JPH0586575A - Antimicrobially active acrylic fiber - Google Patents

Abstract

PURPOSE:To obtain the subject fiber, having high safety and effective against a wide range of mierobial strains by quaternizing amine groups in a fiber surface layer part composed of an acrylonitrile copolymer in which an acrylic monomer containing antimicrobial amino nitrogen is copolymerized with an alkyl halide. CONSTITUTION:Amino groups of a fiber surface layer part composed of a polyacrylonitrile copolymer in which a copolymerization component expressed by formula I [R1 is H or CH3; R2 is CH3 or C2H5; R3 is CH3 or C2H5; R4 is (CH2)n ((n) is 2 or 3) or CH2CH(OH)CH2] is introduced as the amino groups having antimicrobial activity are quaternized with an alkyl halide expressed by the formula R5X [R5 is CnH2n+1 ((n) is 1-20) or C6H5CH2; X is Cl, Br or I] to afford antimicrobial acrylic fiber having the surface layer part composed of the polyacrylonitrile copolymer having immobilized antimicrobially active groups, expressed by formula II introduced thereinto and extremely high safety.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a high safety for human body by introducing plural kinds of immobilizing groups on the surface of synthetic fiber composed of polyacrylonitrile copolymer.
The present invention relates to an acrylic fiber having an effective antibacterial activity against a wide range of bacterial species.

[0002]

2. Description of the Related Art In recent years, the need for a rich and comfortable living environment has increased more and more, and in connection with the maturity of society and the advancement of age, and the demand for maintaining and promoting health, cleaner and more comfortable clothing. , Bedding home products are being developed. In a hot and humid environment like Japan, the reproduction of microorganisms such as bacteria and molds is particularly active.For example, the unpleasant odor caused by the decay of bacteria and bacteria adversely affects the living environment of food, clothing and housing, and the required comfort is required. The hygienic living environment and health are threatened. Therefore,
It is a social need to add antibacterial activity to textiles as a way to prevent and prevent the growth and reproduction of microorganisms that adversely affect our living environment and to maintain a hygienic and clean living environment. Technological development has taken place. Conventionally,
As a method for imparting antibacterial activity to the polyacrylonitrile fiber product, a low-molecular antibacterial agent is contained in the fiber during spinning. A low molecular weight antibacterial agent is added together with a processing agent.
An alkoxysilane quaternary ammonium salt compound having antibacterial activity is bonded onto the fiber. It is known to spin a copolymer component containing an amino group exhibiting antibacterial activity and a quaternary ammonium salt as a copolymer.

In the method of incorporating a low-molecular weight antibacterial agent as an additive during spinning, the additive is mobile and its toxicity causes serious problems. In certain end uses, such as infants, children's clothing, general garments, medical materials, etc., mobile additives are potentially toxic. In addition, during the synthetic fiber manufacturing process and then the textile processing process, the additive may be a toxic by-product (for example, dioxins) due to long-term heat treatment at a considerably high temperature, contact with special solvents and chemicals. ) Or exposed to undesirable side reactions that result in loss of antibacterial activity. On the other hand, the mobile additive is eluted from the fiber and lost after repeated washing, and it is difficult to maintain the antibacterial activity. These instabilities and uncertainties are related to the amount of additives, but depending on the usage situation in the final application, such as the usage period of the final product and the frequency of washing, etc.
Excessive addition levels are usually taken beyond the economic disadvantage. Excessive use of mobile additives is completely unfavorable in view of the above-mentioned toxicity.

It goes without saying that the method of applying a low-molecular weight antibacterial agent together with the processing agent and the like has the same problems as the above-mentioned migrating additive. Additives applied directly or together with a certain kind of processing agent often drop off due to surface abrasion, and are easily removed by washing or the like. As a result, the sustainability of the antibacterial activity is more difficult, the above-mentioned problems are magnified, and there are many undesirable points. In addition, by adding a processing agent, the product performance that the final product originally held,
For example, appearance, texture, color, and other important functions may be impaired.

