JPH0268310A - Antibacterial acrylic fiber - Google Patents

Abstract

PURPOSE:To provide the subject fiber composed of an acrylonitrile polymer component dyeable with cationic dye and a specific amount of an antibacterial component, having excellent dyeability with cationic dye, high whiteness, etc., and producible at a low cost. CONSTITUTION:The objective fiber is composed of (A) an acrylonitrile polymer component dryeable with cationic dye and (B) an antibacterial component (preferably composed of >=60wt.% of acrylonitrile, 0.2-20wt.% of monomer containing amino group, etc., and the remaining part of other monomer), wherein the component B is disposed in concentrated state at a ratio of 5-50%, preferably 10-35% based on the cross-sectional area of the fiber. The arrangement of the component B in concentrated state is preferably carried out by a conjugate spinning means such as a side-by-side spinning to enable the exposure of at least a part of the component B on the surface of the fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an antibacterial acrylic fiber having practical properties such as dyeability with cationic dyes, attractive white skin, and low cost.

(Conventional technology and problems) In recent years, with the maturation of society and the aging of society, the demand for maintaining and improving health has increased, and more clean and healthy clothing,
It is hoped that products such as bedclothes and interior products will emerge. Also,
Infections within hospitals have also become a major social problem.
There is a strong demand for medical TJs and textile materials, such as surgical gowns, patient sheets, bandages, gauze, masks, etc., that can suppress the adhesion and propagation of bacteria.

Therefore, many antibacterial agents, both low molecular weight and high molecular weight, have been proposed, and their mechanisms of action have also been clarified. Among them, cationic anti-drinking agents such as quaternary ammonium salts and protonated amines are widely used because they are known to exhibit strong bactericidal performance by destroying cell membranes.

Typical methods for producing antibacterial fibers include adding an antibacterial agent to the fiber-forming polymer spinning dope (method A), and imparting self-resistance to the fiber-forming polymer itself (method). Examples include. In order to provide satisfactory antibacterial properties using the A method, it is necessary to add a large amount of antibacterial agent, which results in clogging,
Spinning operability such as yarn breakage K rt! There are also problems with washing and durability against friction.

As a typical example of a diol component described in Japanese Patent Publication No. 58-1051O, a polyester or polyurethane diol component having a quaternary amino group in the molecule is used. Shape the fibers,
Next, a method for providing an antibacterial fiber material by introducing a quaternary ammonium base into the fiber by reacting it with halogenated hydrogen chloride can be mentioned. In addition, for example, Japanese Patent Publication No. 49-402 whose main purpose was to provide anionic dye-dyeable acrylamide
Dimethylaminoethyl (methane acrylate) and diethylaminoethyl (methane acrylate) amino group-containing monomers described in No. 38 and JP-A No. 51-26826, or as described in, for example, Japanese Patent Publication No. 46-27814. Fibers are made by copolymerizing quaternary ammonium base-containing monomers such as methacryloxymethyltrimethylammonium chloride and 2-hydroxy-8-methacryloxypropyl-7retrimethylammonium chloride with acrylonitrile (AN). Means for forming the material have also been proposed for a long time.

However, upon further investigation by the present inventors, it became clear that even the wide mouth, which had no problems with durability in terms of spinning operability and antibacterial performance, contained the following essential defects. Ta.

■ Since the antibacterial site and the dyeing site are the same quaternary ammonium base or amino group, when dyeing, the antibacterial site may be blocked by the dye and the antibacterial property may decrease.

■ Acrylic fibers in particular are subject to restrictions on the ability to be dyed with cationic dyes.

■ Monomers containing quaternary ammonium bases and amino groups (hereinafter referred to as amino group-containing monomers) are inherently highly thermally colored, so they become colored during the fiber manufacturing process and deteriorate the white skin.

■ Blending with other fibers significantly reduces antibacterial properties, so there are restrictions on the amount of blending (application development) or high
It is necessary to use a large number of monomers containing amino groups, etc.

