JPH0874131A - Deodorant fiber, manufacturing method thereof and deodorant fiber product using the same - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To have excellent deodorizing performance against malodor of a compound containing a malodorous carbonyl group such as cigarette or an acidic compound, and further to malodor of a basic compound. (EN) Provided are an easy-to-use deodorant fiber which is excellent in safety, processability, washing durability and dyeability, a method for producing the deodorant fiber, and a deodorant fiber product using the same. SOLUTION: The content of amino group per unit of monomer is 1 to 2 equivalents, and the degree of polymerization is 7 or more.
The following water-soluble polyamine compound was contained in the fiber after coagulation of the acrylic synthetic fiber obtained by the wet spinning method and before drying, in an amount of 0.1% owf or more and 10% owf or less.
0.01 mol / kg or more of acidic groups per fiber, 2.5
5% by weight of acrylic synthetic fiber containing less than mol / kg
Above, 0.2 equivalents / kg or more and 10 equivalents / kg or less anionic functional group or a transition in which the anionic functional group is bound to 0.1 equivalent / kg or more and 5 equivalent / kg or less transition metal A deodorant fiber product is obtained by containing 0.1% by weight or more of a fiber containing a metal salt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant fiber, a method for producing the same, and a deodorant fiber product using the same, and more particularly to deodorizing odors of compounds containing a carbonyl group, acidic compounds, basic compounds and the like. The present invention relates to a deodorant fiber having a function to perform, a method for producing the same, and a deodorant fiber product using the same.

[0002]

2. Description of the Related Art In recent years, interest in comfort in a living environment has increased, and various proposals have been made for removing a bad odor existing in a room, a refrigerator, a car, or various environments. In particular, deodorization of cigarette odors in offices, homes, or automobiles has been highlighted as the smoking cessation movement has become popular.

By the way, most of the conventional deodorizing and deodorizing technologies are mainly those using activated carbon or those using a filter for positively sucking and deodorizing malodorous components.
For example, as a filter for removing various malodorous components generated in the living environment, an air cleaning filter in which a plurality of types of carriers impregnated with deodorant effective components having different target odors are combined is disclosed (Japanese Patent Publication No. 02-22673). ). Further, as a filter for removing aldehyde, a filter obtained by coating a tobacco filter with a treatment solution containing polyethyleneimine and carboxylic acid is known (Japanese Patent Laid-Open No. 02-257).
870).

However, in all of these techniques, the deodorant component is adhered to the surface of the fiber by simply impregnating or coating the carrier with the deodorant, so that the texture of the textile product is hard and the laundry is washed. As a result, the deodorant component is easily removed, and application to the clothing field or interior field where washing durability or fashionability is required was impossible.

Further, a deodorant using an amine compound has also been proposed. For example, polyethyleneimine is disclosed in JP-A-3-146064 as a deodorant material containing a nonionic water-absorbing organic substance, but the one proposed by this proposal has a sufficiently satisfactory wash durability and processability. I couldn't say that there was. Further, a material for a cigarette smoking filter in which a reactive group is introduced into a cellulose molecule to react polyethyleneimine is disclosed in JP-A-57-16687. Since it could not be made uniform, the reacted polyethyleneimine was unevenly distributed and polyethyleneimine was likely to fall off. Further, there is disclosed a deodorant acrylic synthetic fiber in which a metal porphyrin having an amino group introduced into a swollen gel fiber at the stage of producing an acrylic fiber is dried and densified for the purpose of improving washing durability and a method for producing the same. As disclosed in Japanese Patent Laid-Open Publication No. JP-A No. 2003-187, although the proposal according to this proposal is at a satisfactory level in washing durability, it cannot be said to be at a sufficiently satisfactory level in dyeing durability. Dyeing durability refers to the performance retention rate when an adhered material on a fiber is peeled off by a strong thermodynamic action due to heat, and shows the loss of a bonded material due to a physically adsorbed material or an ionic bond. Is. Therefore, maintaining deodorant performance against malodorous substances after dyeing has been treated as a very difficult problem. In addition, in the method of using a metal porphyrin having an amino group introduced into the fiber or an amine-based compound, the compound having a carbonyl group and the acidic compound can be deodorized,
It was not possible to deodorize the basic compound, and it was not possible to sufficiently achieve the deodorization of the bad odor including the compound having a carbonyl group, the acidic compound and the basic compound, such as tobacco odor.

[0006]

DISCLOSURE OF THE INVENTION The present invention shows an excellent adsorption performance for a malodor containing a carbonyl group-containing compound such as a tobacco odor, an acidic compound and a basic compound, and moreover has an easy handling property. It is an object of the present invention to provide a deodorant fiber which is easy and has good safety, processability and washing durability as well as good dyeing durability, a method for producing the deodorant fiber, and a deodorant fiber product using the same.

