JPS636173A - Antibacterial acrylic fiber and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an antibacterial acrylic fiber having excellent durability and antibacterial activity, and a method for producing the same.

<Prior art> Various microorganisms such as bacteria and molds exist in the normal living environment. In particular, under high temperature and humidity conditions, these microorganisms will actively reproduce, causing rotting, fermentation, and
It may emit an unpleasant odor or be attacked by athlete's foot. Therefore, various antibacterial agents have been developed, and attempts have been made to impart antibacterial properties to various stem materials.

Acrylic synthetic fibers are widely used for clothing and bedding, but in recent years they have been used in carpets used in the sanitary field, as well as in socks, underwear, blankets, sports clothing, etc. that come in contact with sweat secreted by the human body, and are antibacterial and odor-resistant. There has been a strong demand for books with sexual content.

There was a time when organic tin and organic mercury compounds were used to impart antibacterial properties to fibers, but the toxicity of these compounds has become a problem, and now most of them are no longer used. Part is out of use.

Recently, quaternary ammonium salts have been attracting attention as particularly safe antibacterial and antifungal agents. For example, JP-A-57
Japanese Patent No. 51874 discloses a carpet in which an organosilicone quaternary ammonium salt is adsorbed and a method for producing the same. However, silicone quaternary ammonium salts are reactive towards cellulose fibers and exhibit washable and durable antibacterial effects, but synthetic ffi!
Only temporary antibacterial effects have been obtained against bacterial infections. Moreover, this silicone-based quaternary ammonium salt has water absorbing properties and has the disadvantage of inhibiting water absorbing properties.

It is undesirable for use in underwear, underwear, socks, and other applications where sweat tends to adhere, as it tends to get stuffy and is unpleasant.

On the other hand, as a method for producing an antibacterial material that does not inhibit water absorption, Japanese Patent Publication No. 56-34203 discloses that a polymeric substance having an acidic group and bis-(p-chlorophenyldiguanide)-
A method of reacting hexane or a salt thereof is disclosed. This method has the drawback that although the antibacterial material itself has some durability against washing with water, it lacks resistance to wet washing and dry cleaning.

Furthermore, when the antibacterial material is applied to fibers using fibers as a carrier, the antibacterial properties of the fibers cannot reach a practical level.

Further, JP-A-58-115116 discloses a method for producing antibacterial acrylic synthetic fibers by wet spinning an organic solvent solution of an acrylonitrile polymer and a diphenyl ether derivative. In this method, a diphenyl ether derivative, which is a non-reactive antibacterial component, is dissolved in an organic solvent and then added and mixed into the spinning stock solution.During wet spinning, many needles of diphenyl derivative are eluted during the spinning bath, so the diphenyl ether derivative is not contained in the fiber. The yield of diphenyl ether derivatives is poor,
Furthermore, since the diphenyl ether derivative is dispersed and mixed throughout the fiber, it has the drawback of poor efficiency and increased cost.

<Problems to be Solved by the Invention> The object of the present invention is to have an antibacterial effect that inhibits the growth of bacteria on fibers, and to have an antibacterial effect that is durable against washing and dry cleaning. Our objective is to provide acrylic synthetic fibers. Another object of the present invention is to provide a method for manufacturing such antibacterial acrylic synthetic fibers industrially easily and inexpensively. , an acrylic compound containing an alkylene glycol unit, and an acidic group-containing monomer formed by bonding an antibacterial component as essential comonomers, and a multicomponent copolymer having a monomer equivalent content of the acrylonitrile of 5 or more. This is achieved by using antibacterial acrylic fibers, which are characterized by being present on the surface of the acrylic fibers.

Further, the second object of the present invention is to combine acrylonitrile and
A cationic antibacterial compound is reacted with a multi-component copolymer in which an acrylic compound containing an alkylene glycol unit and an acidic group-containing monomer are essential comonomers, and the content of the acrylonitrile in terms of monomer is 5% by weight or more. This is achieved by a method for producing antibacterial acrylic fibers, which is characterized by immersing the acrylic fibers in a treatment solution containing the antibacterial acrylic copolymer obtained in the bath and treating the acrylic fibers in the bath.