In the method of bonding the alkoxysilane quaternary ammonium salt compounds having antibacterial activity onto the fiber, the reaction group produced by the hydrolysis of the alkoxysilane compound does not have a functional group to be bonded by a condensation reaction. Fibers, acrylic fibers, polyester fibers, and nylon fibers have a problem that they have poor durability because they cannot be bonded by a condensation reaction on the fiber surface. That is, the quaternary ammonium alkoxysilane is used as an aqueous methanol solution for fibers or textile products and intermediate products, but after hydrolysis of the alkoxysilane,
For example, it is bonded to the fiber surface by a condensation reaction with the hydroxyl groups of the cellulose fiber, but the alkoxysilanes cannot be bonded to the surface of the fiber which does not contain a hydroxyl group that undergoes a condensation reaction. As a result, the condensed silane compound locally adheres to the surface of the fiber, and has poor durability against repeated washing and the like.

It is well known that antibacterial activity is imparted by introducing a specific amino group into a polymer forming a synthetic fiber such as polyester, nylon or acrylic fiber. Acrylic fibers are also introduced into the polymer by copolymerization of a monomer containing an amino group, and impart a non-migrating antibacterial activity. Therefore, the amino group portion exhibiting antibacterial activity forms a part of the polyacrylonitrile copolymer forming the fiber, and the durability of the final product does not depend on the frequency and degree of abrasion and washing. In addition, since it is fundamentally different from mobile and diffusible additives that also cause toxicity, which is a problem in antibacterial agents composed of low molecular weight compounds, the part showing antibacterial activity, which itself is part of the polymer, Also, it has extremely excellent characteristics such that it is not modified into toxic by-products such as dioxins from the fiber processing conditions. However, on the other hand, the amino groups that are the antibacterial active sites are present throughout the polymer, and are distributed throughout the fiber as well, and the ratio of effective use on the fiber surface that comes into contact with microorganisms is roughly The antibacterial activity is weakened because it is close to one-tenth and extremely low. In order to reinforce this, when introduced by copolymerizing the amino group portion equivalent to 10 times the necessary amount with a monomer, the content of the copolymerization component becomes too large, and thus the general physical properties of fiber are Not only will the acrylic fibers deviate, but the economical efficiency will be significantly impaired by the use of large amounts of expensive monomers.

[0007]

The antibacterial activity of polyacrylonitrile fibers composed of a copolymer component containing an amino group or the like exhibiting antibacterial activity is remarkably diminished by effective contact on the fiber surface, which is a prerequisite for antimicrobial action. There is a problem. This problem cannot be solved by simply increasing the amount of the copolymerization component to reinforce the activity, because the fiber characteristics are deteriorated.

[0008]

Means for Solving the Problems That is, according to the present invention, in a polyacrylonitrile copolymer fiber in which a copolymerization component of the following general formula (A) is introduced as an amino group having antibacterial activity, its surface layer portion is The amino group is represented by the general formula (B)
Is an antibacterial acrylic fiber obtained by quaternizing with an alkyl halide of (1) to form an immobilized antibacterial active group.

General formula (A):

[Chemical 4]

General formula (B):

[Chemical 5] Through the selective reinforcement of antibacterial activity, the purpose of imparting antibacterial activity from polymers with high durability and safety was realized without introducing many copolymer components and impairing the physical properties of acrylic fiber originally.

Further, the present invention is an antibacterial active acrylic fiber in which a polyacrylonitrile copolymer fiber having a copolymer component of the following general formula (C) introduced as an antibacterial active group is present in the surface layer portion.

General formula (C):

[Chemical 6]

The present invention includes improvements in the effective contact of antimicrobial active groups with microorganisms, which is an essential prerequisite for antimicrobial activity. The first is the quaternization of the amino group, or the selection of an ammonium salt, the second is the selection of the alkyl chain length that quaternizes the amino group, and the third is based on the observation of the antibacterial spectrum in the antibacterial activity. Characterized by selecting and combining alkyl chain lengths that have selective activity for the specified bacterial species to select and remove alkyl chain lengths that show effective activity for specific bacterial species (complexation of selective activity) Have. In contacting the microorganism with the antibacterial active group, the antibacterial active group is said to act on the surface layer structure of the microorganism and the part related to the metabolic action, but there is no definite theory, and the action and effect are the active agent concentration, pH, electrolyte, solvent of the system. It is extremely complicated in relation to the working temperature. On the other hand, in general, the surface layer of microbial cells is covered with a cell wall, which is negatively charged by the residues of constituent protein molecules, and its cytoplasmic membrane and outer membrane are formed by weak interactions between proteins and lipids. It is said to have been done.

