JP3276025B2 - Antibacterial acrylonitrile fiber and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial acrylonitrile (hereinafter abbreviated as AN) having a high practical performance and containing a metal compound which is hardly soluble in water and which can be used in a wide variety of uses such as general materials as well as clothing. The present invention relates to a system fiber and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, with the maturation and aging of society and the tendency for a rich and comfortable living environment, the maintenance of health,
There is a growing demand for enhancement, and there is a demand for the appearance of clothing, bedding, interior products, living materials, and the like having cleaner and more comfortable antibacterial performance.

[0003] As one of the methods for imparting antibacterial performance, it is known that silver ions or copper ions exhibit excellent antibacterial properties, and the properties of these metal ions are used to impart antibacterial properties to fibers. There are known ways to do this. For example, Japanese Patent Application Laid-Open No.
As described in JP-A-2-92000 and JP-A-3-199418, sulfonic acid groups, carboxylic acid groups,
In an acrylic fiber having an ion-exchange group such as a hydroxyl group, an antibacterial AN-based material in which silver ions or copper ions are bonded to part or all of the ion-exchange groups to remain as metallic silver, copper or a compound of the metal Means for providing fibers are mentioned.

[0004] One of the different methods for imparting antibacterial performance is as follows.
First, many antibacterial agents have been proposed, regardless of whether they are low-molecular-weight products or high-molecular-weight products, and the mechanism of action has been clarified. Among them, cationic antibacterial agents such as quaternary ammonium salts and protonated amines are known to exhibit strong bactericidal performance due to cell membrane destruction, and are widely used. For example, as a method for imparting antibacterial properties to a polymer forming a fiber by using this, Japanese Patent Publication No.
Japanese Patent Application Laid-Open No. 8-10510 discloses that a polyester or polyurethane fiber is formed by using a dihydric alcohol having a tertiary amino group in a molecule for a part or all of a diol component, and then reacting with a halogenated hydrocarbon. Means of introducing a quaternary ammonium base into fibers to obtain an antibacterial fiber material has been proposed.

However, when a fiber in which silver or copper metal ions are bonded to an ion-exchange group is dyed with a cationic dye, dyeing properties cannot be obtained because the dyeing seat is blocked by the metal ions, or the dye is not dyed. It is exchanged with metal ions, and the metal ions fall off, causing a problem that the antibacterial performance is alive. Further, when the antibacterial fiber material introduced with a quaternary ammonium base is dyed with an anionic dye,
Since the antibacterial site and the dyeing seat are the same quaternary ammonium base or amino group, when dyeing, there is a problem that the antibacterial site is blocked by the dye and the antibacterial performance may be reduced.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an anionic dye having excellent antibacterial performance which does not have the above-mentioned problems, does not lower the antibacterial property by dyeing, and has a small amount of antibacterial sites. To provide an antimicrobial AN fiber and a method for producing the same.

[0007]

An object of the present invention is to provide an amino group and / or quaternary ammonium base.
(Hereinafter simply referred to as amino group).
For the polymerized anionic dye-dyeable AN fibers,該繊
After the formation of the fibers , an amino group and / or a quaternary amino acid containing a metal compound having antibacterial properties and poor water solubility is contained.
Preferably, the metal compound is at least one selected from the group consisting of silver, copper, and zinc, and the metal ion is 1 to 20 as the antibacterial AN fiber having a monium base as a dyeing seat.
A preferable method for obtaining the antibacterial AN fiber as described above is to combine an anionic dye-dyeable AN fiber with a metal ion to form a poorly water-soluble polymer. After treatment with an aqueous solution of a compound containing an acidic group capable of producing a metal compound, the fiber is treated with an aqueous solution of a compound containing a metal ion having antibacterial properties, and the fibers have antibacterial properties and are hardly water-soluble. Metal compound, preferably 1 to 200 m as metal ion
-A means characterized by introducing mol / kg is provided.

