JPS6312723A - Deodorizing acrylic synthetic fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled deodorizing fibers without unpleasant smell, by drawing and washing wet spun acrylic synthetic fibers with water into a gelatinous and swelled state, applying and impregnating an aqueous solution containing a specific metal salt of an acid and organic acid into the fibers, heat-treating and densifying the resultant fibers. CONSTITUTION:A spinning solution of a polymer, consisting of >=80wt% acrylonitrile, <20wt% vinyl based monomer and sulfonic acid group-containing monomer and constituting acrylic synthetic fibers is wet spun, drawn and washed with water to give fibers in a gelatinous and swelled state. An aqueous solution consisting essentially of (A) sulfate, chloride, nitrate or acetate of a metal, e.g. Cu, Zn, Al, Fe, Ni, Sn, Pb, Ti, Mn, Co, Ag, etc., and (B) an organic acid, e.g. malic acid, etc., is applied and impregnated into the fibers. The obtained fibers are then heat-treated and densified to afford the aimed fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a deodorizing acrylic synthetic fiber having an excellent deodorizing effect and a method for producing the same.

[Conventional technology]

In short, methods for deodorizing and deodorizing include methods of masking malodors with aromatic substances, methods of oxidizing and decomposing malodorous substances with oxidizing agents such as potassium permanganate, salts, nitric acid, etc.
A method of neutralizing with a neutralizing agent such as sodium hydroxide or sodium carbonate, a method of adsorbing bad odors with activated carbon, and a method of containing an aqueous solution of ferrous salt and L-ascorbic acid in a carrier, the deodorizing effect is achieved by the action of both. There is a way to make it work.

However, among these methods, the method using a masking agent has the disadvantage that the odor of the aromatic substance to be masked causes discomfort, and other methods such as oxidative decomposition neutralization, immobilization, or adsorption do not remove the odor of the odor substance. The disadvantage is that the selectivity for Also, ferrous salt and L
- When using an aqueous solution of ascorbic acid, since L-ascorbic acid has poor heat resistance and light resistance, L-ascorbic acid is destroyed and the ability to reduce ferric salt to ferrous salt is lost; It has the disadvantage of losing its deodorizing effect and causing discoloration.

And the deodorizing and deodorizing methods mentioned above are deodorizing.

The deodorizing component is solidified and left in an air atmosphere to deodorize and deodorize, and the fiber itself has the above deodorizing and a.
There are very few examples of containing odor components.

[Problem that the invention seeks to solve]

As an attempt to impart deodorizing properties to the fibers themselves, there is a method of preventing bad odors by incorporating an antibacterial agent into the fibers to prevent the proliferation of bacteria, and this method has been implemented in some cases. However, in this case, it is an indirect method of preventing the proliferation of bacteria, and it has the disadvantage that it cannot eliminate odor caused by causes other than the proliferation of bacteria.

In addition, other methods of imparting deodorizing properties to the fibers themselves include:
There is also a method of incorporating an aromatic substance into the fiber itself, but in this case, as mentioned earlier, the problem is that the odor of the aromatic substance stains the entire surrounding atmosphere, causing discomfort. be.

The present invention was developed in view of the above circumstances, and is a deodorizer that can eliminate all kinds of bad odors without making the surrounding atmosphere unpleasant with the fragrance of the masking agent, and which also maintains the texture of the fiber itself. The purpose of the present invention is to provide a synthetic acrylic fiber and a method for producing the same.

[Means for solving problems]

In order to achieve the above object, the present invention provides the following A
The first gist is deodorizing acrylic synthetic ta11i containing component and B component, (A) Cu, Z
n, AllFe+NilSn+Pb+Ti
tMn+ One or more of a sulfate of a metal selected from the group consisting of Go and Ag, a chloride of the metal, a nitrate of the metal, and an acetate of the metal.

(B) Organic acid.

Wet-spinning a spinning solution of acrylic synthetic fiber;
It includes a stretching process and a water washing process, and through these processes, the fibers in a gel-swollen state are adhered and impregnated with an aqueous liquid mainly composed of A and B below, and then heat-treated to form the fibers. The second gist is a method for producing deodorizing acrylic synthetic fibers that densify the fibers.

(A) Cu, Zn, Al, Fe+Nil
Sn+ Pb+ Ti+Mn+ One or more of the following: a sulfate of a metal selected from the group consisting of Co and Ag, a chloride of the metal, a nitrate of the metal, and an acetate of the metal.