[0007]

The present inventors have found that the object of the present invention can be achieved by the following constitution, and have completed the present invention. That is, the invention claimed in the present application is as follows. (1) After coagulating an acrylic synthetic fiber obtained by a wet spinning method with a water-soluble polyamine compound having an amino group content of 1 equivalent to 2 equivalents per monomer unit and a polymerization degree of 7 or more and 2400 or less, 0.1 to the fiber before drying
% Owf or more, 10% owf or less, acidic group per fiber is 0.01 mol / kg or more, 2.5 mol / kg
5% by weight or more of acrylic synthetic fiber containing not more than kg,
0.2 equivalent / kg or more and 10 equivalent / kg or less anionic functional group or 0.1 equivalent / kg of the anionic functional group
The deodorant fiber product is characterized by containing 0.1% by weight or more of a fiber containing a transition metal salt bound to 5 equivalents / kg or less of a transition metal.

(2) After coagulation of the acrylic synthetic fiber obtained by the wet spinning method and before drying, the content of amino groups per unit of monomer in the fiber is 1 to 2 equivalents,
A water-soluble polyamine compound having a degree of polymerization of 7 or more and 2400 or less is uniformly attached, and the obtained fiber is heated to 100 ° C. or more 18
A method for producing a deodorant fiber, which comprises treating the acidic group in the fiber with a water-soluble polyamine compound in a wet heat treatment by treating with steam at 0 ° C or lower.

(3) The deodorant fiber as described in (2), wherein the bonding ratio between the acidic groups of the acrylic synthetic fiber and the amino groups of the water-soluble polyamine compound is 50 mol% or more and 100 mol% or less. (4) 0.2 equivalents / kg or more and 10 equivalents / kg or less anionic functional group or a transition in which the anionic functional group is bound to 0.1 equivalent / kg or more and 5 equivalent / kg or less transition metal A deodorant fiber containing a transition metal salt containing an anionic functional group or a transition metal bound to a transition metal, which contains a metal salt.

(5) In (4), the fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bonded to a transition metal is an acrylic synthetic fiber, which is anionic before fiber formation. A deodorant fiber obtained by copolymerizing a monomer having an ionic functional group, or an anionic functional group-containing fiber thus obtained is treated with an alkaline aqueous solution containing a salt having a monovalent cation as a counterion. Deodorized fiber treated with a transition metal compound after treatment.

(6) In (4), the fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bonded to a transition metal is a monomer having an anionic functional group after fiber formation. The deodorant fiber obtained by graft polymerization, or the anionic functional group-containing fiber thus obtained is treated with an aqueous alkaline solution containing a salt having a monovalent cation as a counterion, and then treated with a transition metal compound. Deodorized fiber reacted.

(7) In (4), a fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bound to a transition metal is an acrylic synthetic fiber or a regenerated cellulose fiber in a wet spinning method. In the deodorizing fiber obtained by applying a polymer having an anionic functional group after coagulation and before drying, or a fiber containing an anionic functional group thus obtained, a monovalent cation is used as a counter ion. Deodorant fiber treated with a transition metal compound after being treated with an alkaline aqueous solution containing a salt.

(8) In (4), a fiber containing an anionic functional group or a transition metal salt in which the ionic functional group is bound to a transition metal is a polymer having an anionic functional group before fiber formation. The deodorant fiber obtained by polymer blending, or the anionic functional group-containing fiber thus obtained is treated with an alkaline aqueous solution containing a salt having a monovalent cation as a counterion, and then treated with a transition metal compound. Deodorized fiber reacted.

(9) In (4), the fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bonded to a transition metal is an acrylic synthetic fiber which is hydrolyzed in the presence of an alkali. After treating the deodorant fiber introduced with an anionic functional group by decomposition, or the fiber containing an anionic functional group thus obtained with an alkaline aqueous solution containing a salt having a monovalent cation as a counter ion, Deodorant fiber reacted with a transition metal compound.

The present invention will be described in more detail below. In the present invention, as the water-soluble polyamine compound, one or more polymers containing an amino group such as polyethyleneimine, polyallylamine, and amino-modified acrylic polymer are used, and the content of amino group per one unit of the monomer is used. The amount is 1 equivalent to 2 equivalents. Outside this range, it is difficult to achieve the object of the present invention.

The water-soluble polyamine compound having an amino group content of 1 to 2 equivalents per unit of monomer preferably has a degree of polymerization of 7 or more and 2400 or less. Yes 2400
If it exceeds, the viscosity is too high and it is difficult to handle, which is not preferable. Content of the water-soluble polyamine compound is 0.1%
It is preferably owf or more and 10% owf or less, more preferably 0.5% owf or more and 5% owf or less. When the content of the water-soluble polyamine compound is less than 0.1% owf, the deodorizing effect of acetaldehyde is weak, and when it exceeds 10% owf, the fiber is cured, which is not preferable. Content of water-soluble polyamine compound is 0.5% owf or more, 5% ow
When it is at most f, the acetaldehyde deodorizing effect will be strong and the fibers will not be cured.

The acrylic synthetic fiber according to the present invention is prepared by spinning a stock solution for spinning through a spinneret into a coagulating bath, washing with water, and then stretching in boiling water to obtain a water-soluble polyamine compound having an amino group in the obtained undried fiber. It is immersed in an aqueous solution containing water, dehydrated, dried, and then heat-treated under pressure with steam to wet-bond the water-soluble polyamine compound containing an acidic group and an amino group in the acrylic synthetic fiber. A deodorant fiber having an improved binding rate and better washing durability and dyeing durability can be obtained. The acidic group content of the acrylic synthetic fiber is 0.01 mol / kg or more per fiber,
2.5 mol / kg or less, preferably 0.03 m
It is ol / kg or more and 2.0 mol / kg or less. The moist heat bond in the present invention is a bond formed under moist heat, and it is preferably treated with pressurized steam at a temperature of 100 ° C. or higher and 180 ° C. or lower, and particularly preferably treated with pressurized steam at a temperature of 105 ° C. or higher and 130 ° C. or lower. Preferably.