Hereinafter, the present invention will be described in detail. In the antimicrobial AN fiber having the specific performance as described above, the AN fiber is
Anionic dye dyeable A copolymerized with amino group-containing monomer
There is no restriction as long as it is formed by N-based polymer,
Preferably 60% by weight or more, more preferably 80% by weight or more of AN and 0.5 to 10% by weight of an amino group-containing monomer and, if necessary, vinyl esters such as vinyl acetate; vinyl chloride, odor Vinyl halides such as vinyl chloride and vinylidene chloride or vinylidenes; lower alkyl esters of (meth) acrylic acid such as methyl acrylate and methyl methacrylate; A consisting of acrylamide, styrene, etc.
It is desirable to use AN-based fibers formed from an N-based copolymer.

The amino group-containing monomer is not particularly limited. For example, it is preferable to use at least one of the monomers represented by Chemical Formulas 1, 2, and 3 in the present invention. (Provided that R ₁ is hydrogen or an alkyl group of C ₄ or less, R ₂ , R ₃ and R ₄
The C ₄ to an alkyl group, respectively, R ₅ is C ₄ following alkylene or hydroxyalkylene group, R ₆ is C ₄
The following alkylene groups, X is Cl, Br, I, CH ₃ CO
O, CH ₃ SO ₄ or indicates SCN, m is an integer of 2 to 4, n is an integer of 0 or 1).

[0010]

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[0011]

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[0012]

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In the present invention, the antibacterial metal compound contained in the fiber must have a poor solubility in water. By having such properties, even when a bleaching treatment, a dyeing treatment, and a washing treatment are performed, excellent antibacterial properties can be imparted permanently without the metal compound in the fibers falling off or being easily eluted. The term “poorly water-soluble” as used in the present invention means that the weight of the metal compound dissolved in 100 g of pure water at 25 ° C. is 0.1 g or less.

Such metal compounds include mercury, silver, copper, zinc,
Iron, lead, and those containing metal ions exhibiting antibacterial activity such as bismuth can be mentioned, but in the present invention, more preferably, from the viewpoint of safety on use, antibacterial effect, silver, copper, zinc This is carried out by adopting at least one kind of the metal ions. Of course, a plurality of types may be used in combination.

In the present invention, the metal compound exhibiting antibacterial properties to be contained in the fiber is not particularly limited.
More preferably, 1 to 20 as metal ions with respect to the fiber.
It is good to contain 0mmol / kg. That is, the content of the metal compound varies depending on the required antibacterial level.If the content is less than the lower limit of the range, it is difficult to obtain sufficient antibacterial performance in a living environment. In a heat treatment step such as drying, a problem of remarkable coloring easily occurs. Further, within this range, sufficient antibacterial performance for daily use or industrial use can be obtained permanently, so that the inclusion beyond the above-mentioned range unnecessarily increases costs and is not industrially advantageous.

As a preferable method for obtaining the above-mentioned antibacterial acrylic fiber, the following means can be used. That is, the above-mentioned AN-containing polymer containing an amino group is subjected to ordinary spinning, and the anionic dye-dyeable acrylonitrile fiber obtained by performing water washing, drawing, and heat treatment as known or known, is bonded to metal ions. It is necessary to introduce an acidic group into an amino group in the fiber by treating with an aqueous solution of a compound containing an acidic group capable of producing a metal compound which is hardly soluble in water. By such treatment, the AN-based fiber is bonded to the metal ion of the compound containing a metal ion exhibiting antibacterial properties as described later without using a functional group present in the AN-based fiber , that is, an amino group-containing monomer.
Group and / or quaternary ammonium salt derived from
The metal compound can be introduced into the fiber with the group maintained as a dye seat for the anionic dye . As a result, problems such as inability to obtain staining properties, reduction in antibacterial properties, and life and death are solved. The aqueous compound solution is appropriately selected depending on the metal exhibiting the antibacterial property to be employed. However, as described later, it is important to generate a metal compound which is hardly water-soluble after binding to the metal ion.