When the antibacterial active group is an amino group, depending on its basicity (pKb), the range of pH at which a proton is added and a positive charge is obtained is determined. It is strongly affected by the medium conditions such as pH and temperature. On the other hand, the quaternized amino group or quaternary ammonium salt is positively charged and negatively charged regardless of the conditions of the medium such as pH, electrolyte and temperature of the system acting on the microorganism. Microorganisms can be stably and reliably captured in a charged manner.

The copolymer introduced in the copolymer as the alkyl chain length of the alkyl halide which quaternizes the amino nitrogen according to the claims and claim 1 or the active group according to the claims and claim 2. The alkyl chain length of the quaternary ammonium salt of the component is
Regarding the inhibition of the growth of microorganisms by the action with the proteins and lipids forming the cytoplasmic membrane and outer membrane, and by destroying the wall membrane with the action of the proteins and lipids forming the cytoplasmic membrane and outer membrane There is a deep relevance for killing. In addition, the increase in hydrophobicity due to the length of the alkyl chain, for example, the introduction of hydrophilicity due to the hydroxypropyl group, depends on the degree of hydrophobicity / hydrophilicity of the surface layer and wall membrane of the microorganism with which they are in contact. It is also related to accessibility to work. It is believed that what is described here in relation to each other results in the introduced alkyl chain length and the introduced hydrophilic group exhibiting selective antibacterial activity in the antibacterial activity of different bacterial species.

The long-chain alkyl group and the hydrophilic group introduced in the present invention are claimed in claims 1 and 2.
However, the characteristic effect obtained by introducing these long-chain alkyl groups and hydrophilic groups is that they are hardly deactivated by washing. The alkoxysilane quaternary ammonium salt compound bonded to the fiber surface is more stable than being easily deactivated by washing. It is speculated that the contact with microorganisms is not hindered because the masking phenomenon of the long-chain alkyl anion surfactant used as a detergent is sterically hindered by the introduced long-chain alkyl.

In the present invention, as a method for strengthening the antibacterial active group, utilization of selective antibacterial activity for each different bacterial species as described above and selective antibacterial activity for a plurality of bacterial species Select the method to combine and combine. Combines selective antibacterial activity to cover a wide spectrum of antibacterial properties.

In the present invention, as a method of strengthening the antibacterial active group without deteriorating the physical properties of the acrylic fiber, the active group immobilized on the surface layer of the fiber is effective for effective contact between the antibacterial active group and microorganisms. The amount should be at least 5 to 30 mmol per fiber weight (Kg).
The means, of course, does not include the provision of an effective amount of the immobilized active group by the copolymerization component according to the claims and claim 2 within the range of not impairing the fiber physical properties of the acrylic fiber. Needless to say, here, in the core-sheath composite spinning method, the core portion is made of a polymer constituting a normal polyacrylonitrile fiber, and the spinning stock solution / sheath portion is the scope of claims and the polyacrylonitrile copolymerization according to claim 2. A method is selected in which a combination of spinning dope prepared by coalescence is spun out and the immobilized alkyl quaternized antibacterial active group is present on the surface layer of the fiber. As another means, there is a method of quaternizing an amino nitrogen in a surface layer portion with an alkyl halide according to claim 1.

The non-migratory antibacterial activity in the present invention is a functional group having an antibacterial activity immobilized on the polyacrylonitrile copolymer itself, and the fiber made of the copolymer is hydrolyzed or oxidized or reductively decomposed. Unless it is exposed to a severe chemical reaction, it is not detached from the fiber, and the fiber itself has an antibacterial active ingredient.