The water-soluble polyamine compound of the present invention has a binding rate of amino groups and acidic groups of 50 mol% or more and 100 mol.
% Or less, particularly preferably 60 mol% or more and 100 mol% or less. Next, the anionic functional group in the present invention refers to a carboxyl group or a sulfone group, and the content is 0.2 equivalent / kg fiber or more and 10 equivalent /
Less than or equal to kg fiber is required, and 0.4 equivalent / kg
Fibers or more and 5 equivalents / kg or less of fibers are preferable. If the amount of the anionic functional group is less than 0.2 equivalent / kg fiber, the deodorizing effect is small, and if it exceeds 10 equivalent / kg fiber, the moisture absorption and water absorption of the fiber itself become too high and the morphological stability during washing is high. Also, it is not preferable because the durability is deteriorated and the texture after washing is hardened. When the content is 0.4 equivalent / kg fiber or more and 5 equivalent / kg fiber or less, the deodorant effect is large, the shape stability and durability of the textile product at the time of washing are good, and the texture is hardened after washing. Nothing. The carboxyl group and the sulfone group may be used alone or in combination, but the carboxyl group is preferable because the carboxylic acid is easier to introduce in a large amount and is superior in performance.

The transition metals referred to in the present invention are copper, zinc,
It refers to iron, nickel, chromium, cobalt, etc., and transition metal compounds are copper compounds (CuSO ₄ , Cu (NO ₃ )).
₂ etc.), zinc compounds (ZnSO ₄ , Zn (NO ₃ ))
₂ ), iron compounds (FeSO ₄ , Fe (NO ₃ ) ₂ ),
Nickel compounds (NiSO ₄ , Ni (NO ₃ ) _2, etc.),
Chromium compounds (CrSO ₄ , Cr (NO ₃ ) _2, etc.), cobalt compounds (CoSO ₄ , Co (NO ₃ ) _2, etc.) can be used, but copper compounds or zinc compounds are effective in that they are remarkable. Is preferred. The content is preferably 0.1 equivalent / kg fiber or more and 5 equivalent / kg fiber or less, more preferably 0.2 equivalent / kg fiber or more and 3 equivalent / kg fiber or less. If it is less than 0.1 equivalent / kg fiber, the deodorizing effect is small, and if it is more than 5 equivalent / kg fiber, the content of anionic functional groups becomes small, so that the deodorizing effect of ammonia and the like becomes small, which is not preferable. 0.2 equivalent / k
If it is g fiber or more and 3 equivalents / kg fiber or less, the deodorizing effect is particularly excellent, and since the content of the anionic functional group can be kept appropriate, the ammonia deodorizing effect is also good.

The acrylic synthetic fiber having an anionic functional group referred to in the present invention contains an acidic group such as a carboxyl group and a sulfonic acid group, preferably a sulfonic acid group, and / or a strong acid by copolymerization. Acrylic synthetic fiber containing a sulfonic acid group introduced into an end group when polymerized by a reactive catalyst, wherein 50% by weight or more of acrylonitrile and acrylic acid, methyl acrylate, ethyl acrylate, itaconic acid, methacrylic acid , Methyl methacrylate, styrene, acrylamide, methacrylamide,
One or more vinyl monomers such as vinyl acetate, vinyl chloride, vinylidene chloride, methallyl sulfonic acid, methallyl sulfonate, styrene sulfonic acid, styrene sulfonate, allyl sulfonic acid and allyl sulfonate. It is a synthetic fiber obtained by copolymerizing. Particularly preferably used in the present invention is 80% by weight or more of acrylonitrile and acrylic acid, methyl acrylate, methyl methacrylate, acrylamide, vinyl acetate, vinylidene chloride, vinyl monochloride such as methallyl sulfonate and styrene sulfonate. It is a synthetic fiber obtained by copolymerizing one kind or two or more kinds of monomers.

In the present invention, a method of introducing a carboxyl group into the fiber as an anionic functional group is as follows:
Although not particularly limited, a method of graft-polymerizing acrylic acid or the like by utilizing amide group, amino group, hydroxyl group or the like in the fiber, or a method of hydrolyzing acrylic fiber with alkali, such as acrylic acid Examples of the method include copolymerizing a polymer having a different carboxyl group, or polymer blending. Further, there is also a method in which after wet spinning, it is immersed in an aqueous solution of the polymer in an undried state and then dried. In the present invention, as a method of incorporating a transition metal salt by binding a transition metal to the anionic functional group of the fiber having an anionic functional group, a fiber having an anionic functional group is used as a monovalent cationic group. A method of treating with an alkaline aqueous solution containing a salt having an ion as a counter ion, for example, impregnating and then reacting with a transition metal compound can be mentioned.