Here, as the compound containing an acidic group capable of forming a metal compound which is hardly water-soluble by binding to a metal ion, for example, thiocyanic acid, antimonic acid, polyphosphoric acid, pyrophosphoric acid, phosphoric acid, tungstic acid, An aqueous solution of a compound having an acidic group such as molybdate, sulfuric acid, or oxalic acid is preferred because it exhibits poor water solubility when bonded to a metal ion having antibacterial properties.

In treating the fiber with the aqueous compound solution having an acidic group, the concentration of the aqueous compound solution is determined by dissolving the AN-based fiber or disturbing the physical properties. Is not particularly limited as long as an acidic group capable of imparting a predetermined amount can be introduced.
A concentration of 00 mmol / l is recommended. The treatment temperature may be any range as long as it does not impair the physical properties of the AN-based fiber, and is appropriately selected within the range of 30 to 140 ° C., and the treatment time is set according to the treatment temperature. After performing such treatment, the fibers are washed with water, dried, and subjected to the next treatment.

Next, it is necessary to treat the fiber into which the acidic group has been introduced with an aqueous solution of a compound containing a metal ion having antibacterial properties. As described above, the acidic group introduced from the inside of the fiber to the surface thereof is required. And the metal ions in the aqueous solution are bonded to each other, whereby a metal compound having antibacterial properties and poorly water-soluble property can be introduced into all layers of the fiber.

The metal compound may be any one containing at least one of compounds containing a metal ion exhibiting antibacterial activity. In particular, silver, copper, and zinc are preferably used, and the compound is used as an aqueous solution. Thereby, a metal ion can be bonded to the acidic group introduced into the fiber.

In treating the fiber into which the acidic group has been introduced with an aqueous solution of a compound containing a metal ion exhibiting antibacterial properties, the treatment concentration does not dissolve the AN fiber or impair the physical properties. It is not particularly limited as long as a metal ion capable of providing a predetermined amount of a metal compound having antibacterial properties in the fiber can be bound to the acidic group, but is generally about 10 to 1000 m · m.
A concentration of ol / l is recommended. The treatment temperature may be any range as long as it does not impair the physical properties of the AN-based fiber, and is appropriately selected within the range of 30 to 140 ° C., and the treatment time is set according to the treatment temperature. The pH of the aqueous solution when treated with an aqueous solution of a compound containing a metal ion exhibiting antibacterial properties
May be bonded to a metal ion exhibiting antibacterial properties and the above-described acidic group.However, if the pH is too high, a metal hydroxide is generated, and it is easy to introduce the metal ion as an aqueous solution into the fiber. If the pH is too low, problems such as difficulty in binding metal ions to the acidic groups introduced into the fiber occur. Therefore, it is generally preferable to treat at pH = 2-4. After performing such treatment, the fibers are washed with water and dried,
An antimicrobial AN fiber that achieves the object of the present invention can be obtained.

In addition to the above-mentioned treatment method, for example, the above treatment may be continuously performed after a water washing step of removing a spinning solvent using a gel structure fiber which is in a fiber forming process after being spun. Alternatively, heat-treated and dried tow-like fibers may be continuously treated.

[0023]

The antimicrobial AN fiber according to the present invention is obtained by introducing a predetermined acidic group to an amino group present in the fiber by ionic bonding using an anionic dye-dyable fiber, and then applying an aqueous solution of a metal compound having antimicrobial properties. By the treatment, the acidic group introduced into the fiber and the metal ion are bonded to each other, whereby the acidic group and the metal ion are bonded to form a fine water-insoluble antibacterial metal compound of a molecular order, and the fiber is formed. It is thought to be retained. Such a specialty would manifest the various characteristics and functions of the present invention.