In the above method, an electrolyte is allowed to coexist in the processing solution, and
It is preferable to immerse ordinary acrylic synthetic fibers in this treatment liquid and then heat-treat the fibers.

In the present invention, the presence of acrylonitrile in the antibacterial acrylic copolymer exhibits excellent contact properties with respect to acrylic synthetic fibers. In addition, as a result of the acrylic compound containing alkylene glycol units depositing and adhering to the surface of acrylic synthetic fibers, it has excellent durability and can exhibit a high level of antibacterial properties. It shows its effectiveness.

The acrylic fiber used in the present invention has acrylonitrile as its main component, and contains methyl acrylate, methyl methacrylate, sodium styrene sulfonate, sodium allyl sulfonate, 2-
Examples include fibers copolymerized with one or more types of methyl-5-vinylpyridine, and fibers copolymerized or blended with vinylidene chloride for the purpose of imparting flame retardance. In addition, acrylic synthetic fibers can be used alone, as well as synthetic fibers such as polyester, polyamide, polyurethane, polyolefin, cellulose-based semi-synthetic fibers, etc.
It may be mixed with natural fibers such as cotton, silk, and wool, and its form is not limited and may be any suitable material such as thread, cotton, knitted fabric, carpet, or nonwoven fabric.

Although the antibacterial component used in the present invention is not limited, antibacterial components that react with acidic group-containing polymers (including copolymers) are preferred.

Such reactive antibacterial components include basic groups such as amidine groups and guanidine groups, or their sodium salts;
Examples include compounds having salts such as potassium salts and ammonium salts, and quaternary ammonium salts. Compounds containing an amidine group include 4,4'-stilpene-dylepooxamidine-diisethionate (i.e., stilbamidine isethionate), N'-(4-chloro-
2-Methyl-phenyl)-N,N-dimethyl-metanimide (i.e., chlordimeform), etc.; as compounds containing a guanidine group, 1.17-cyguanidino-9-azaheptadecane (i.e., guazatine); p-(
Chlorophenyl diguanide)-hexane (i.e., chlorhexidine), p-benzoquinone-amidino-hyde 2
Examples of quaternary ammonium salts include syn-thiosemicarbazone (i.e., ambazone), benzalkonium, etc.
Examples include chloride and benzethonium chloride. Of course, these compounds are just examples, and it goes without saying that compounds other than those mentioned above can also be used. Among the above compounds, p
-(chlorophenyldiguanide)-hexane (i.e., chlorhexidine) or a salt thereof is preferred.

The antibacterial component having such a basic functional group is used by being reacted with an acidic group-containing copolymer that reacts with the antibacterial component. The acidic group-containing monomer constituting the acidic group-functionalized polymer includes acidic groups such as sulfonic groups, carboxyl groups, phosphonic groups, and phenolic hydroxyl groups, or salts thereof such as sodium salts, potassium salts, and ammonium salts. Examples include monomers having the following.

Examples of monomers having a sulfonic group include styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, nurphopropyl acrylate, sulfopropyl methacrylate, 3
-Chloro-4-vinylbenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloyloxybenzenesulfonic acid, 2-acryloyloxynaphthalene-2-sulfonic acid, 2-methacryloyloxynaphthalene-2-sulfonic acid , 2-hydroxy-
3-methacryloyloxypropylsulfonic acid, etc.
Examples of monomers containing carboxyl groups include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, 3-butene-1,2,3-tricarboxylic acid, 4-pentenoic acid, etc. Examples of monomers having a phosphonic group include allylphosphonic acid, acidophosphoxyethyl methacrylate, 3-chloro-2-acidophosphoxypropyl methacrylate, 1-methylvinylphosphonic acid, 1-phenylvinylphosphonic acid, 2-
Phenylvinylphosphonic acid, 2-methyl-2-phenylvinylphosphonic acid, 2-(3-chlorophenyl)vinylphosphonic acid, 2-diphenylvinylphosphonic acid, etc.
Examples of the monomer having a phenolic hydroxyl group include O-oxystyrene and O-vinylaniline. Such monomers may be used alone or in combination with 2a1 or more.

Examples of the acrylic compound having an alkylene glycol unit in the present invention include the following compounds (4) and
can be opened.

