JP3228382B2 - Acrylic fiber having antibacterial and antifungal properties and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an acrylic fiber having antibacterial and antifungal properties.

[0002]

2. Description of the Related Art Antibacterial properties have been imparted to sheets, blankets, futons, carpets, mats, etc. for preventing infection of pathogenic bacteria in hospitals and other sanitary fields, or antibacterial deodorization for socks, sports clothing and the like. With regard to imparting properties, various methods have been proposed for incorporating an antibacterial agent into fibers by kneading or post-processing during fiber formation. For example, a method of kneading an inorganic antibacterial agent such as zeolite carrying an antibacterial metal such as silver or zinc into a polymer at a spinning stage, or an organic antibacterial agent such as a quaternary ammonium salt type at a finishing stage of a fiber product. A method of attaching to a fiber by using a binder together is known, and when attaching an antibacterial agent to the fiber in the finishing step by the applicant himself,
An antibacterial treatment method having no restriction on the application time of post-processing is disclosed in
-106165.

On the other hand, antibacterial agents used for imparting antibacterial properties rarely have fungicidal properties, that is, they also have antifungal properties very rarely. Usually, when they also have antifungal properties, a separate antifungal agent is used for kneading. It is carried out by embedding or post-processing, or in combination with an antibacterial agent. Generally, a method of imparting antifungal properties by attaching an antifungal agent to fibers by post-processing is used.

[0004]

However, in the post-processing method, whether individually or simultaneously imparting antibacterial and antifungal properties, the antibacterial and / or antifungal agent usually adheres to the fiber via a binder. However, if a large amount of binder is used to improve the durability of the imparted antibacterial and antifungal properties, the effect of imparting those effects will be insufficient, and the amount of binder used will decrease. When used or not used, of course, it is not durable, and particularly, the antibacterial agent and the antifungal agent are largely dropped off by washing. An object of the present invention is to provide an acrylic fiber having an antibacterial property and an antifungal property excellent in washing durability by a post-processing treatment for imparting the antibacterial property and the antifungal property at the same time.

[0005]

The present invention provides an antibacterial agent (A)
And the adhesion rate of the antifungal agent (B) to the acrylic fiber satisfies the following formulas (1) and (2), a poor solvent for the acrylic fiber, and a good solvent for (A) and (B) Acrylic fiber having antibacterial and antifungal properties, characterized in that the total extraction ratio of (A) and (B) with a solvent is 50% by weight or less.
Wei, located in 0.05% by weight ≦ a + b ≦ 5.0% by weight Equation (1) 0.3 ≦ a / b ≦ 1.0 Equation (2) (where, a is the concentration of the (A) in the fiber (weight %),
b indicates the concentration (% by weight) in the fiber of (B))

[0006] In the acrylic fiber of the present invention, the antibacterial agent (A) and the antifungal agent (B) are required to have an adhesion rate to the fibers satisfying the above formulas (1) and (2). If the sum of the concentrations of the antimicrobial agent (A) and the antifungal agent (B) a + b is less than 0.05% by weight, the intended effect cannot be obtained. Fiber properties, texture, etc. The ratio a / b of the concentrations of the antibacterial agent (A) and the antifungal agent (B) is such that the maximum dilution of the antifungal agent against fungi is larger than the maximum dilution of the antifungal agent against fungi. From 0.3 to 1.0, if it is less than 0.3, the antibacterial property is not sufficiently expressed, and if it exceeds 1.0, the antifungal property is not sufficiently expressed, and the antibacterial property and the antifungal property are simultaneously well-balanced. For expression, preferably,
The antibacterial agent (A) and the antifungal agent (B) are composed of the antibacterial agent (A) 0.1
1.0 to 3.0% by weight, antifungal (B) 1.0 to 3.0% by weight
Is attached to the fiber so that the concentration in the fiber satisfies the above formulas (1) and (2).