[0024]

EXAMPLES Examples will be shown below to facilitate understanding of the present invention, but these are merely examples, and the gist of the present invention is not limited thereto. In the examples, parts and percentages are shown on a weight basis unless otherwise specified. The metal ion concentration, antibacterial performance (increase / decrease value difference), and fiber whiteness described in Examples are measured by the following methods. (1) A metal fiber concentration of 0.1 gr sample fiber was wet-decomposed with a 95% concentrated sulfuric acid and a 62% concentrated nitric acid solution, and the solution was atomized using an atomic absorption spectrometer AA855 manufactured by Jarre Ash Co., Ltd. The absorbance was measured and determined. (2) Difference in increase / decrease value Based on “Processing effect test of antibacterial and deodorant processed products” of Textile Sanitary Processing Council, the number of bacteria was measured using Staphylococcus aureus, and the difference in increase / decrease value was obtained from Equation 1.

[0025]

(Equation 1)

Here, the difference between the increase and decrease values means the average number of bacteria immediately after inoculation of the unprocessed sample as A, the average number of bacteria after 18 hours of culture as B, and the average number of bacteria of the antibacterial processed sample after 18 hours of culture. C is calculated by Equation 1. Here, the number of measurements is three, and in general, it is considered that there is antibacterial performance if the difference between the increase and decrease values is 1.6 or more. (3) Fiber whiteness The sample fibers were aligned in the same direction, and 45 were measured using a spectrophotometer.
The reflectance with respect to the wavelength of 8, 558, 595 nm is obtained based on the magnesium oxide plate, and is shown by the yellowness calculated by Expression 2. A smaller value indicates better whiteness, and a larger value indicates lower whiteness.

[0027]

(Equation 2)

However, R458, R558, R5 in the formula
95 indicates the reflectance for light of 458, 558, and 595 nm, respectively.

[0029]

【Example】

[1] AN 85.6% obtained by polymerization according to a conventional method,
An AN polymer composed of 11.2% of vinyl acetate and 3.2% of N, N-dimethylaminoethyl methacrylate is dissolved in a 45% aqueous solution of rodane soda to prepare a spinning solution having a polymer concentration of 12%. did. 10% of the stock solution,
Extruded into 3% rodin soda aqueous solution, then washed with water,
Drawing and heat treatment were performed to prepare an anionic dye-dyeable AN-based fiber. 200 g of the fiber was put into 2 l of each solution of rodin soda, pyrophosphoric acid decahydrate, and sodium oxalate at 100 mmol / l, treated at 95 ° C. for 30 minutes, washed with water, and dried. SCN ^-,
P ₂ O ₇ ^4- and C ₂ O ₄ ^2- acidic groups were introduced into the fiber.
Next, an aqueous silver nitrate solution as a silver ion solution was added to copper (I
I) An aqueous solution of copper sulfate as an ionic solution and an aqueous solution of zinc chloride as a zinc ion solution were each adjusted to 10 mmol·l / l.
After H3, 10 g of the fiber treated above was added, treated at 98 ° C. for 30 minutes, washed with water and dried. Seven kinds of antibacterial AN fibers 1 to 7 were prepared. Table 1 also shows the metal content of the fiber and the difference in the increase / decrease in the number of bacteria showing antibacterial properties.

[0030]

[Table 1]

As shown in Table 1, it is found that the fibers introduced with the metals and metal contents recommended in the present invention exhibit excellent antibacterial properties.

[0032]

【Example】

[2] Next, 0.1, 0.2, 1.5, 6.0, 10.
Example 1 100 ml of each silver nitrate aqueous solution adjusted to 0.13.0 molmol / l was adjusted to pH 3 with a 1% nitric acid aqueous solution, and
10 g of each of the fibers into which SCN ^- was introduced prepared at No. 1 were added, and treated at 98 ° C. for 30 minutes, washed with water and dried. Six types of fibers 9 to 14 were prepared.
An aqueous solution of copper sulfate was prepared in the same manner as described above, and the fiber into which P ₂ O ₇ ^4- introduced in Example 1 was introduced was treated. Sixteen antibacterial AN fibers of 15 to 20 were prepared. In addition, No. Reference numeral 8 denotes an untreated reference sample that has not been subjected to acid group introduction and metal ion treatment.