(B) Organic acid.

The deodorizing acrylic synthetic fiber of the present invention contains the above-mentioned component A and component B, and both of these components evaporate little by little from the inside of the fiber, thereby deactivating the malodorous component. be. In other words, unlike conventional masking agents, both of the above components do not have an odor themselves, so
It does not cause the surrounding atmosphere to become uncomfortable, and it does not prevent the growth of bacteria like antibacterial agents do, but instead actively deactivates malodorous components, so it is effective against all It has the ability to prevent various types of bad odors. In addition, since both the A component and the B component are well compatible with the components of the acrylic synthetic fiber, the fiber performance and texture of the acrylic synthetic fiber itself are not impaired in any way.

Therefore, the deodorizing acrylic synthetic fiber of the present invention can be used in the same way as ordinary acrylic synthetic fiber. According to the manufacturing method of the present invention, the deodorizing acrylic synthetic fiber as described above can be efficiently manufactured.

The deodorizing acrylic synthetic fiber of the present invention comprises the above-mentioned A component, B
Obtained using ingredients and acrylic synthetic fibers.

The above A component is Cu, Zn+ Al+ Fe, N
i, Sn, Pb.

One or more of a sulfate of a metal selected from the group consisting of Ti, Mn, Co, and Ag, a chloride of the metal, a nitrate of the metal, and an acetate of the metal. That is, the various metal salts mentioned above may be used alone or in combination as component A. Among them, Cu+ Zn+
Aj! + The above groups of Fe and Nl are effective.

Typical examples of the above metal salts are as follows. Ferrous sulfate, cupric sulfate, stannous sulfate, nickel sulfate, manganous sulfate.

Zinc sulfate, aluminum chloride, titanium tetrachloride, lead nitrate,
Cobaltous sulfate, silver nitrate, nickelous acetate.

Further, the organic acid of component B used together with the metal salt of component A is not particularly limited, and all kinds of organic acids can be used.

Among them, aliphatic saturated dicarboxylic acids and aliphatic saturated oxycarboxylic acids are particularly effective. Representative examples of the above organic acids are as follows. Examples of aliphatic saturated oxycarboxylic acids include malic acid, citric acid, tartaric acid, and D-gluconic acid. As aliphatic saturated dicarboxylic acids,
Examples include oxalic acid, malonic acid, glutaric acid, and succinic acid. In addition, tricarballylic acid, which is an aliphatic saturated tricarboxylic acid, is also mentioned.

The ratio of the metal salt as component A and the organic acid as component B to each other is preferably set so that the amount of the metal salt is equal to or 200 times the amount of the organic acid on a weight basis. Most preferably, the amount of metal salt is set to be equal to or twice as much as the amount of organic acid.

The acrylic synthetic fiber containing the above A component and B component is not particularly limited, but is preferably composed of a polymer containing at least 40% by weight (hereinafter abbreviated as "%") of acrylonitrile. . for example,
Examples include those copolymerized with 40% or more of acrylonitrile and less than 60% of other vinyl monomers.

Examples of the other vinyl monomers include acrylic acid.

Methacrylic acid or its alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride.

Examples include sodium allylsulfonate, sodium methacrylsulfonate, sodium vinylsulfonate, and sodium styrenesulfonate. These may be used alone or in combination.

In particular, a copolymer of 80% or more acrylonitrile and less than 20% of a vinyl monomer and a sulfonic acid group-containing monomer, or a copolymer of at least one of vinyl chloride and vinylidene chloride and 20 to 60% of a sulfonic acid group-containing monomer and 40% or more A copolymer of acrylonitrile and acrylonitrile is particularly preferred from the viewpoint of deodorizing effect. Further, the acrylic polymer may contain a resin such as cellulose acetate, polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate copolymer, polyvinyl butyral, or the like. In particular, porous acrylic synthetic fibers made of the acrylic polymer containing 2 to 30% cellulose acetate are preferred from the standpoint of retaining and containing the A and B components.

The acrylic synthetic fiber is composed of the acrylic polymer described above, and examples of polymerization solvents for the acrylic polymer include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone, aqueous zinc chloride solution, and rhodan salt. Examples include solvents such as aqueous solutions and concentrated nitric acid. The above-mentioned acrylic synthetic fiber is preferably obtained by wet spinning using an organic solvent that tends to produce many voids during wet spinning.