The fiber containing the anionic functional group or the transition metal salt in which the anionic functional group is bound to a transition metal according to claim 6 of the present invention is, for example, cellulose fiber, acrylic synthetic fiber or polyamide fiber. One or more kinds of fibers obtained by graft-polymerizing a monomer having an anionic functional group after fiber molding, or a fiber containing an anionic functional group thus obtained is treated with a monovalent cation. A fiber treated with a transition metal compound after being treated with an alkaline aqueous solution containing an ion salt.

The fiber containing the anionic functional group or the transition metal salt in which the anionic functional group is bound to a transition metal according to claim 8 of the present invention is, for example, an acrylic synthetic fiber, a polyamide fiber, a polyester, or a regenerated fiber. One or more kinds of fibers obtained by polymer blending a cellulose fiber with a polymer having an anionic functional group before fiber formation, or a fiber having an anionic functional group thus obtained is monovalent. A fiber treated with a transition metal compound after being treated with an alkaline aqueous solution containing a salt having a cation as a counter ion.

A fiber containing a water-soluble polyamine compound embedded in the fiber and an anionic functional group or a fiber containing a transition metal salt in which the anionic functional group is bonded to a transition metal is used. The combination method may be any of mixed spinning, mixed twisting, mixed woven, mixed knitting, etc., and is not particularly limited. The composition ratio is 5% by weight or more and 99.9% by weight or less, preferably 10% by weight or more and 99% by weight or less, of the fiber contained in a state where the polymer containing an amino group is embedded in the fiber. If it is less than 5% by weight, the effect of deodorizing the malodor of the compound having a carbonyl group and the acidic compound is weak. Further, if it is 10% by weight or more, the deodorizing effect of the compound having a carbonyl group and the acidic compound becomes remarkable. The fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bonded to a transition metal is preferably 0.1% by weight or more and 95% by weight or less, more preferably 1% by weight or more, 90 It is preferably less than or equal to weight%. If it is less than 0.1% by weight, the effect of deodorizing the malodor of the basic compound is weak. If it is 1% by weight or more, the deodorizing effect against the malodor of the basic compound becomes remarkable. When using a fiber containing a transition metal salt in which a water-soluble polyamine compound is present in a state of being embedded in the fiber and an anionic functional group or the anionic functional group is bonded to a transition metal, The former alone can eliminate the bad odor of compounds having a carbonyl group and acidic compounds, but it is difficult to eliminate the bad odor of basic compounds, and the latter alone can eliminate the bad odor of basic compounds. The deodorizing effect of the compound and the acidic compound may be weakened.

[0025]

EXAMPLES Examples of the present invention will now be described in more detail, but the present invention is not limited thereto. The washing test was carried out in accordance with JIS-L-0217-103 method. The capacity to measure the deodorant performance of malodorous substances is 60
1 g of the textile product was placed in a 0 ml Meyer flask together with the malodorous component, and the residual gas concentration after 60 minutes was measured with a Kitagawa gas detector tube. The initial concentration of malodorous components is 100 ppm acetaldehyde as a compound containing a carbonyl group, 40 ppm acetic acid as an acidic compound and 25 pp hydrogen sulfide.
m, 140ppm of trimethylamine as a basic compound
And 140 ppm of ammonia.

The texture was evaluated by the following three-step evaluation. ○ -Not hard △ -Slightly hard × -Hard Furthermore, cigarette smoke was used as a sensory evaluation, and the volume was 600 ml.
Inject 0.5 ml of cigarette (mild seven) smoke into the Mayer flask of No. 1, leave it for 2 hours, and then have 16 monitors make the following judgments about the smell inside the flask and the smell of the fiber itself, and evaluate it with a total score. did.

Sensory evaluation No effect at all: 1 point Almost no effect: 2 points Some effect: 3 points Significant effect: 4 points Significant effect: 5 points The binding rate of acidic groups is measured by the total amount of acidic groups in the fiber. And the amount of residual acidic groups not bound to the functional groups of the polyamine compound (hereinafter referred to as the amount of residual acidic groups), which was obtained from the following formula. Bonding rate of acidic groups (mol%) = (total acidic group amount-residual acidic group amount) / total acidic group amount x 100 However, the unit of the total acidic group amount and the residual acidic group amount is [mo
1 / kg].

To measure the amount of residual acidic groups, 1 g of fiber was placed in 300 ml of a 10% by weight aqueous sodium chloride solution, shaken in a constant temperature bath at 40 ° C. for 30 hours, and then thoroughly washed with purified water to remove the attached sodium chloride. It was dried at ℃ for 1 hour to give a residual acidic group sodium-substituted fiber. The fiber is then 96
Wet decomposition was carried out for 5 hours on an electric heater in a mixed solution of 5% by weight sulfuric acid, 40 ml of 62% by weight nitric acid and 2 ml of 70% by weight perchloric acid. The liquid obtained here is diluted with purified water to 10
Diluted to 0 times, quantitative analysis of sodium was performed by flame photometry, and the amount of residual acidic groups was measured from the amount of sodium.