In the acrylic fiber of the present invention,
Solvents which are poor solvents for acrylic fibers and good solvents for both the antibacterial agent (A) and the antifungal agent (B), for example, alcohols such as methanol and ethanol, and acetone;
Antibacterial agent (A) with ketones such as methyl ethyl ketone,
The total extraction rate of the antifungal agent (B) is 50% by weight or less, preferably 30% by weight or less, and the antibacterial agent (A) and the antifungal agent (B) adhere very firmly to the fiber. Antibacterial and antifungal properties have excellent durability.

[0008] When the acrylic fiber of the present invention is produced by treating the acrylic fiber with an antibacterial agent (A) and an antifungal agent (B), a specific affinity promoter (C) is used during the treatment. It can be produced by being present and treating at a temperature above the second order transition point. Hereinafter, the production of the acrylic fiber of the present invention will be described.

The antimicrobial agent (A) used in the present invention is desirably poorly water-soluble from the viewpoint of durability. 4,4'-Trichlorocarbanilide is used as the most preferred. For example 3,
4,4'-Trichlorocarbanilide has a very strong antibacterial activity against Staphylococcus aureus and lactic acid bacteria, which are a kind of Gram-positive bacteria, and has excellent safety against oral toxicity and skin irritation. Has the property. As the antifungal agent (B), oxybenzoic acid esters are most preferably used because they have antifungal performance and high safety for the human body. This oxybenzoic acid ester has excellent antifungal performance against black mold, blue mold, koji mold and the like, and has extremely high safety which is also recognized as a food additive.

Examples of the oxybenzoic acid ester include methyl oxybenzoate, ethyl oxybenzoate, propyl oxybenzoate, and butyl oxybenzoate, and may be used alone or as a mixture.

Affinity promoter (C) used in the present invention
Acts as a dissolving agent on the antibacterial agent (A) and the antifungal agent (B) to stably disperse in water, and also acts as a carrier for the fiber, and acts as a carrier for the fiber. ) Very strongly adheres to the fibers. The affinity promoter (C) is represented by the above general formula, and is a compound in which alkylene oxide is added to alcohol or phenol, a compound in which 2 to 10 mol of ethylene oxide is added to 2-ethylhexyl alcohol, and a compound in which phenol is ethylene oxide. Are preferably used.

The polyoxyethylene nonionic activator (D) used in the production of the fiber of the present invention is a dispersant for obtaining a stable aqueous dispersion used for the treatment, Ether, polyoxyethylene alkyl phenyl ether, etc., wherein the alkyl group of the polyoxyethylene alkyl ether has 12 carbon atoms.
~ 18, the number of moles of ethylene oxide is 20 ~ 30, and the polyoxyethylene alkyl phenyl ether has 8 ~ 12 carbon atoms, and the number of moles of ethylene oxide is 10 ~ 30. It is preferably used in terms of affinity for

The antibacterial agent (A) is 3, 4, 4 'since it is preferably used for producing the fiber of the present invention.
In the case where trichlorocarbanilide and oxybenzoate are used as the antifungal agent (B), the concentration of 3,4,4'-trichlorocarbanilide and oxybenzoate in the aqueous dispersion is 0. 0.05-5.0
%, And 0.05 to 15.0% by weight, and the affinity promoter (C) was 3, 4, or 3, as shown in Examples described later .
5 to 16.7 times that of 4'-trichlorocarbanilide , preferably
Properly is a concentration of about 5-fold, polyoxyethylene-based nonionic surfactant (D), the affinity accelerator (C) and the same degree of concentration. The aqueous dispersion is prepared by adding a predetermined amount of each component of 3,4,4'-trichlorocarbanilide, oxybenzoate, an affinity promoter (C) and a nonionic activator (D) directly to water. To form a composition containing 3,4,4'-trichlorocarbanilide, oxybenzoic acid ester, an affinity promoter (C), and a nonionic activator (D) in a predetermined component ratio. The method is performed by, for example, adding and dispersing the mixture, and is not particularly limited, but the latter method is preferably used.

