JP2005213682A - Cellulosic fiber carrying nitrogen-containing compound or solvate thereof and having deodorant function - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a warm-colored cellulosic fiber having deodorant function. <P>SOLUTION: The cellulosic fiber having the deodorant function carries a nitrogen-containing compound represented by general formula (I) [wherein, m1, m2, m3 and m4 are each an integer of 1-4; R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each -COO- or -SO<SB>3</SB>-; A is -(CH<SB>2</SB>)<SB>m5</SB>- or -(CH<SB>2</SB>)<SB>m6</SB>-N[-(CH<SB>2</SB>)<SB>m7</SB>-R<SP>5</SP>]-(CH<SB>2</SB>)<SB>m8</SB>- (wherein, m5, m6, m7 and m8 are each an integer of 1-4; and R<SP>5</SP>is -COO- or -SO<SB>3</SB>-); M is a transition metal; p is 2 or 3; q is an integer of 1-3; r is an integer of 0-2; L is NH<SB>4</SB>or Na; with the proviso that when A is -(CH<SB>2</SB>)<SB>m5</SB>-, p+q+r is 4, and when A is -(CH<SB>2</SB>)<SB>m6</SB>-N[-(CH<SB>2</SB>)<SB>m7</SB>-R<SP>5</SP>]-(CH<SB>2</SB>)<SB>m8</SB>-, p+q+r is 5] or a solvate thereof. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cellulosic fiber having a deodorizing function in which a nitrogen-containing compound or a solvate thereof is supported.

  Conventionally, as a cellulosic fiber having a deodorizing function, a fiber in which a phthalocyanine compound is supported on the fiber (see Patent Document 1) has been known. Since the phthalocyanine compound or the like is also a dye, the supported cellulosic fiber was dyed in a dark blue cold color.

  There is no problem if this dark blue cold color is used as it is, but for use in products such as bedding, clothing and interior goods, colors other than cold, that is, warm colors are often preferred. It was difficult to develop a variety of textile products.

Such a cold-colored cellulosic fiber can be easily made into a multipurpose product by dyeing and re-dying. However, since the dyeing process is required, there is a problem that the process of manufacturing the fiber product becomes complicated.
JP-A 64-68578

  An object of this invention is to provide the cellulosic fiber which has a deodorizing function and has a warm color.

  As a result of diligent research, the present inventors have found that a cellulosic fiber carrying a nitrogen-containing compound or a solvate thereof has a deodorizing function and has a warm color of orange to skin color to bright yellow. The present invention has been reached.

  The present invention is a cellulosic fiber having a deodorizing function in which a nitrogen-containing compound represented by the following general formula (I) (hereinafter referred to as nitrogen-containing compound (I)) or a solvate thereof is supported.

In the above formula, m1, m2, m3 and m4 may be the same or different and are integers of 1 to 4,
R ¹ , R ² , R ³ and R ⁴ may be the same or different and are —COO ^— or —SO ₃ ^— groups;
A represents a group represented by — (CH ₂ ) _m5 — or — (CH ₂ ) _m6 —N [— (CH ₂ ) _m7 —R ⁵ ] — (CH ₂ ) _m8 — (where m5, m6, m7 and m8 may be the same or different and each represents an integer of 1 to 4, and R ⁵ is a —COO 2 ^— or —SO ₃ ^— group.
M is a transition metal,
p is 2 or 3, q is an integer of 1 to 3, r is an integer of 0 to 2,
L is NH ₄ or Na;
However, when A is a group represented by — (CH ₂ ) _m5 —, p + q + r = 4,
A is _{- (CH 2) m6 -N [} - (CH 2) m7 -R 5] - (CH 2) m8 - when a group represented by a p + q + r = 5.

  The cellulosic fiber of the present invention has a deodorizing function and has a warm color.