Regarding the method of adding the above-mentioned A component and B component to the acrylic synthetic fiber, it is particularly preferable to add them simultaneously during the production of the acrylic synthetic fiber from the viewpoint of maintaining the fiber performance and texture of the acrylic synthetic fiber itself.

To describe an example of its production, first, the above-mentioned A component and B component are respectively dissolved in water, and the A component and B component are 0.
Make an aqueous solution with a concentration of 5-15%. In this case, it is preferable to add a surfactant to the aqueous solution in terms of preventing fiber adhesion and generation of static electricity, and improving spinning and knitting properties. Suitable examples of such surfactants include:
Weak cations containing alkylamide ammonium salts,
and an anion containing at least one of polyoxyethylene (n=10-30) alkyl ether phosphate and a salt thereof;
Mention may be made of nonionic activator mixtures. Furthermore, anionic and nonionic surfactant mixtures containing at least one of polyoxyethylene (n=10 to 30) alkyl phenyl ether phosphate and salts thereof may be mentioned (n is the number of moles of ethylene oxide added). As the alkylamide ammonium salt, laurylamide ethyldimethylamine is used.

laurylamide ethyldiethylamine, oleylamide ethyldimethylamine, oleylamide ethyl diethylamine, cetylamide ethyl dimethylamine, cetylamide ethyl diethylamine sulfate, nitrate, hydrochloride,
Phosphates, acetates, etc. are preferred. In addition, as polyoxyethylene (n=10-30) alkyl ether phosphate and its salt, polyoxyethylene (n=10-30)
30) Lauryl ether phosphate, polyoxyethylene (n=10-30) cetyl ether phosphate,
Polyoxyethylene (n=10-30) Stearyl ether phosphate polyoxyethylene (n=10-30
) oleyl ether phosphate and their respective soda and potassium salts.

Ammonium salts are preferred. Furthermore, as polyoxyethylene (n=10-30) alkyl phenyl ether phosphate and its salt, polyoxyethylene (n
-10-30) nonylphenyl ether phosphate,
Polyoxyethylene (n=10-30) dodecyl phenyl ether phosphate and their respective soda and potassium salts.

Ammonium salts are preferred.

Next, a spinning stock solution of the above-mentioned acrylic synthetic fiber is produced by a normal method, and after wet spinning in a normal coagulation bath,
Wash with water and remove solvent. Then, the acrylic fibers in a gel-swollen state are adhered and impregnated with the mixed solution of the A component and B component via this water washing and solvent removal. In this case, the acrylic fibers are in a gel-swollen state, and when observing each individual fiber, minute voids have occurred in each fiber, and the mixed solution has penetrated into these voids. Become. Then, after adhesion and impregnation with the mixed solution, drying and densification are performed. The conditions for this drying and densification are not particularly limited, but when using a roller dryer, it is preferable to set the surface temperature to 120 to 160°C. Moreover, in the case of dry heat drying, it is suitable to dry using a hot air dryer at 120 to 180°C. Drying time is 1
It is preferable to set the time to 7 minutes. Through such drying and densification, components A and B that have penetrated and impregnated into the voids are
The mixed solution of the components becomes trapped within the acrylic fibers as the water evaporates and the voids close and disappear. Therefore, the above-mentioned components A and B are evaporated from the acrylic fibers very little at a time over a long period of time, and as a result, a long-term deodorizing effect is exerted. After this drying, if the surfactant is further applied again or heat treatment is performed at a temperature of 100 to 135°C, the deodorizing effect of the obtained deodorant acrylic synthetic fiber can be improved and the spinability and knitting properties can be improved. Particularly preferred from the viewpoint of improvement.

〔Effect of the invention〕

As mentioned above, the deodorizing acrylic synthetic fiber of the present invention is
Because it directly deodorizes by inactivating the malodorous components with the A and B components it contains, it deodorizes without making the surrounding atmosphere unpleasant with its own scent, unlike conventional masking agents. You will be able to do this. In addition, unlike conventional antibacterial agents, the antibacterial effect does not prevent the occurrence of malodors themselves, but instead acts directly on the malodors that occur and deodorizes them by inactivating the components of the malodors. Deodorization becomes possible. Moreover, since the above-mentioned components A and B have good compatibility with the acrylic synthetic fiber component, they do not impair the fiber performance or texture of the acrylic synthetic fiber itself. Therefore, the deodorizing acrylic synthetic fiber of the present invention can be used in the same way as ordinary acrylic synthetic fiber. For example, regular acrylic synthetic fibers, polyester, nylon, and cotton.

