.01・ 0.05H ₂ O
The median diameter was 2.1 μm, the maximum particle size was 10.0 μm, and the D10 diameter was 0.81 μm. Details are shown in Table 3.

<Comparative Examples 7 and 8>
A zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. was dispersed in water at 10%, 50 wt% of 30 μm zirconia beads were added, and wet pulverized with a disper at 3000 rpm for 2 hours. The median diameter was 0.52 μm, the maximum particle size was 5.1 μm, and the D10 diameter was 0.07 μm. Details are shown in Table 3.

<Comparative Examples 9 and 10>
A zirconium phosphate-based deodorant "Kesmon NS-10" manufactured by Toagosei Co., Ltd. was dispersed in water at 10%, 50 wt% of 10 μm zirconia beads were added, and wet pulverized with a disper at 3000 rpm for 2 hours. The median diameter was 0.2 μm, the maximum particle size was 4.5 μm, and the D10 diameter was 0.05 μm. Details are shown in Table 3.

<Comparative Examples 11 and 12>
228.75 mL of deionized water was placed in a 500 mL round bottom flask, 202.7 g of 75% phosphoric acid was added, 68.55 g of titanyl sulfate was added with good stirring, and stirring was continued for 10 minutes. Then, the temperature was raised to 100 ° C. in 1 hour, and the mixture was stirred and refluxed for 100 hours. After cooling, the obtained precipitate was thoroughly 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.
When the composition formula of this α-titanium phosphate was measured, the composition formula was
TiH _2.02 (PO ₄ ) _2.01・ 0.05H ₂ O
The median diameter was 1.05 μm, the maximum particle size was 5.8 μm, and D10 was 0.51 μm. Details are shown in Table 3.

<Comparative Examples 13 and 14>
Titanium α-phosphate synthesized in Comparative Example 6 was dispersed in water at 10%, 50 wt% of 30 μm zirconia beads were added, and wet pulverization was performed at 3000 rpm at 3000 rpm for 2 hours. The median diameter was 0.49 μm, the maximum particle size was 5.2 m, and D10 was 0.06 μm. Details are shown in Table 3.

<Comparative Examples 15 and 16>
An aluminum dihydrogen trihydrophosphate deodorant "K-FRESH 100P" manufactured by TAYCA CORPORATION was used. The median diameter was 1.1 μm, the maximum particle size was 5.9 μm, and D10 was 0.55 μm. Details are shown in Table 3.

<Reference example>
The deodorant was evaluated by spinning without adding a deodorant and knitting into a cylinder.

The deodorant used in the examples was excellent in spinnability, and there was no concern about yarn breakage. The fiber to which the deodorant of the example was added was excellent in deodorizing performance, and maintained the deodorizing performance even after washing.
On the other hand, the deodorant used in the comparative example did not have good spinnability, deodorant performance, or both. The weight loss rate by alkaline treatment was 13-18% in all samples.

The deodorant of the present invention is excellent in spinnability because it is fine particles and has a narrow particle size distribution. In addition, those kneaded into fibers have excellent ammonia deodorizing performance and high washing resistance.

Claims (8)

Fibers containing zirconium α-phosphate and / or titanium α-titanium phosphate having a median diameter of 0.2 to 0.7 μm, a maximum particle size of 5.0 μm or less, and a D10 diameter of 0.1 μm or more. Deodorant for. The deodorant for fibers according to claim 1, wherein the α-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, and x is a positive number of 0 ≦ x ≦ 0.2. , N is a positive number of 0 ≦ n ≦ 2.0. The deodorant for fibers according to claim 1, wherein the α-titanium phosphate is represented by the following formula (2).
TiH _a (PO ₄ ) _b · nH ₂ O (2)
In equation (2), a and b are positive numbers satisfying 3b−a = 4, b is 2.0 <b ≦ 2.1, and n is a positive number 0 ≦ n ≦ 2.0. .. The deodorant for fibers according to any one of claims 1 to 3, wherein the water content of zirconium α-phosphate and titanium α-phosphate is 1.0% by weight or less. The deodorant for fibers according to any one of claims 1 to 4, wherein zirconium α-phosphate and titanium α-titanium phosphate are synthesized in an aqueous solution. The deodorant for fibers according to any one of claims 1 to 5, which is used for kneading fibers. A deodorant fiber containing at least one of the deodorants for fibers according to claims 1 to 6. The deodorant fiber according to claim 7, wherein the fiber is at least one selected from polyester, polyurethane, nylon, rayon, acrylic, vinylon and polypropylene.