  As described above, the present invention is a cellulosic fiber having a deodorizing function in which the nitrogen-containing compound (I) or a solvate thereof is supported. Since the cellulosic fiber of the present invention has a warm color of orange to skin color to bright yellow, it is possible to omit the step of dyeing with a commonly used synthetic dye such as an aromatic compound when processing into a fiber product. Therefore, since it can suppress generation | occurrence | production of dioxins when it burns, it is preferable.

  In the cellulosic fiber, the supported amount of the nitrogen-containing compound (I) or a solvate thereof is preferably 0.1% by mass or more and 10% by mass or less, more preferably based on the weight of the cellulosic fiber. 1 mass% or more and 5 mass% or less. If the amount of the nitrogen-containing compound (I) or a solvate thereof is 0.1% by mass or more, the deodorizing function is excellent.

  Examples of the cellulose fibers include known cellulose fibers such as natural cellulose fibers such as cotton and hemp, and regenerated cellulose fibers such as rayon.

  Examples of the solvate of the nitrogen-containing compound (I) include a solvate of water or an organic solvent and the nitrogen-containing compound (I). Examples of the organic solvent include lower alcohols such as methanol and ethanol.

In the nitrogen-containing compound (I) or a solvate thereof, in the formula (I), R ¹ , R ² , R ³ and R ⁴ are preferably a —COO 2 ^— group. The nitrogen-containing compound (I) or a solvate thereof preferably has 1 in m1, m2, m3 and m4 in the formula (I). Examples of the transition metal include elements from groups 3 to 12 (groups 1A to 1B) of the periodic table, and among them, elements of the first transition element series are preferable. Among the elements of the first transition element series, Fe, Cr, Mn and Co are preferable.

When the transition metal is Fe, the nitrogen-containing compound (I) or a solvate thereof is a group in which A is represented by — (CH ₂ ) _m5 — in the formula (I), and p is 3 Preferably, q is 1 and r is 0. In the nitrogen-containing compound (I) or a solvate thereof, m5 is more preferably 2 or 3 in the formula (I). Alternatively, when the transition metal is Fe, the nitrogen-containing compound (I) or a solvate thereof is the same as the formula (I) in which A is — (CH ₂ ) _m6 —N [— (CH ₂ ) _m7 — R ⁵ ] — (CH ₂ ) _m8 —, preferably p is 3, q is 1, and r is 1. In the nitrogen-containing compound (I) or a solvate thereof, in the formula (I), m6, m7 and m8 are 1, and R is more preferably a —COO 2 ^— group. In the nitrogen-containing compound (I) or a solvate thereof, in the formula (I), L is more preferably NH ₄ .

  Such a nitrogen-containing compound (I) is preferably ethylenediaminetetraacetic acid iron ammonium, ethylenediaminetetraacetic acid iron sodium salt, diethylenetriaminepentaacetic acid iron diammonium salt or 1,3-diaminopropanetetraacetic acid iron ammonium salt.

When the transition metal is Cr, Mn or Co, the nitrogen-containing compound (I) or a solvate thereof is a group in which A is represented by — (CH ₂ ) _m5 — in the formula (I). , P is 2, q is 2, and r is preferably 0. In the nitrogen-containing compound (I) or a solvate thereof, m5 is more preferably 2 or 3 in the formula (I). Alternatively, when the transition metal is Cr, Mn, or Co, the nitrogen-containing compound (I) or a solvate thereof is represented by the following formula (I), wherein A is — (CH ₂ ) _m6 —N [— (CH ^{_{2) m7 -R 5] - (}} CH 2) m8 - with a group represented, p is 2, q is 2, r is preferably 1. In the nitrogen-containing compound (I) or a solvate thereof, in the formula (I), m6, m7 and m8 are 1, and R is more preferably a —COO 2 ^— group. In the nitrogen-containing compound (I) or a solvate thereof, L is more preferably NH ₄ in the formula (I).

The nitrogen-containing compound (I) or a solvate thereof can be purchased commercially, but can also be produced by a conventionally known method.