In the present invention, 3,4,4'-trichlorocarbanilide and oxybenzoic acid ester are dispersed in water in the presence of an affinity promoter (C) and a nonionic activator (D). An aqueous dispersion is prepared, and the resulting aqueous dispersion is immersed in acrylic fiber, impregnated with a pad or the like, and heated while the fiber is impregnated with the aqueous dispersion. Heating may be either wet heat or dry heat, but the processing temperature is determined by the above formula.
In order to adhere so as to satisfy (1) and (2), the temperature must be equal to or higher than the second transition point of the acrylic fiber. At a temperature lower than the second transition point, 3,4,4'-trichlorocarbanilic acid is required. Unsatisfactory adhesion results between the lid and the oxybenzoate are produced. The specific processing temperature is 80 ° C. or higher, and the processing time varies depending on the processing method, but is several minutes to several tens of minutes. In the present invention, as long as the object of the present invention is not hindered, it is also possible to produce the fiber of the present invention by performing treatment simultaneously with other treatments such as dyeing. As the form of the acrylic fiber in the present invention, cotton, tow, yarn, woven fabric,
It may be a knitted fabric, a nonwoven fabric, or the like, or may be in a state in which these are being formed.

[0015]

The present invention will be described below in more detail with reference to examples. In the examples, the concentrations of antibacterial agent and antifungal agent in the fiber, antibacterial property and antifungal property were determined by the following methods. Concentration of antibacterial agent and antifungal agent in fiber; Dissolve a certain amount of acrylic fiber for measurement in dimethylformamide, dilute with dimethylformamide, and add dropwise to methanol to elute antibacterial agent and antifungal agent in methanol It was determined from a calibration curve previously determined by liquid chromatography. Antibacterial activity: The difference between the increase and decrease in the number of bacteria caused by Staphylococcus aureus and resistant Staphylococcus aureus was determined based on the bacterial count method defined by the Textile Sanitary Processing Council. The difference of 1.6 or more of the increase and decrease values of the number of bacteria is a criterion for antibacterial activity. Antifungal property: According to JIS Z2911 mold resistance test method. Grade 2 or higher exhibits mold resistance.

Example 1 Cotton (bright, 3 denier, cut length 76 mm) of Super Balzer (flame-retardant acrylic fiber manufactured by Mitsubishi Rayon Co., Ltd.) was treated under the conditions shown in Table 1. Table 1 shows the state of adhesion of the obtained cotton antibacterial agent and antifungal agent to the fibers. In addition, the total extraction rate of the antibacterial agent and the antifungal agent showed the result of performing the Soxhlet extraction method with methanol for 2 hours.

[0017]

[Table 1]

A 32-meter-count worsted spun yarn prepared by blending the obtained cotton and untreated cotton in a ratio of 1: 1 is used to prepare a raw material for a Mayer blanket having a pile length of 6 mm and a basis weight of 700 g / m ^2. Had made. This blanket for blanket was dyed by a pad steam method under the following dyeing conditions with a cationic dye, a cationic softening agent was applied thereto, and dried, followed by splitting and shaving to prepare a blanket. Table 2 shows the antibacterial and antifungal properties of the blanket obtained. The blankets according to Nos. 1 and 2 have high antibacterial properties and antifungal properties even after 10 washes. The blanket according to No. 3 has insufficient antifungal properties, and Blanket No. 4 had insufficient antibacterial properties. Dyeing conditions: Katilon Yellow K-3RLH 0.2% by weight (cationic dye manufactured by Hodogaya Chemical Industry Co., Ltd.) Katilon Red K-GLH 0.1% by weight 40% Acetic acid 0.1% by weight 10% Maypro gum solution 5% by weight Drawing ratio 80%, steaming 98 ° C x 15 minutes

[0019]

[Table 2]

Example 2 A double-sided smooth knitted fabric using 100% spun yarn 100% acrylic fiber was treated under the conditions shown in Table 3. Table 3 shows the state of adhesion of the antibacterial agent and the antifungal agent to the fibers of the obtained knitted fabric.

[0021]

[Table 3]

The antibacterial and antifungal properties of the obtained knitted fabric are shown in Table 4. The knitted fabrics of Nos. 5 to 6 and 8 have durable antibacterial and antifungal properties.
The knitted fabrics of Nos. 7 and 9 lacked anti-mold durability.