(Problems to be Solved by the Invention) The object of the invention is to avoid the above-mentioned problems, be dyeable with cationic dyes, have good white skin, not have its antibacterial properties reduced by dyeing, and have a small amount of An object of the present invention is to provide an acrylic fiber that can exhibit excellent antibacterial performance with a large amount of antibacterial sites.

(Means for Solving the Problems) The object of the present invention described above is to obtain a cationic dye-dyeable AN yarn combination component (4), an anti-I component (B), and a component (9).
B) is achieved by antibacterial acrylic fibers in which 95 to 50% of fiber cross-sectional area is concentrated.

Hereinafter, the present invention will be described in detail, but first of all, the component () is not limited to being formed by a cationic dye-dyeable AN yarn dot coalescence, and is approximately 50% or more, preferably 60% or more, and Preferably an AN of 80% or more, and if necessary,
For example, sodium methallyl sulfonate, sodium p-styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, methacryl ester sulfopropyl ester,
Cationic dye-dyeable monomers such as methacrylic acid and itaconic acid and other monomers, such as vinyl esters such as vinyl acetate; vinyl halides or vinylidene compounds such as vinyl chloride, vinyl bromide, and vinylidene chloride; acrylics; A co-electrolyte consisting of (meth)acrylic acid lower alkyl esters such as methyl acid, acrylamide, styrene, etc. is recommended.

In addition, the antibacterial component can be used as long as it has antibacterial properties and fiber forming ability, but from the viewpoint of peeling of both components A and B, fiber performance, durable antibacterial property, etc., 50% by weight is recommended. As mentioned above, an antibacterial AN-based polymer preferably comprises 60% or more of AN, 0.2 to 20% by weight of a monomer containing amino groups, etc., and the balance being the other monomers mentioned above.

The monomer containing amino groups, etc. is not particularly limited, but preferable examples include monomers represented by the following general formulas if) to 1) (provided that R1 is hydrogen or C4 The following alkyl groups, 7 and 9, each represent an alkyl group of C4 or less, and m represents an integer of 2 to 4.) (However, R1-Ra means the same as in formula 1, & each represents an alkyl group of 04 or less. group, Rs is a C4 or less alkylene group or hydroxyalkylene group, xv, C1, Br, ■
, CH3CO01C1-13804 or SCN.

(However, R+-抛 means the same thing as 1 type, and 抛 means C.
an alkylene group of 4 or less; n represents an integer of 0 or 1;

In addition, component (B) is an antibacterial AN polymer, a phenol derivative, a diphenyl ether derivative,
Pyrethroid and organophosphorus insecticides, 2-(4-thiazolylbenzimidazole, and other known bactericidal, insecticidal, and fungicidal agents) may be added.

The component direction and the ratio of component (B) vary depending on the desired antibacterial performance, the amount of antibacterial sites in BJ, etc., and it is difficult to define it unambiguously. It is desirable to set it within the range of 5 to 50%, preferably 10 to 85%.

When the proportion of component (B) is less than the lower limit of the above range,
Problems arise with antibacterial performance, fiber manufacturing technology, etc., and when the upper limit is exceeded, there are problems with dark dyeing, white skin, economic efficiency, etc. The amount of antibacterial sites in the final fiber is:
0.5 X l Oeq/(1 or more, preferably 1.6
X 10 to 10XIOeq/y is desirable.

As a method for concentrating component tB+, component (B)
Known polymer spinning methods include side-pie-side type, sandwich-inch type, and random type, which allow at least a portion of the fiber to be exposed on the fiber surface, but the side-pie-side type is preferable from the viewpoint of antibacterial performance. In addition, the component (B
), if side-pie-side type composite spinning is performed while violating the polymer concentration and viscosity of the spinning stock solution, the component direction will be convex, component (B) will be concave (crescent shape), and component (B) will be concave (crescent shape). -m is desirable because the two components can be bonded together so as to surround the inside, and the antibacterial performance can be further improved.