  Cellulosic fibers having a deodorizing function on which the nitrogen-containing compound (I) of the present invention or a solvate thereof is supported can be produced, for example, by the following method.

  First, by treating the cellulosic fiber with a cationizing agent having a reactive group directly bonded to the hydroxyl group of cellulose in the presence of alkali, and then treating with the nitrogen-containing compound (I) or a solvate thereof. Cellulosic fibers carrying the nitrogen-containing compound (I) or a solvate thereof can be produced.

  Examples of the cationizing agent having a reactive group directly bonded to the hydroxyl group of cellulose in the production method of the present invention include a quaternary ammonium salt type chlorohydrin derivative, a quaternary ammonium salt type polymer, and a cationic polymer. , Cross-link type polyalkylimine, polyamine type cationic resin, glyoxal type fiber reaction type resin and the like. Examples of the quaternary ammonium salt type chlorohydrin derivative include compounds represented by the following general formula (II) and general formula (III).

In the formulas (II) and (III), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different, and are lower alkyl groups having 1 to 4 carbon atoms, and n is 2 to 6 It is an integer and X is a halogen atom.

In the formula (II), R ¹¹ , R ¹² and R ¹³ are preferably CH ₃ , and X is preferably Cl. Specific examples of the compound represented by the general formula (II) include cationone CT (trade name) (manufactured by Yushi Kogyo Co., Ltd.) and the like. In the formula (III), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably methyl groups and X is preferably Cl. Specific examples of the compound represented by the general formula (III) include Cationone UK (trade name) (manufactured by Yushi Kogyo Co., Ltd.).

  Examples of the quaternary ammonium salt type polymer include compounds represented by the formula (IV).

  In the formula (IV), X is a halogen atom. In the formula (IV), X is preferably Cl. Specific examples of the compound represented by the general formula (IV) include Dunshade 185 (trade name) (manufactured by Nittobo).

  Examples of the cationic polymer include polyvinylamine. Examples of the crosslink type polyalkylimine include polyethyleneimine. Examples of the polyamine-based cation resin include polystyrene tetramethylammonium chloride. Examples of the glyoxal fiber-reactive resin include dimethylol dihydroxyethylene urea. Of these, quaternary ammonium salt type chlorohydrin derivatives are preferred. The cationizing agents can be used alone or in combination of two or more.

  The treatment of the cellulosic fiber with the cationizing agent in the presence of an alkali is performed by, for example, mixing the cellulosic fiber with an aqueous mixture of the cationizing agent and an alkali such as anhydrous sodium carbonate (soda ash) or sodium hydroxide. The treatment can be performed at a temperature of about 100 ° C. to 100 ° C. for 10 minutes to 1 hour. The amount of the cationizing agent is preferably about 1 g / liter to 100 g / liter. The cellulosic fibers are preferably scoured in advance as a pretreatment using an Overmeier dyeing machine, a cheese dyeing machine, or the like.

  After the treatment with the cationizing agent, the cellulosic fiber is preferably neutralized by treatment with an aqueous solution of an acid such as acetic acid at a temperature of about 30 ° C. to 60 ° C. for 5 minutes to 1 hour. After the neutralization treatment, the cellulose fibers are preferably washed, dehydrated and dried.

  Next, as described above, by treating the cellulosic fiber with the nitrogen-containing compound (I) or a solvate thereof, the cellulosic fiber carrying the nitrogen-containing compound (I) or a solvate thereof. Can be manufactured. The treatment is performed by treating the cellulosic fiber with an aqueous solution of the nitrogen-containing compound (I) or a solvate thereof at a temperature of about 30 ° C. to 100 ° C. for 10 minutes to 1 hour. be able to.

  As the nitrogen-containing compound (I) or a solvate thereof, those described above can be used. The amount of the nitrogen-containing compound (I) or a solvate thereof used in the treatment is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% with respect to the cellulose fiber. It is about mass% or less. After the treatment, the cellulose fibers are preferably washed, dehydrated and dried.