The dyeing process is carried out by using Astrazon as a dye.
Blue F2RL 200% (manufactured by Bayer Japan K.K.) was used, the dye concentration was set to 0.5% owf, and p
The pH was adjusted to 4 using acetic acid as the H adjuster, and the bath ratio was 1:
30 minutes at 50 and 100 ℃, washed with water, ammonia 1
After soaping with a 5% by weight aqueous solution for 5 minutes, it was thoroughly washed with water.

Example 1 A polymer obtained by copolymerizing 94.5% by weight of acrylonitrile, 5.0% by weight of methyl acrylate and 0.5% by weight of sodium methallylsulfonate was dissolved in 70% by weight of nitric acid. Then, a spinning dope having a polymer concentration of 15.5% by weight was prepared. The spinning solution was spun into a 37% by weight nitric acid-based coagulation bath kept at 0 ° C. through a spinneret having pores of 0.06 mm, washed with water and stretched 9 times in boiling water to obtain an undried fiber.

The undried fiber was dehydrated by immersing it in an aqueous solution of 2.5% by weight of polyethyleneimine (Nippon Shokubai Co., Ltd.) having a molecular weight of about 70,000 at 20 ° C. for 1 minute. The draw ratio at this time was 80% by weight. Polymer obtained by dehydration and drying at 80 ° C for 1 hour and heat-moisture treatment in an autoclave at 120 ° C for 5 minutes with wet steam, and acrylonitrile and acrylic acid at a mixing ratio of 80:20 by weight. A woven fabric was composed of spun yarn obtained by spinning fibers obtained by spinning in a 75% nitric acid bath and ordinary acrylic fibers (Cashimilon FK manufactured by Asahi Kasei Kogyo Co., Ltd.) in a ratio of 3: 1: 6.

Example 2 A polymer obtained by copolymerizing 94.5% by weight of acrylonitrile, 5.0% by weight of methyl acrylate and 0.5% by weight of sodium methallylsulfonate was dissolved in 70% by weight of nitric acid. Then, a spinning dope having a polymer concentration of 15.5% by weight was prepared. The spinning solution was spun into a 37% by weight nitric acid-based coagulation bath kept at 0 ° C. through a spinneret having pores of 0.06 mm, washed with water and stretched 9 times in boiling water to obtain an undried fiber.

The undried fiber was dehydrated by immersing it in an aqueous solution of 2.5% by weight of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd.) having a molecular weight of about 70,000 at 20 ° C. for 1 minute. The draw ratio at this time was 80% by weight. Polymer obtained by dehydration and drying at 80 ° C for 1 hour and heat-moisture treatment in an autoclave at 120 ° C for 5 minutes with wet steam, and acrylonitrile and acrylic acid at a mixing ratio of 80:20 by weight. Of the fiber obtained by spinning the above in a 75% nitric acid bath containing 1.5 mol / l sodium chloride at 20 ° C. 20%
Of a transition metal-containing fiber obtained by immersing in an aqueous solution of sodium hydroxide, then immersing in a 10% aqueous solution of copper sulfate, and then washing with water, dehydration, and drying, and ordinary acrylic fiber (casimiron manufactured by Asahi Kasei Kogyo KK). The woven fabric was composed of spun yarn in which FK) was mixed and spun at a ratio of 3: 1: 6.

Comparative Example 1 Polyethyleneimine 1 having a molecular weight of 70,000 was added to a woven fabric of acrylic fibers containing 0.06 mol / kg of sulfonic acid groups.
Immersion treatment was carried out for 1 minute in a 2% by weight aqueous solution at 20 ° C. to dehydrate. The draw ratio at this time was 17% by weight. Then 8
The fiber of Comparative Example 1 was obtained by drying at 0 ° C. for 1 hour.

With respect to the fabrics of Examples 1 and 2 and Comparative Example 1, the deodorizing performance against various malodors was evaluated together with the performance after 10 times of washing. The evaluation results are shown in Table 1.

[0036]

[Table 1]

According to Table 1, Examples 1 and 2 deodorize not only the carbonyl group-containing compound and the acidic compound but also the basic compound as compared with Comparative Example 1, and the performance is after 10 times of washing. It turns out that was also good. Further, it can be seen that the textures of Examples 1 and 2 were good. Examples 3-6, Comparative Examples 2-3 Acrylonitrile 74.7% by weight, vinylidene chloride 2
5.0% by weight, sodium metasulfonate 0.3% by weight
The polymer obtained by copolymerizing the above was dissolved in dimethylformamide to prepare a spinning dope having a polymer concentration of 18.0% by weight. The spinning solution was spun through a spinneret having pores of 0.15 mm into a 75% by weight dimethylformamide-based coagulation bath kept at 30 ° C., and then 5% in a 75% by weight dimethylformamide-based stretching bath kept at 80 ° C. It was stretched 0.0 times, washed with water, and then stretched 1.2 times in boiling water. The obtained undried fiber was changed from 0.05% by weight of polyallylamine pH 10 aqueous solution having a molecular weight of about 30,000 to 15.0% by weight to obtain 25
Immersion treatment was performed at 1 ° C. for 1 minute to dehydrate. The draw ratio at this time was 100% by weight. After dehydration, dry at 80 ℃ for 1 hour,
Acrylic acid was added to the fibers obtained by heat-moisture treatment at 120 ° C. for 5 minutes in an autoclave and regenerated cellulose fiber cupra (manufactured by Asahi Kasei Kogyo Co., Ltd.) so that the carboxyl groups contained 2.0 equivalents / kg. A woven fabric is composed of spun yarns in which graft-polymerized fibers and ordinary acrylic fibers (casimiron FK) are mixed in a ratio of 3: 0.5: 6.5, respectively, and deodorant for bad odors as in Example 1 is performed. The performance was evaluated.