(In the formula, R is H or a lower alkyl group, R' is CL, Br
, I, OCHs, OC2H5, SCH3,5CzHs, and m and t are 0≦m and 10.10≦L)
Compounds represented by: Specific examples include methoxypolyethylene glycol acrylate, ethoxypolyethylene glycol acrylate, ethoxypolyethylene glycol methacrylate, chlorine polyethylene glycol methacrylate, and methoxypolypropylene glycol polyethylene glycol methacrylate.

(B) The molecular weight of the polyoxyethylene segment is 4
A block polymer of polyoxyethylene glycol having a molecular weight of 00 to 10,000, or a polyoxyethylene segment having the molecules 1,100 to 100
A block polymer consisting of two segments of polypropylene segments having 0.
Vinyl compounds having a polymerizable vinyl group consisting of acrylic or methacrylic or polymers thereof; Specific examples thereof include polyethylene glycol dimethacrylate, polyethylene glycol trimethacrylate, block polyethylene polypropylene glycol dimethacrylate, and derivatives thereof or their polymers. Examples include vinyl polymers.

Such an acidic group-containing monomer and an acrylic compound having an alkylene glycol unit in an amount of 5% by weight or more, preferably 10 to 60% by weight! An antibacterial reaction product can be obtained by reacting an acrylic copolymer copolymerized with a basic antibacterial component, particularly preferably 20 to 50% by weight of acrylonitrile.

A typical example of a method for applying the antibacterial acrylonitrile-containing acrylic copolymer to acrylic synthetic fibers is as follows:
There is a method in which the acrylic synthetic fiber is immersed in the same treatment bath in which an electrolyte is added to an antibacterial treatment agent made of an aqueous dispersion of the above-mentioned antibacterial acrylonitrile-containing acrylic copolymer.

The electrolyte is used to precipitate the acrylic compound having alkylene glycol units contained in the antibacterial acrylic copolymer. Specific examples include sodium, potassium, ammonium, sulfuric acid, hydrochloric acid, phosphoric acid, etc.
Examples include inorganic salts such as magnesium, organic salts such as sodium and ammonium salts of various organic carboxylic acids such as acetic acid and formic acid, and their salts. Sodium sulfate (mirabilite) is particularly preferred.

In the present invention, the amount of the antibacterial reaction product attached to the fibers is 0.05 to 30% by weight, particularly 0.4 to 10% by weight, in terms of solid content.
Weight percent is preferred. As an antibacterial component, it is o, o for fibers.
A range of os to 5% by weight, particularly 0.04 to 1% by weight is preferred. If the amount of adhesion is too small outside of this range, it will be difficult to achieve the purpose of the present invention, and the durable antibacterial performance will be inferior; conversely, if it exceeds the above range, the texture will be rough and hard.
% As a normal clothing and interior material, it loses its commercial value and is also unsafe.

Undesirable.

If necessary, a softener, an antistatic agent, a water repellent, a surfactant, etc. may be added to the treatment solution for the antibacterial reaction product.

<Effects of the Invention> The antibacterial acrylic fiber of the present invention is an acrylic copolymer containing an antibacterial component containing acrylonitrile, which is the same substrate and has strong adhesive properties with affinity for acrylic synthetic fibers, as a copolymer component. Since it uses coalescence, it has the effect of firmly fixing it to acrylic synthetic fibers. In addition, since the acrylic compound having alkylene glycol units in the acrylic copolymer containing antibacterial components precipitates and adheres to the surface of the acrylic synthetic fiber, it is more firmly fixed and exhibits more durable self-cutting resistance. The antibacterial acrylic synthetic fiber of the invention exhibits antibacterial and deodorizing effects that suppress the growth of bacteria attached to sweat and prevent sweaty odors, especially in underwear, socks, etc. where sweat is easily absorbed due to perspiration. It is.

Furthermore, since an acrylic compound having an alkylene glycol unit is used as the main component of the acrylic copolymer containing an antibacterial component, water absorbency can also be imparted to the acrylic synthetic fiber at the same time.