  The present invention is a fiber product including a cellulosic fiber having a deodorizing function on which the nitrogen-containing compound (I) or a solvate thereof is supported. Examples of the textile products include intermediate textile products such as spun yarn, woven and knitted fabric, nonwoven fabric, and paper, bedding products such as futons, blankets, and sheets, underwear, shirts, pants, outer garments, hats, socks, and the like. Clothing products such as gloves, interior products such as curtains, tablecloths, cushions, stuffed animals and carpets, industrial material products such as masks, filters, dust bags, artificial leather and car interior materials, towels, Living items such as towels, tissue paper, wipers for home use, kitchen sheets, decorative sheets, closet / tass sheets, clothes covers, futon bags, mats, sandals, bandages, diapers, napkins, insoles, wrapping paper, etc. Final fiber product. These fiber products may be used alone or in combination with other fibers, depending on the application, and may be used in combination with other fiber products. The cellulosic fibers are preferably contained in an amount of 20% by mass or more, more preferably 50% by mass in order to develop a deodorizing function.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not limited to a following example. In addition, the loading amount of the nitrogen-containing compound (I) or its solvate in the examples and the loading amount of the phthalocyanine in the reference example were calculated by the following equations.

Regular rayon staple cotton (manufactured by Daiwabo Rayon Co., Ltd.) was scoured (washed at 60 ° C.) with an overmeier dyeing machine. Thereafter, with respect to the cotton, a bath ratio of 1:10, 2 cc / liter of clean N-15 (trade name) (manufactured by Yushi Kogyo Co., Ltd., penetrant), 30 g / liter of Kathionon UK (trade name) (On the other hand, manufactured by Yushi Kogyo Co., Ltd., in the above formula (III), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are methyl groups and X is Cl, a cationizing agent) and 9 g / liter of hydroxylation A cationization solution containing sodium was prepared. The cotton and the cationization solution were treated at 80 ° C. for 40 minutes for cationization. Thereafter, the mixture was neutralized with a 1 cc / liter acetic acid aqueous solution at 30 ° C. for 10 minutes.

Next, the cotton was washed with water. The bath ratio is 1:10 with respect to the cotton, and 2.5% by mass of Kirest FNZ (trade name) (made by Kirest Co., Ltd., containing 98% by mass of the compound of the formula (I). The compound is a monohydrate. And in formula (I), m1, m2, m3 and m4 are 1, R ¹ , R ² , R ³ and R ⁴ are —COO 2 ^— groups, and A is —CH _{2 -N [-CH 2 -COOH] -CH 2} - is a group represented by, M is Fe, p is 3, q is 1, r is 1), the cotton Was treated at 0 ° C. for 20 minutes. Next, the cotton was washed with water and dried to obtain cellulosic fibers carrying 2% by mass of the nitrogen-containing compound (I) of the present invention or a solvate thereof. The obtained cellulosic fiber can be used as a deodorizing cotton filling such as a futon, a cushion, and a stuffed animal, or as a raw cotton for a deodorizing nonwoven fabric and a deodorizing paper. In addition, by using the deodorant non-woven fabric, paper, etc., the industrial material products such as masks, filters, artificial leather, etc., and the deodorant fiber products as the daily necessities such as wipers, gauze can be obtained.

  20s cotton yarn (manufactured by Daiwabo Co., Ltd.) was scoured and bleached with a cheese dyeing machine. The scouring bleaching treatment is carried out in a mixture of 4 g / liter of caustic soda aqueous solution, 5 cc / liter of hydrogen peroxide solution and 0.25 cc / liter of clean N-15 (trade name) (manufactured by Yushi Kogyo Co., Ltd.) The treatment was performed at 80 ° C. for 30 minutes. Thereafter, the cotton yarn is washed with water, and then a 10 g / liter Dunshade 185 (trade name) (manufactured by Nitto Boseki Co., Ltd., formula (IV), with X = Cl at a bath ratio of 1:20 with respect to the cotton yarn. And a cationization solution of 10 g / liter soda ash. The 20s cotton yarn was treated with the cationization solution at 60 ° C. for 30 minutes for cationization. Thereafter, the mixture was neutralized with a 1 cc / liter acetic acid aqueous solution at 30 ° C. for 10 minutes.