[0033]

[Table 2]

As shown in Table 2, No. less than the metal content preferably recommended in the present invention. 9 and No. 9 No. 15 shows antibacterial properties as compared with the untreated fiber, but has a small value due to the difference in increase / decrease, and the metal content exceeds the range which is preferably recommended in the present invention. 14 and No. No. 20 shows sufficient antibacterial properties, but has low whiteness. In addition, the sample No. which is not this invention. 8 (Reference sample) and Sample No. of the present invention.
The dyeing test for anion dye No. 12 was conducted according to a conventional method using Suminol Fast Cyanine Green G (Sumitomo Chemical Co., Ltd.).
5% owf solution and sulfuric acid at pH = 3
And at a bath ratio of 1: 100 at 93 ° C. for 60 minutes. As a result, the exhaustion rate of the dye was no. 8 is 67.3
%, No. 12 was 67.0%. Thus N
o. No. 12 is No. It shows that the dyeing property is not inferior to that of No. 8 and has both the antibacterial property and the dyeing property that overcome the conventional disadvantages.

[0035]

【Example】

[3] No. 2 obtained in Example 2 JI using 12 fibers
According to SL-0217,103 method, 2 to 1 liter of water
g of synthetic detergent (Monogen Yuni Co., Ltd., manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved, the washing liquid was set to 40 ° C., and fibers were added so that the bath ratio was 1:30, and washing was performed. 5,
Table 3 shows the antibacterial properties after washing 10 or 20 times repeatedly.

[0036]

[Table 3]

The antimicrobial AN fiber according to the present invention shows sufficient antimicrobial properties even after 20 washes, and it is found that the antimicrobial AN fiber according to the present invention contains a poorly water-soluble metal compound and has antimicrobial durability.

[0038]

The antimicrobial AN fiber of the present invention described above is
An acidic group is introduced into the fiber by introducing an acidic group using an amino group in the anionic dye-dyeable AN-based fiber and binding a metal ion having an antibacterial property to the acidic group. Is considered to be bound by the acid group and the metal ion to generate a fine water-insoluble antibacterial metal compound of a molecular order, which is retained in the fiber. Permanent and excellent antibacterial properties are imparted, and fiber properties, fiber whiteness,
It is a remarkable effect of the present invention to provide a fiber which does not impair the dyeability of the fiber and to provide a method for producing the fiber in an industrially advantageous manner. The fiber of the present invention having such excellent advantages can be processed into yarn, knitted fabric, non-woven fabric and the like, and is used for comfortable clothing, bedding, interior products, living materials, industrial materials, medical fiber materials, and the like. Widely used in the field.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D01F 6/54 D06M 11/00-11/84 D06M 13/00-13/535

Claims (4)

(57) [Claims] 1. An amino group and / or quaternary ammonium
For the monomer containing an abasic in copolymerized anionic dye-dyeable acrylonitrile fiber, after the fiber formation, for the additional inclusion of a metal compound which is and poorly water-soluble have antimicrobial properties
Amino group and / or quaternary ammonium base
Acrylonitrile fiber with a dyed seat . 2. The antibacterial acrylonitrile-based fiber according to claim 1, wherein the metal compound having antibacterial properties and poor water solubility is at least one selected from the group consisting of silver, copper and zinc salts. 3. The content of a metal compound having antibacterial properties and being hardly soluble in water is 1 to 200 mmol as a metal ion.
3. The antibacterial acrylonitrile-based fiber according to claim 1 or 2, wherein 4. An anti-microbial metal after treating an anionic dye-dyable acrylonitrile fiber with an aqueous solution of a compound containing an acidic group capable of forming a metal compound which is hardly soluble in water by binding to a metal ion. A method for producing an antibacterial acrylonitrile-based fiber, comprising treating with an aqueous solution of a compound containing ions and introducing a metal compound having antibacterial properties and poorly water-soluble property into the fiber.