It can also be used in combination with fibers such as rayon and wool, and has a deodorizing effect, allowing it to be used in a wide range of applications such as blankets, bed mats, bed sheets, sheets, and futon cotton. Become. Furthermore, according to the manufacturing method of the present invention, deodorizing ingredients are incorporated into the fiber during the manufacturing process of the acrylic synthetic fiber, so that the deodorizing acrylic synthetic fiber exhibits a deodorizing effect for an extremely long period of time. It has the advantage of being able to be manufactured efficiently.

Next, examples will be described together with comparative examples.

[Examples 1 to 14, Comparative Examples 1 to 4] Acrylonitrile (AN)/methyl acrylate) (
MA)/sodium methacryl sulfonate (SMAS) = 9
A dimethylformamide (DMF) solution of an acrylic polymer consisting of 1.2/8.010.8 was prepared. Then, this solution was spun into a 60% DMF aqueous solution at 20°C,
The acrylic synthetic fiber in a gel-swollen state is subjected to a normal stretching and water washing process, and the A and B components shown in Table 1 below and polyoxyethylene (n=16) nonylphenyl ether phosphate potassium salt (1,5 %) (a solution prepared by dissolving the above-mentioned components, component B, and surfactant in water) was adhered and impregnated, and then dried and densified using a roller dryer. Then, the obtained acrylic synthetic fiber was subjected to a heat treatment at 125°C.

A circular knitted fabric was prepared using the deodorizing acrylic synthetic fiber thus obtained, and the trimethylamine removal rate and ethyl mercaptan removal rate were measured and shown in Table 1 below.

As is clear from Table 1, it can be seen that the actual height measurements have superior deodorizing performance compared to the comparative height measurements.

(Left below) (Deodorizing effect test method) [Trimethylamine removal rate measurement method] 15 g of sample in a 350cI11 sealed container (35C
IIIX20cm) and 1ml of 1% trimethylamine! was added and sealed. After leaving it for 24 hours, take 1 ml of headspace gas and add 1 ml of diglycerol.
Gas chromatography analysis was performed using a column containing 5% + tetraethylenepentamine 5% + KOH 2%. Similarly, a blank test (
1%-trimethylamine (1 ml only) was carried out to determine the removal rate.

[Ethyl mercaptan removal rate measurement method]

15g sample in a 350d sealed container (35cm x 20cm)
m), 0.6 mg of ethyl mercaptan was added, and the mixture was sealed. After standing for 24 hours, a headspace gas of 1 mA was applied, and gas chromatography analysis was performed using a 1,2.3-)lis(2-cyanoethoxy)propane column. Similarly, a blank test was conducted to determine the removal rate.

[Examples 15 and 16, Comparative Examples 5 to 7] DMF solution of mixed polymer of 90 parts by weight of acrylic polymer consisting of AN/MA/SMAS = 91.9/7.510.6 and 10 parts by weight of cellulose acetate prepared. Then, this solution was spun into a 55% DMF aqueous solution at 18°C, passed through the usual stretching and water washing process, and was applied to the gel-swollen acrylic synthetic fibers containing the components A and B shown in Table 2 below. After adhering and impregnating the ingredients and an aqueous solution of laurylamide ethyl dimethylamine sulfate (1.5%) (A, B, a solution in which surfactants are dissolved in water), dry and densify using a roller dryer. temperature at 115°C.
Heat treatment was performed.

The deodorizing acrylic synthetic fiber thus obtained was
A circular knitted fabric was prepared by blending 0% and 50% of acrylic synthetic fiber obtained in a conventional manner, and the trimethylamine removal rate and ethyl mercaptan removal rate were measured in the same manner as above. The results are shown in Table 2, and it can be seen from the height measurements that excellent deodorizing performance is achieved even when blended.