Next, the cotton yarn was washed with water. Clewat FeH (trade name) with a bath ratio of 1:20 with respect to the cotton yarn (produced by Nagase ChemteX Corporation, containing 30% by mass of the compound of the formula (I). , M1, m2, m3 and m4 are 1, R ¹ , R ² , R ³ and R ⁴ are —COO 2 ^— groups, and A is a group represented by —CH ₂ CH ₂ —. , M is Fe, p is 3, q is 1 and r is 0), and the cotton yarn was treated at 80 ° C. for 20 minutes. Next, the cotton yarn was washed with water and dried to obtain a cotton yarn carrying 4% by mass of the nitrogen-containing compound (I) of the present invention or a solvate thereof. The obtained cotton yarn is used as a raw material for deodorant knitted fabrics and woven fabrics, and as a raw fabric for the obtained deodorant woven and knitted fabrics. Deodorant fiber products can be obtained as the interior products such as clothing products, curtains and carpets.

(Reference example)
A rayon staple having a primary swelling degree of about 240% and a length of 31 m / m was immersed in an aqueous solution of cobalt phthalocyanine / polysulfonic acid (aqueous solution concentration: 0.2 g / liter) at 80 ° C. for 30 minutes. Thereafter, the staple was dehydrated and dried to obtain a rayon staple carrying about 2% by mass of cobalt phthalocyanine / polysulfonic acid.

(Evaluation)
1. LAB color system A sample was measured with a spectrocolorimeter, and the color difference was shown in a Lab color system chromaticity diagram (JIS Z8729). As a sample, the cellulosic fibers of Example 1 and Reference Example were used. The results are shown in Table 1 below.

  As shown in Table 1, the cellulosic fiber of the reference example was a dark blue cold color, but the cellulosic fiber carrying the nitrogen-containing compound (I) of the present invention or a solvate thereof was a warm skin color. Met.

2. Deodorizing performance test 1 g of a sample was placed in a 5-liter Tedlar bag, and a gas having a predetermined concentration was injected. After deaeration, the operation of injecting gas was repeated. After 24 hours, the gas concentration in the bag was measured with a gas detector tube. The deodorizing performance was calculated as a gas removal amount (g / g). As a sample, the cellulosic fibers of Example 1 and Reference Example were used. As the gas, ammonia, methyl mercaptan and trimethylamine were used. The predetermined concentration is 250 ppm for ammonia, 35 ppm for methyl mercaptan, and 85 ppm for trimethylamine. The results are shown in Table 2 below.

  As shown in Table 2, the cellulosic fiber carrying the nitrogen-containing compound (I) of the present invention or a solvate thereof has a deodorizing function equivalent to a conventional cellulosic fiber having a deodorizing function. Was confirmed.

3. Deodorant life test 1 g of a sample was placed in a 5 liter Tedlar bag, and hydrogen sulfide gas having a concentration of 850 ppm was injected. The gas concentration in the bag was measured with a gas detector tube over time. After deaeration, the operation of injecting gas was repeated. The deodorizing performance was calculated as a gas removal amount (g / g). As a sample, the cellulosic fibers of Example 1 and Reference Example were used. The results are shown in Table 3 below.

  As shown in Table 3, the cellulosic fiber carrying the nitrogen-containing compound (I) of the present invention or a solvate thereof has a deodorizing life equivalent to that of a conventional cellulosic fiber having a deodorizing function. Was confirmed.