[0023]

[Table 4]

(Example 3) Polyester fiber 50 was used for the warp.
%, Mixed yarn 32/1 of 50% cotton, and spun yarn 1/52 of 100% colax (water-absorbing acrylic fiber manufactured by Mitsubishi Rayon Co., Ltd.) as the weft, a plain weave sheet fabric with a basis weight of 150 g / m ^2. Was subjected to desizing and scouring with a normal pressure liquid jet dyeing machine, and then dyed under the following dyeing conditions with a cationic dye. This dyed fabric was used in Example 1 as No. 1. The composition was treated under the conditions shown in Table 5 using a composition containing an antibacterial agent and an antifungal agent in a component ratio of 1.
Table 5 shows the state of adhesion of the antibacterial agent and the antifungal agent to the fibers of the obtained dough. Dyeing conditions: Katilon Blue K-GLH 0.1% by weight Cationogen PAN 1.0% by weight (Cationic slow dyeing agent manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Acetic acid 1.0% by weight Bath ratio 1:30, temperature × time 100 ° C x 45 minutes

[0025]

[Table 5]

The antibacterial and antifungal properties of the obtained dough are shown in Table 6. The fabric according to 12-13 has high antibacterial properties not only against normal Staphylococcus aureus but also against resistant Staphylococcus aureus (MRSA),
Although the antibacterial effect was confirmed even after the test, The fabrics of Nos. 10 to 11 lacked antibacterial and antifungal durability.

[0027]

[Table 6]

[0028]

The acrylic fiber according to the present invention is prepared by Soxhletley extraction using a solvent such as alcohols and ketones.
Even if extracted for a time, the total extraction rate of the antibacterial agent and the antifungal agent is 50
% Or less, and an antibacterial agent and an antifungal agent are extremely firmly attached to the fiber, and are acrylic fibers having antibacterial and antifungal properties excellent in durability, especially in washing durability. Because it has no adverse effect on dyeability and high safety, it can be used in textiles such as clothing, blankets, sheets, etc. used in hospitals and special nursing homes, sports clothing, blankets, sheets, etc. It can be suitably used.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Ochiai 4-160 Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Research Center (72) Inventor Kunio Iwase 4-1-1 Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture No. 60 Mitsubishi Rayon Co., Ltd. Product Development Laboratory (56) References JP-A-5-106165 (JP, A) JP-A-2-112474 (JP, A) JP-A-2-259169 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) D06M 13/00-15/715

Claims (3)

(57) [Claims] An adhesion ratio of the antibacterial agent (A) and the antifungal agent (B) to the acrylic fiber satisfies the following formulas (1) and (2), a poor solvent for the acrylic fiber, and (A) ),
Acrylic fiber having antibacterial and antifungal properties, wherein the total extraction ratio of (A) and (B) with a solvent that is a good solvent for (B) is 50% by weight or less. 0.05% by weight ≦ a + b ≦ 5.0% by weight Equation (1) 0.3 ≦ a / b ≦ 1.0 Equation (2) (where, a is the concentration of the (A) in the fiber (weight %),
b indicates the concentration (% by weight) in the fiber of (B)) 2. The antibacterial agent (A) is 3,4,4'-trichloro
Locarbanilide, antifungal agent (B) is oxybenzoic acid S
2. The antimicrobial and antifungal agent according to claim 1, which is
Krill fiber . 3. Antibacterial agent (A), 3,4,4'-trichlorocarbanilide, antifungal agent (B) oxybenzoic acid ester, antibacterial agent (A) 0.05-5.0 times
% And the antifungal agent (B) 0.05 to 15.0% by weight
The concentration of the general formula R- (O-R ') n-OH in the concentration of 5 to 16.7 times that of the fungicide (A) (where R is an alkyl group, a phenyl group, R' is an alkylene group, and n is An aqueous solution dispersed in water in the presence of an affinity promoter (C) represented by an integer of 1 to 20) and a polyoxyethylene nonionic surfactant (D) at the same concentration as the affinity promoter (C). Acrylic fibers are impregnated with the dispersion and impregnated
3. The process for producing an acrylic fiber having antibacterial and antifungal properties according to claim 2 , wherein the fiber is subjected to a heat treatment at a temperature not lower than the secondary transition point of the fiber.