<Example> Example 1゜ Monomer mixture consisting of 20 parts of acrylonitrile, 20 parts of methoxypolyethylene glycol methacrylate (total molecular weight: 1000), and 3 parts of 2-acrylamido-2-methylpropanesulfonic acid as the acidic group-containing monomer. water 10
Dissolve in a mixed solvent of 0 parts of Improper Tool and 70 parts of N
Copolymerization was carried out by heating and stirring for 1 hour at 60 to 70° C. in a two-gas atmosphere. Thereafter, the copolymer obtained in this way (solid content) was cooled, and chlorhexidine 10-fold fj
A solution obtained by heating and dissolving r% in ethylene glycol monomethyl ether is added and reacted. Next, unpolymerized acrylonitrile was removed under reduced pressure and the water was drained to obtain a hydrogen dispersion of an acrylic copolymer containing chlorhexidine having a solid content of 15.

Next, as shown in Table 1, an antibacterial treatment solution was prepared by adding anhydrous Ajiao to this hydrogen dispersion of the acrylic copolymer containing an antibacterial component.

Therefore, acronitrile 95, which was refined and dried according to the conventional method,
Copolymerized acrylonitrile fiber m1 consisting of 7 moles, 4 moles of methyl acrylate, and 1 mole of sodium allylsulfonate
．． A 100-t acrylic knitted fabric spun and knitted using 5 denier and 76 m fiber length was dyed using the following dyeing recipe and conditions.The dyed knitted fabric was immersed in the antibacterial treatment solution prepared above, and 70 t: It was treated for 30 minutes.

This antibacterial treatment solution was added to the dyeing treatment solution to carry out antibacterial treatment simultaneously with dyeing.

The antibacterial acrylic synthetic l# fibers thus obtained were washed or dry cleaned to evaluate their antibacterial properties. As shown in Table 1, the results showed that a durable and high level of antibacterial activity was obtained, and water absorption was hardly inhibited.

Evaluation method A. Washing method Using a household washing machine, New Beads (manufactured by Kao Soap) 2
1/1. Wash for 5 minutes at a temperature of 40°C and a bath ratio of 1:50, then remove liquid, dehydrate, and rinse for 5 minutes with overflow. This is carried out once per wash, and dry cleaning is performed using a rotary dry cleaning machine with Park Clean 3.7
t, room temperature, and bath ratio of 1:12 for 15 minutes. Then, remove the liquid and air dry in a fume hood. This is considered as one dry cleaning.

C. Antiphylaxis (halo test) Prepare a mixture of Staphylococcus aureus 1X10'' bacteria/- in tryptone ear agar 100+n/! at a ratio of 0.1-.

Next, 10- was placed in a Petri dish to make a thin layer medium, and a test piece of 3 m x 3 α was placed on top of the medium, and the medium was placed in an oven at 37° C. for 24 hours to be cultured. Bacterial growth was visually observed and antibacterial properties were determined.

Judgment: ◎: There is a transparent zone under and around the sample that inhibits the growth of bacteria.

○: There is a zone of inhibition of bacterial growth under and around the sample, but there is a slightly opaque area.

Δ: There are about 7 bacterial growth inhibition zones under and around the sample.

×: There is an inhibition zone only under the sample, but the area of the surrounding inhibition zone is extremely small and it is quite opaque.

×X: There is no inhibition zone at all.

2. ffJ'f Meltability The sample was brought into contact with a copper rod having a diameter of 8 cm heated to a predetermined temperature for 5 seconds under its own weight, and whether or not the contact area melted and a hole was formed was judged with the naked eye.

E. Fix a water-absorbing sample to a plate with a diameter of 10 m or more so that the surface is horizontal, and drop one drop of distilled water from a height of 50 m using a syringe. Measure the water absorption time until it stops absorbing water.

Comparative Example 1゜The 100-inch acrylic knitted fabric used in Example 1 was dyed in the same manner as in Example 1 without antibacterial treatment. As shown in Table 1, no antibacterial properties were obtained.

Comparative Example 2 Instead of the antibacterial treatment liquid of the present invention, an antibacterial treatment liquid consisting of silicone quaternary ammonium salt antibacterial agent AX-43-021 (Tone Silicone ■) was prepared as shown in Table 1. did.

The 100-inch acrylic knitted fabric used in Example 1 was subjected to antibacterial treatment after or simultaneously with dyeing in the same manner as in Example 1 using the antibacterial treatment solution prepared above. The antibacterial properties of the acrylic 10096 knitted fabric thus obtained were evaluated.