4). Washing fastness test The sample was washed 10 times continuously with Akron (trade name) (manufactured by Lion Corporation, neutral detergent) or Top (trade name) (trade name, manufactured by Lion Corporation, alkaline detergent). The washing treatment was performed according to JIS L0217 (1976) No. 103. The laundered sample was subjected to the following deodorization performance test.

Deodorizing performance test 1 g of a sample was placed in a 5 liter Tedlar bag, and 250 ppm of ammonia gas was injected. After deaeration, the operation of injecting gas was repeated. After 24 hours, the gas concentration in the bag was measured with a gas detector tube. The deodorizing performance was calculated as a gas removal amount (g / g).

  The cellulosic fiber of Example 1 was used as a sample. A sample not subjected to the washing treatment was used as a control. The results of the test are shown in Table 4 below.

  As shown in Table 4, it was confirmed that the cellulosic fiber carrying the nitrogen-containing compound (I) of the present invention or a solvate thereof had high washing fastness.

5). Skin irritation test The skin irritation test was carried out in accordance with the Kawai method described in “Kawai method (a method for determining a sticking test by microscopic observation)” (1988, second edition, edited by Japan Industrial Skin Hygiene Association). Specifically, a sample having a size of 1.5 cm ² was placed on the inner side of the upper arm portion, pressed from two galvanic gauze pieces having a size of 2 cm ² from the top, and stuck and fixed with a paper bandage. 24 hours after application, the sample is removed and the skin of the upper arm is observed with the naked eye. If erythema, edema, or papules that can be observed with the naked eye occurred on the skin, it was determined as D-stage. For other skins, a replica specimen of the skin at the application site was created by the sump method. The specimen was determined for each stimulation rank under a microscope, and the difference obtained by subtracting the control stimulation index from the test body stimulation index of 20 subjects was used as the determination result. Examples of the stimulation rank include A-stage, B-stage, and C-stage. For example, if it is a triangular cuticle surrounded by a straight skin groove with a clear skin pattern, it is determined as an A-stage. If the skin of the A-stage is deepened due to edema (recessed skin groove), it is determined as the B-stage. In addition, the edema progresses, and the skin groove becomes shallower and disappears, or the continuity of the skin groove is damaged, due to irregular skin prickly skin, a kind of skin degreasing, dehydration, crustum, and delamination of the stratum corneum If filmy scales are generated, it is determined as the C-stage. Individual differences in panel group responses can be eliminated by the use of control samples that have been confirmed to be safe. There are four criteria, negative, quasi-negative, quasi-positive and positive. This was determined from the results of a follow-up survey on the correlation between the judgment results and post-marketing dermatitis-like claims. For example, it is positive if there are one or more D-stages, and it is positive even if there are one or more C-stages. In the case of the B-stage, if the difference number of (test body stimulation index) − (control stimulation index) is 4 or more, it is positive. If the difference is 3, it is quasi-positive, 1 or 2 is quasi-negative, and 0 or less is negative.

  When tested in the skin irritation test, the determination result was negative, and the cellulosic fiber of Example 1 was not irritating.

  From the test results, the cellulosic fiber of the present invention was excellent in deodorizing performance and washing fastness, and had a skin color (warm color) that felt warm.

  As described above, the cellulosic fiber of the present invention can be applied to intermediate fiber products such as spun yarn, woven and knitted fabric, non-woven fabric, and paper, and final fiber products such as bedding, clothing, interior goods, daily necessities, and industrial materials. .

Claims (14)

A cellulosic fiber having a deodorizing function on which a nitrogen-containing compound represented by the following general formula (I) or a solvate thereof is supported.