Table 2 shows the polyallylamine content of the fibers constituting each woven fabric and the evaluation results of the deodorizing performance against bad odors.

[0039]

[Table 2]

According to Table 2, those having a polyallylamine content of 0.1 to 10% owf (Examples 3 to 6) deodorize not only the carbonyl group-containing compound and the acidic compound but also the basic compound. And also excellent in deodorizing performance of cigarettes,
It can be seen that the texture was good. Examples 7 to 10 and Comparative Examples 4 to 5 70% by weight of a polymer obtained by copolymerizing 94.5% by weight of acrylonitrile, 5.0% by weight of methyl acrylate and 0.5% by weight of sodium methallylsulfonate. % Nitric acid to prepare a spinning dope having a polymer concentration of 15.5% by weight. The spinning solution was spun into a 37% by weight nitric acid-based coagulation bath kept at 0 ° C. through a spinneret having pores of 0.06 mm, washed with water and stretched 9 times in boiling water to obtain an undried fiber.

The undried fiber was dehydrated by immersing the undried fiber in an aqueous solution of 2.5% by weight of polyallylamine pH 10 having a molecular weight of about 30,000 at 25 ° C. for 1 minute. The draw ratio at this time was 100% by weight. After dehydration, dry at 80 ℃ for 1 hour,
The fibers obtained by performing a wet heat treatment for 5 minutes in a saturated steam of 120 ° C. in an autoclave and the same undried fiber as described above are immersed in polyacrylic acid, and the content of the carboxyl group is from 0.1 mol / kg. A woven fabric was composed of spun yarn obtained by mixing fibers of 15.0 mol / kg and ordinary acrylic fibers (Cashimilon FK manufactured by Asahi Kasei Kogyo Co., Ltd.) at a ratio of 3: 0.5: 6.

Table 3 shows the evaluation results of the content of carboxyl groups of the fibers constituting each woven fabric and the deodorizing performance against bad odor.
It was shown to.

[0043]

[Table 3]

According to Table 3, those having a carboxyl group content of 0.2 to 10 mol / kg (Examples 7 to 10)
It is found that not only the carbonyl group-containing compound and the acidic compound but also the basic compound are deodorized and the tobacco deodorizing performance is also excellent. It also has good washing durability,
It can be seen that the texture after washing was also good. Examples 11-14, Comparative Examples 6-7 Acrylonitrile 74.7% by weight, vinylidene chloride 2
5.0% by weight, sodium metasulfonate 0.3% by weight
The polymer obtained by copolymerizing the above was dissolved in dimethylformamide to prepare a spinning dope having a polymer concentration of 18.0% by weight. The spinning solution was spun through a spinneret having pores of 0.15 mm into a 75% by weight dimethylformamide-based coagulation bath kept at 30 ° C., and then 5% in a 75% by weight dimethylformamide-based stretching bath kept at 80 ° C. It was stretched 0.0 times, washed with water, and then stretched 1.2 times in boiling water. The obtained undried fiber was mixed with 3.8% by weight of polyethyleneimine having a molecular weight of about 70,000.
Immersion treatment in a 20 ° C. aqueous solution for 1 minute gives a squeezing ratio of 80
%, Dehydrated to 80%, dried at 80 ° C. for 1 hour, and then subjected to wet heat treatment in an autoclave at 120 ° C. for 5 minutes to obtain a fiber, acrylonitrile and acrylic acid in a weight ratio of 80:20. The content of copper bonded to the carboxyl group of the fiber obtained by polymer blending the polymer copolymerized with the above and polyacrylonitrile at a ratio of 30:70 was changed in the range of 0.05 to 6.0 equivalent / kg. Acrylic fiber and normal polyester fiber 3: 0.5:
A woven fabric was composed of spun yarn mixed at a ratio of 6.5, and the same deodorizing performance against bad odor as in Example 1 was evaluated.

Table 4 shows the evaluation results of the copper content of the fibers constituting each woven fabric and the deodorizing performance against bad odor.

[0046]

[Table 4]

According to Table 4, those having a copper content of 0.1 to 5 equivalents / kg (Examples 11 to 14) not only eliminate carbonyl group-containing compounds and acidic compounds but also basic compounds. It can be seen that the odor and the deodorizing performance of tobacco were excellent, and the texture was good. Examples 15-19, Comparative Examples 8-11 70% by weight of a polymer obtained by copolymerizing 94.5% by weight of acrylonitrile, 5.0% by weight of methyl acrylate and 0.5% by weight of sodium methallylsulfonate. % Nitric acid to prepare a spinning dope having a polymer concentration of 15.5% by weight. The spinning solution was spun into a 37% by weight nitric acid-based coagulation bath kept at 0 ° C. through a spinneret having pores of 0.06 mm, washed with water and stretched 9 times in boiling water to obtain an undried fiber.