(Margin below)

Claims (18)

[Claims] (1) A deodorizing acrylic synthetic fiber, characterized in that the following components A and B are contained in at least one of the interior and surface of the acrylic synthetic fiber. (A) Cu, Zn, Al, Fe, Ni, Sn, Pb, T
one or more of the following: a sulfate of a metal selected from the group consisting of Mn, Co, and Ag, a chloride of the metal, a nitrate of the metal, and an acetate of the metal. (B) Organic acid. (2) The acrylic synthetic fiber is composed of a polymer of 80% by weight or more of acrylonitrile and less than 20% by weight of a vinyl monomer and a sulfonic acid group-containing monomer. Odorable acrylic synthetic fiber. (3) The deodorant acrylic according to claim 1, wherein the acrylic synthetic fiber is composed of a polymer of 40% by weight or more of acrylonitrile and 20 to 60% by weight of vinylidene chloride and a sulfonic acid-containing monomer. synthetic fiber. (4) Acrylic synthetic fiber contains cellulose acetate 2 to 30%
The deodorizing acrylic synthetic fiber according to claim 1, which is a porous fiber containing % by weight. (5) The metal in component A is Cu, Zn, Al, Fe.
The deodorizing acrylic synthetic fiber according to any one of claims 1 to 4, which is Ni or Ni. (6) Deodorizing acrylic synthesis according to any one of claims 1 to 5, wherein the organic acid in component B is at least one of an aliphatic saturated dicarboxylic acid and an aliphatic saturated oxycarboxylic acid. fiber. (7) Deodorant acrylic synthesis according to claim 6, wherein the aliphatic saturated dicarboxylic acid is at least one organic acid selected from the group consisting of oxalic acid, malonic acid, succinic acid, and glutaric acid. fiber. (8) Claim 6, wherein the aliphatic saturated oxycarboxylic acid is at least one organic acid selected from the group consisting of malic acid, citric acid, tartaric acid, and D-gluconic acid.
The deodorizing acrylic synthetic fiber described in Section 1. (9) The spinning solution of acrylic synthetic fibers is wet-spun, stretched, and washed with water, and the fibers in the gel-swollen state are subjected to the following A and B through these steps. A method for producing deodorizing acrylic synthetic fibers, which is characterized by adhering and impregnating the fibers with an aqueous liquid as the main component, and then heat-treating the fibers to densify them. (A) Cu, Zn, Al, Fe, Ni, Sn, Pb, T
one or more of the following: a sulfate of a metal selected from the group consisting of Mn, Co, and Ag, a chloride of the metal, a nitrate of the metal, and an acetate of the metal. (B) Organic acid. (10) Deodorizing property according to claim 9, wherein the polymer forming the acrylic synthetic fiber comprises 80% by weight or more of acrylonitrile and less than 20% by weight of a vinyl monomer and a sulfonic acid group-containing monomer. Manufacturing method for acrylic synthetic fibers. (11) Deodorizing acrylic synthesis according to claim 9, wherein the polymer forming the acrylic synthetic fiber comprises 40% by weight or more of acrylonitrile and 20 to 60% by weight of vinylidene chloride and sulfonic acid-containing monomers. Fiber manufacturing method. (12) The method for producing deodorant acrylic synthetic fibers according to claim 9, wherein the deodorant acrylic synthetic fibers produced are porous fibers containing 2 to 30% by weight of cellulose acetate. (13) The metal in the component is Cu, Zn, Al, Fe.
or Ni. The method for producing a deodorizing acrylic synthetic fiber according to any one of claims 9 to 11. (14) Deodorizing acrylic synthesis according to any one of claims 9 to 13, wherein the organic acid in component B is at least one of an aliphatic saturated dicarboxylic acid and an aliphatic saturated oxycarboxylic acid. Fiber manufacturing method. (15) Deodorizing properties according to claim 9, wherein the aliphatic saturated dicarboxylic acid in component B is at least one organic acid selected from the group consisting of oxalic acid, malonic acid, succinic acid, and glutaric acid. Manufacturing method of acrylic synthetic fiber. (16) The aliphatic saturated oxycarboxylic acid in component B is at least one organic acid selected from the group consisting of malic acid, citric acid, tartaric acid and D-gluconic acid. Manufacturing method of odorous acrylic synthetic fiber. (17) A method for producing a deodorizing acrylic synthetic fiber according to any one of claims 9 to 16, wherein a surfactant is contained in an aqueous liquid containing components A and B as main components. . (18) The surfactant is an acrylamide ammonium salt, a polyoxyethylene alkyl ether phosphate with a repeating number n of 10 to 30, and a repeating number n of 10 to 30.
polyoxyethylene alkyl phenyl ether phosphate with a repeating number n of 10 to 30, a polyoxyethylene alkyl phenyl ether phosphate with a repeating number n of 10 to 3
18. The method for producing a deodorizing acrylic synthetic fiber according to claim 17, wherein the surfactant is at least one surfactant selected from the group consisting of salts of polyoxyethylene alkylphenyl ether phosphates.