In the above formula, m1, m2, m3 and m4 may be the same or different and are integers of 1 to 4,
R ¹ , R ² , R ³ and R ⁴ may be the same or different and are —COO ^— or —SO ₃ ^— groups;
A represents a group represented by — (CH ₂ ) _m5 — or — (CH ₂ ) _m6 —N [— (CH ₂ ) _m7 —R ⁵ ] — (CH ₂ ) _m8 — (where m5, m6, m7 and m8 may be the same or different and each represents an integer of 1 to 4, and R ⁵ is a —COO 2 ^— or —SO ₃ ^— group.
M is a transition metal,
p is 2 or 3, q is an integer of 1 to 3, r is an integer of 0 to 2,
L is NH ₄ or Na;
However, when A is a group represented by — (CH ₂ ) _m5 —, p + q + r = 4,
A is _{- (CH 2) m6 -N [} - (CH 2) m7 -R 5] - (CH 2) m8 - when a group represented by a p + q + r = 5.   The cellulose according to claim 1, wherein the amount of the nitrogen-containing compound represented by the formula (I) or the solvate thereof supported is 0.1% by mass or more and 10% by mass or less based on the weight of the cellulosic fiber. Fiber. The cellulosic fiber according to claim 1 or 2, wherein R ¹ , R ² , R ³ and R ⁴ are -COO ^- groups.   The cellulosic fiber according to any one of claims 1 to 3, wherein m1, m2, m3 and m4 are 1.   The cellulosic fiber according to any one of claims 1 to 4, wherein the transition metal is Fe, Cr, Mn, or Co.   The cellulosic fiber according to claim 5, wherein the transition metal is Fe. The cellulosic fiber according to claim 6, wherein A is a group represented by — (CH ₂ ) _m5 —, p is 3, q is 1, and r is 0. A is _{- (CH 2) m6 -N [} - (CH 2) m7 -R 5] - (CH 2) m8 - with a group represented, p is 3, q is 1, r is The cellulosic fiber according to claim 6, which is 1.   The nitrogen-containing compound represented by the general formula (I) is ethylenediaminetetraacetic acid iron ammonium, ethylenediaminetetraacetic acid iron sodium salt, diethylenetriaminepentaacetic acid diammonium salt or 1,3-diaminopropanetetraacetic acid iron ammonium salt. Cellulosic fiber in any one.   The cellulosic fiber according to claim 5, wherein the transition metal is Cr, Mn or Co. A is - (CH _{2) m5} - In a group represented, p is 2, q is 2, cellulosic fibers according to claim 10 r is 0. A is a group represented by — (CH ₂ ) _m6 —N [— (CH ₂ ) _m7 —R ⁵ ] — (CH ₂ ) _m8 —, p is 2, q is 2, and r is The cellulosic fiber according to claim 10, which is 1. A step of treating a cellulosic fiber with a cationizing agent having a reactive group directly bonded to a hydroxyl group of cellulose in the presence of an alkali, and a general formula (I):

[Wherein, m1, m2, m3 and m4 may be the same or different and are integers of 1 to 4,
R ¹ , R ² , R ³ and R ⁴ may be the same or different and are —COO ^— or —SO ₃ ^— groups;
A represents a group represented by — (CH ₂ ) _m5 — or — (CH ₂ ) _m6 —N [— (CH ₂ ) _m7 —R ⁵ ] — (CH ₂ ) _m8 — (where m5, m6, m7 and m8 may be the same or different and each represents an integer of 1 to 4, and R ⁵ is a —COO 2 ^— or —SO ₃ ^— group.
M is a transition metal,
p is 2 or 3, q is an integer of 1 to 3, r is an integer of 0 to 2,
L is NH ₄ or Na;
However, when A is a group represented by — (CH ₂ ) _m5 —, p + q + r = 4,
When A is a group represented by — (CH ₂ ) _m6 —N [— (CH ₂ ) _m7 —R ⁵ ] — (CH ₂ ) _m8 —, p + q + r = 5]
A step of treating with a nitrogen-containing compound or a solvate thereof,
A method for producing a cellulosic fiber having a deodorizing function in which a nitrogen-containing compound represented by the general formula (I) or a solvate thereof is supported.   A fiber product comprising the cellulosic fiber according to any one of claims 1 to 12.