As shown in Table 1, almost no antibacterial properties were observed and water absorption was inhibited.

Example 2 In the same manner as in Example 1, an antibacterial treatment liquid was prepared by adding Glauber's salt (anhydrous) to an aqueous dispersion of an acrylic copolymer containing an antibacterial component.

Therefore, acrylic No. 42 cotton yarn was dyed with cheese in a dark blue color according to a conventional method. Next, Fix processing was performed using the following Fix prescription and conditions. This Fix-treated nine-knit fabric was immersed in the antibacterial treatment solution prepared above and heated at 60°C
Processed for minutes. After that, a softening treatment was performed using a nonionic softener.

Fix prescription/conditions: Add this antibacterial treatment liquid to the Fix treatment liquid,
Antibacterial treatment was performed at the same time as ix. Thereafter, a softening treatment was performed using a nonionic softener.

As shown in Table 1, the antibacterial properties of the antibacterial acrylic No./cotton yarn obtained in this way show that it has excellent and durable antibacterial properties, and at the same time has almost no inhibition of water absorption. Ta.

Example 3 Socks made of 36 wool count acrylic 80/nylon 15/wool blended yarn dyed pale blue and 38 wool count acrylic 72/wool blend yarn were treated with the same antibacterial ingredients as those made in Example 1. It was immersed in an antibacterial treatment solution prepared by adding Glauber's salt (anhydrous) to an aqueous dispersion of the containing acrylic copolymer, and heated at 65°C.
×20 minutes of treatment. Thereafter, a soft finish was applied using a nonionic softener.

The antibacterial properties of the antibacterial socks obtained in this way are shown in Table-
As shown in 1, excellent antibacterial activity was obtained. It was also observed that water absorption was not inhibited.

Comparative Example 3 20 parts of ethyl acrylate, 20 parts of butyl acrylate, 2-acrylamide-2- as acidic group-containing monomer
A monomer mixture consisting of 3 parts of methylpropanesulfonic acid was dissolved in a mixed solvent of 100 parts of water and 70 parts of Improper Tool, and copolymerized by heating and stirring at 60 to 70°C for 5 hours in a N2 gas atmosphere. .

Thereafter, the copolymer (solid content) obtained in this way is heated and dissolved with 10 parts by weight of chlorhexidine in ethylene glycol monomethyl ether and reacted. The drained water was added to obtain a hydrogen dispersion of a chlorhexidine-containing acrylic copolymer having a solid content of 15%.

Next, as shown in Table 2, Glauber's salt (anhydrous) was added to the aqueous dispersion of the antibacterial acrylic copolymer to prepare an antibacterial treatment liquid.

Therefore, the same acrylic 100-chi knitted fabric used in Example 1 was treated with the antibacterial treatment solution prepared above instead of the antibacterial treatment solution used in Example 1, and was treated with the same antibacterial treatment as in Example 1. Antibacterial treatment was also performed at the same time as staining.

The results of evaluating the antibacterial properties of the acrylic synthetic fibers treated in this way are as shown in Table 2. Antibacterial treatment agents have not been shown to have durable antibacterial activity on acrylic synthetic fibers.

Table-2

Claims (1)

[Scope of Claims] 1. Acrylonitrile, an acrylic compound containing an alkylene glycol unit, and an acidic group-containing monomer formed by bonding an antibacterial component are essential comonomers, and the monomer equivalent content of the acrylonitrile is 5% by weight. % or more of a multicomponent copolymer is present on the surface of the acrylic fiber. 2. The antibacterial acrylic fiber according to claim 1, wherein the content of the antibacterial component is 0.005% by weight or more based on the weight of the acrylic fiber. 3. A multicomponent copolymer containing acrylonitrile, an acrylic compound containing an alkylene glycol unit, and an acidic group-containing monomer as essential comonomers, and in which the monomer content of the acrylonitrile is 5% by weight or more, is added with a cationic antibacterial agent. 1. A method for producing antibacterial acrylic fibers, which comprises immersing acrylic fibers in a treatment liquid containing an antibacterial acrylic copolymer obtained by reacting an antibacterial compound and treating the acrylic fibers in the bath. 4. The method according to claim 3, wherein the treatment liquid contains an electrolyte.