The undried fiber was immersed in a 5.0% by weight aqueous solution of polyallylamine pH 10 having a molecular weight of about 30,000 at 25 ° C. for 1 minute, dehydrated to a draw ratio of 100% by weight, and dried at 80 ° C. for 1 minute. After drying for an hour, the autoclave was subjected to wet heat treatment at 120 ° C for 5 minutes in saturated steam, and the obtained nylon fiber and the nylon fiber had 0.8 carboxyl groups.
The knitted fabric was made of spun yarn that was mixed and spun by changing the mixing ratios of the fibers graft-polymerized with acrylic acid so as to contain mol / kg and ordinary acrylic fibers (casimiron FK). The deodorizing performance was evaluated.

Table 5 shows the evaluation results of the mixing ratio of the polyallylamine-containing acrylic fiber and the carboxyl group-containing nylon fiber of the fibers constituting each knitted fabric, and the deodorizing performance against bad odor.

[0050]

[Table 5]

According to Table 5, fibers having a polyallylamine-containing acrylic fiber content of 5% by weight or more and a carboxyl group-containing nylon fiber content of 0.1% by weight or more (Examples 15 to 19) were used. ) Deodorizes not only the carbonyl group-containing compound and the acidic compound but also the basic compound and is also excellent in the deodorizing performance of tobacco.

Examples 20 to 24, Comparative Examples 12 to 15 Acrylonitrile 74.7% by weight, vinylidene chloride 2
5.0% by weight, sodium metasulfonate 0.3% by weight
The polymer obtained by copolymerizing the above was dissolved in dimethylformamide to prepare a spinning dope having a polymer concentration of 18.0% by weight. The spinning solution was spun through a spinneret having pores of 0.15 mm into a 75% by weight dimethylformamide-based coagulation bath kept at 30 ° C., and then 5% in a 75% by weight dimethylformamide-based stretching bath kept at 80 ° C. It was stretched 0.0 times, washed with water, and then stretched 1.2 times in boiling water. The fiber has a molecular weight of about 30.
000 polyallylamine 5.0 wt% pH10 aqueous solution at 25 ℃ for 1 minute, dehydration so that the squeezing ratio becomes 100 wt%, and then dried at 80 ℃ for 1 hour, saturated steam at 120 ℃ in an autoclave. Obtained by heat-moisture treatment for 5 minutes at room temperature and ordinary acrylic fiber (casimiron F
K) an acrylic fiber in which the content of zinc bonded to the carboxyl group of the fiber obtained by graft polymerization of acrylic acid so that the carboxyl group is contained in the amount of 2.0 equivalent / kg is 0.2 equivalent / kg, Each woven fabric was made of spun yarn prepared by mixing ordinary acrylic fibers (casimiron FK) in a ratio of 3: 0.5: 6.5, and the deodorizing performance against bad odor was evaluated in the same manner as in Example 1. .

The mixing ratio of the polyallylamine-containing acrylic fiber and the zinc-containing acrylic fiber of the fibers constituting each woven fabric,
Table 6 shows the evaluation results of the deodorizing performance against the malodor.

[0054]

[Table 6]

According to Table 6, fibers having a polyallylamine-containing acrylic fiber content of 5% by weight or more and a zinc-containing acrylic fiber content of 0.1% by weight or more (Examples 20 to 24) were used. Deodorizes basic compounds as well as carbonyl group-containing compounds and acidic compounds,
It is also understood that the cigarette deodorant performance is also excellent. Example 25, Comparative Example 16 A polymer obtained by copolymerizing 94.6% by weight of acrylonitrile, 5.0% by weight of methyl acrylate and 0.4% by weight of itaconic acid was dissolved in 70% by weight of nitric acid. A spinning stock solution having a polymer concentration of 16.0% by weight was prepared. This spinning dope was spun through a spinneret having pores of 0.06 mm into a 35% by weight nitric acid-based coagulating bath kept at 0 ° C., washed with water and stretched 8 times in boiling water to obtain undried fibers. The fiber has a molecular weight of about 7
Immersion treatment was carried out for 1 minute in a 20 ° C. aqueous solution of 2.5% by weight of polyethyleneimine of 0000, and dehydration was performed so that the squeezing ratio was 80%, followed by drying at 80 ° C. for 1 hour, followed by autoclave 1
The weight ratio of the fibers obtained by performing heat treatment for 5 minutes in saturated steam at 20 ° C., acrylonitrile and acrylic acid to 80:
A fiber is obtained by blending a polymer copolymerized at a mixing ratio of 20 and polyacrylonitrile at a ratio of 30:70 and a spun yarn obtained by mixing ordinary acrylic fibers at a ratio of 3: 1: 6. (Example 25). As a comparative example, a woven fabric was formed in the same manner as in Comparative Example 16 except that the fiber of Example 25 was not subjected to wet heat treatment. With respect to Examples and Comparative Examples, the same deodorant performance against malodor as in Example 1 and the deodorant performance against malodor after 10 times of washing and after dyeing were evaluated. The evaluation results are shown in Table 7.