(Effects of the Invention) Since the antibacterial acrylic fiber of the present invention described above is mainly composed of a cationic dye 11rQ tQ A N-based polymer,
Like general-purpose acrylic fibers, it can be cationically dyed, and its antibacterial properties do not deteriorate in any way due to dyeing.Furthermore, because the antibacterial components are concentrated, it has excellent antibacterial performance with a relatively small amount of antibacterial sites. The present invention has been able to provide fibers with these advantages without problems such as spinning operability and economic efficiency, which are advantageous under the T Treaty. This is a noteworthy effect.

As described above, the fiber (lO) of the present invention, which has various advantages, can be used as a raw material for medical textile materials such as surgical skin covering materials, surgical gowns, patient clothes, sheets, masks, bandages, gauze, diapers, and napkins. It is widely used in fields such as clean and comfortable clothing, bedding, and interior products.

(Example) Examples are provided below to facilitate understanding of the present invention.

The percentages in the examples are based on weight unless otherwise specified.

In addition, antibacterial properties, dyeability, and white skin were determined as follows.

tl) Antibacterial properties (yellow based on % AATCC-100-1974) The number of Daurocci was determined and expressed as the bacterial reduction rate calculated by the following formula.

Dyeing test fibers were dyed using a cationic dye, Eisen Cachilon Black SBH (manufactured by Hodogaya Chemical Co., Ltd.) 4% OWF, according to a conventional method under the conditions of pn=4.98CX60 minutes, and congratulatory judgments were made.

(8) Whiteness Align the fibers in the same direction and measure 458.558.5 using a spectrophotometer.
The reflectance for light with a wavelength of 95 mμ was determined using a magnesium oxide plate as a reference, and is expressed in yellowness calculated using the following formula.

Example 1 An AN-based polymer consisting of 90% AN, 9.8% methyl acrylate (MA) and 0.2% sodium methallylsulfonate obtained by polymerization according to a conventional method was added to a 45% aqueous Rodan soda solution. Dissolved spinning stock solution 1 with a polymer concentration of 12%
a) was prepared.

In addition, AN89%, M
A 4.7% and 2-hydroxy-8-methacryloxypropyltrimethylammonium chloride 6.8
A spinning dope (bl) was prepared in the same manner as above from the AN-based polymer consisting of %.

Similarly, AN consisting of 86% AN, 08% vinyl acetate 1O, and 3.2% dimethylaminoethyl methacrylate
A spinning dope (b2) of the polymer was prepared.

Each of the spinning stock solutions a and bl and a and b2 was mixed at a composite ratio of 7.
Side-pie-side type composite spinning was carried out so that the fiber size was 5/25, and subjected to water washing, stretching, heat treatment, etc. according to conventional methods to produce test fibers (1 and 2) having a single fiber fineness of 8d.

For comparison, a test edge #(8) of 8d was prepared by single-component spinning of the spinning stock #b1. In addition, the 8d fiber obtained by spinning the spinning dope a as a single component and the test fiber 8 were mixed at 75/2.
A sample fiber (4) was prepared using a ratio of 5.

The results of evaluating the antibacterial properties of these fibers are shown in Table 1 below.

From the table above in Table 1, it is clear that the products of the present invention (Nal and 2) exhibit excellent anti-malignant properties in a small amount of anti-bacterial sites, maintain their anti-bacterial properties even after dyeing, and are also effective against staining and white skin. It is clear that there is no.

Example 2 Test fibers (5 to 10) were produced in the same manner as in Example 1 (test fiber 1) except that the composite ratio was changed. The results are shown in Table 2 below.

As is clear from the above table, the products of the present invention (NL6-9) have excellent overall performance.

Example 8 The polymer concentration of the spinning stock solution bl was set to 10%, and the composite ratio was set to 90.
A test fiber (11) was produced in the same manner as in Example 1 (sample fiber 1) except that /l O was used.

The cross section of this fiber has antibacterial components in a crescent shape, and antibacterial properties (%n is raw cotton, 97.4.96.8
Met.

Claims (1)

[Claims] Cationic dye dyeable acrylonitrile polymer component (A
) and an antibacterial component (B), and the component (B) is concentrated at a ratio of 5 to 50% per fiber cross-sectional area.