[0056]

[Table 7]

According to Table 7, moist heat treatment was performed when polyethyleneimine was applied to acrylic synthetic fibers after being coagulated by a wet spinning method and before being dried, so that the binding rate between the acidic groups and polyethyleneimine was 50 mol / kg or more. It can be seen that the deodorized products exhibited good deodorizing performance against the carbonyl group-containing compound and the acidic compound after 10 times of washing and after dyeing.

[0058]

According to the invention described in claim 1 of the present application, it has an excellent deodorizing performance against a bad odor composed of a compound having a carbonyl group such as a cigarette odor, an acidic compound and a basic compound, Moreover, it is possible to obtain a deodorant fiber product whose deodorizing performance has washing durability and dyeing durability.

According to the invention of claim 2 of the present application, it has an excellent deodorizing performance against a bad odor composed of a carbonyl group-containing compound such as a cigarette odor, an acidic compound and a basic compound, and A method for producing a deodorant fiber having deodorant performance having washing durability and dyeing durability can be obtained. According to the invention described in claims 3 to 9 of the present application, it has excellent deodorizing performance against a bad odor composed of a carbonyl group-containing compound such as a cigarette odor, an acidic compound, and a basic compound, and further eliminates the odor. A deodorant fiber whose odor performance has washing durability and dyeing durability can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D04H 1/42 R D06M 15/61

Claims (9)

[Claims] 1. The content of amino groups per unit of monomer is 1 to 2 equivalents, and the degree of polymerization is 7 or more and 2400.
The following water-soluble polyamine compound was contained in the fiber after coagulation of the acrylic synthetic fiber obtained by the wet spinning method and before drying, in an amount of 0.1% owf or more and 10% owf or less.
0.01 mol / kg or more of acidic groups per fiber, 2.5
5% by weight of acrylic synthetic fiber containing less than mol / kg
Above, 0.2 equivalents / kg or more and 10 equivalents / kg or less anionic functional group or a transition in which the anionic functional group is bound to 0.1 equivalent / kg or more and 5 equivalent / kg or less transition metal A deodorant fiber product containing 0.1% by weight or more of a fiber containing a metal salt. 2. Acrylic synthetic fiber obtained by a wet spinning method, after coagulation and before drying, has a content of amino groups per monomer unit of 1 to 2 equivalents and a degree of polymerization of 7 to 2400. The following water-soluble polyamine compounds are evenly attached, and the resulting fiber is heated to 100 ° C or higher and 180 ° C
A method for producing a deodorant fiber, which comprises subjecting an acidic group in a fiber and a water-soluble polyamine compound to wet-heat bonding by treatment with the following steam. 3. The deodorant fiber according to claim 2, wherein the bonding ratio between the acidic groups of the acrylic synthetic fiber and the amino groups of the water-soluble polyamine compound is 50 mol% or more and 100 mol% or less. 4. Equivalent to 0.2 equivalent / kg or more, 10 equivalent / kg
The following anionic functional group or the anionic functional group contains a transition metal salt bound to a transition metal in an amount of 0.1 equivalent / kg or more and 5 equivalent / kg or less. A deodorant fiber containing a transition metal salt in which a group or the ionic functional group is bonded to a transition metal. 5. The fiber according to claim 4, wherein the fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bonded to a transition metal is an acrylic synthetic fiber, which is an anion before fiber formation. Deodorant fiber obtained by copolymerizing a monomer having a functional group, or the fiber having an anionic functional group thus obtained is treated with an aqueous alkaline solution containing a salt having a monovalent cation as a counterion. After that, the deodorant fiber was reacted with a transition metal compound. 6. The fiber according to claim 4, which contains an anionic functional group or a transition metal salt in which the anionic functional group is bonded to a transition metal, grafts a monomer having an anionic functional group after fiber formation. The deodorant fiber obtained by polymerization or the fiber having an anionic functional group thus obtained is treated with an alkaline aqueous solution containing a salt having a monovalent cation as a counter ion, and then reacted with a transition metal compound. Deodorized fiber. 7. The wet spinning method according to claim 4, wherein the fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bonded to a transition metal is an acrylic synthetic fiber or a regenerated cellulose fiber. After coagulation and before drying, the deodorant fiber obtained by adding a polymer having an anionic functional group, or the fiber containing an anionic functional group thus obtained, has a monovalent cation as a counter ion. Deodorized fiber treated with a transition metal compound after being treated with an alkaline aqueous solution containing salt. 8. The fiber according to claim 4, wherein the fiber containing an anionic functional group or a transition metal salt in which the ionic functional group is bound to a transition metal is a polymer having an anionic functional group before fiber formation. The deodorant fiber obtained by blending or the fiber having an anionic functional group thus obtained is treated with an alkaline aqueous solution containing a salt having a monovalent cation as a counterion, and then reacted with a transition metal compound. Deodorized fiber. 9. The fiber according to claim 4, wherein the fiber containing an anionic functional group or a transition metal salt in which the anionic functional group is bound to a transition metal is an acrylic synthetic fiber and is hydrolyzed in the presence of an alkali. By treating the deodorant fiber having an anionic functional group introduced therein, or the anionic functional group-containing fiber thus obtained, with an aqueous alkaline solution containing a salt having a monovalent cation as a counter ion, the transition Deodorant fiber reacted with metal compounds.