In the present invention, the antibacterial activity is measured by the Shake flask method (hereinafter abbreviated as SF method) by the "Fabric Products Hygiene Processing Council""Evaluation test of antibacterial and deodorant processed products", and is displayed as a bacterial reduction rate. .. Further, the antibacterial activity of the antibacterial and deodorant processed textile product was quantitatively evaluated by a new antibacterial activity evaluation method (hereinafter abbreviated as NAP method). In the NAP method, the initial bacterial count is a, the raw bacterial count after culturing is b,
If the number of bacteria of the processed product is c, and if a <c <b, it is considered that the product has a bacteriostatic action and the bacteriostatic activity (Bacterio-static Activ
ity [SA]) is calculated by the following formula and evaluated. SA = 100 × (bc) / (ba) In addition, a> c indicates a bactericidal action, and bactericidal activity (Bactericida)
l Activity [CA]) is calculated and evaluated by the following formula. CA = 100 × (a−c) / a The value determined by the above two equations is 0 <SA <100, and the closer the SA is to 100, the higher the bacteriostatic activity. Further, 0 <CA <100, and the closer CA is to 100, the higher the bactericidal activity. These evaluation test methods are not limited to processed products, and include various copolymer fibers according to the present invention, fibers into which amino groups quaternized with an alkyl chain by various methods, and quaternary ammonium salts are introduced. We presented effective evaluation results of the relative antibacterial activity and antimicrobial activity against a wide range of bacterial species and microorganisms for the products and intermediate products consisting of the fiber. Regarding these evaluation test methods, the method is described in the above-mentioned manual "Processing effect evaluation test of antibacterial and deodorant processed products" in the same conference, and the method is Hironori Komali, Takayo Nakagawa Journal of the Society for Antibacterial and Antifungal Society 16
Volume February 1988, pp. 49-57.

[0021]

INDUSTRIAL APPLICABILITY The antibacterial active acrylic fiber of the present invention exhibits a bactericidal power of 85% or more against cocci such as Staphylococcus aureus in the above-mentioned NAP method. Effective against Gram-negative bacilli such as Pseudomonas aeruginosa, showing bacteriostatic power of 80% or more, effective to reduce the number of growing microorganisms, and against Gram-negative fungi such as Escherichia coli 85 It has a bactericidal power of more than%, and is effective for killing and inhibiting the growth of microorganisms. In addition, the immobilized antibacterial active group of the present invention can trap bacteria and microorganisms in a charged manner. Furthermore, by selecting an antibacterial active group, it is possible to show selective antibacterial activity against fungi and microorganisms. Therefore, it is possible to combine a plurality of kinds of antibacterial activities with a wide range of fungal species and to provide a highly safe antibacterial activity. Antibacterial active acrylic fibers and composites thereof can be provided.

Therefore, the acrylic fiber to which the antibacterial activity is applied according to the present invention is used in a product field requiring an antibacterial and deodorant function, for example, sports clothing, socks, kitchen, bath, toilet mat, toilet seat cover, clothing for the elderly. , Bedding, fibers formed by polymer molecules themselves that have immobility and immobilized antibacterial active groups, and product fields that take advantage of their extremely high safety, such as underwear and diapers for infants and children. , Sanitary goods such as napkins, medical clothes for preventing pathogen infection in hospitals, materials such as bandages, wound protection cloths, therapeutic clothes, surgical gowns, barrier cloths, doctor's and nurse's outerwear, sweaters, Anti-bacterial water and air filters for gowns, tights, socks, sterilization, separation and purification, longevity and long shelf life of fruits and high-quality vegetables Antimicrobial packaging material in many other applications and in contact with the microorganisms to be effectively used.

The present invention will be described below with reference to examples.
The present invention is not limited to this. Example 1 Acrylonitrile (AN) / methyl acrylate (MA) / methacryloxy-glycidyl trimethylammonium chloride (MAGM) = 87 / 6.7 / 6.3 [Composition A], AN / vinyl acetate (VA) /MAGM=85.6/11.3/ 3.1 [Composition B], AN / MA / methacryloxyethyltrimethylammonium chloride (MATM) = 86 / 10.2 / 2.8 [Composition C], AN / VA / N, N-dimethylaminoethylmethacrylate (MADM) = 85.6 / 1
2.1 / 2.3 [Composition D], same = 85.6 / 11.4 / 3.0 [Composition E],
Same = 85.6 / 10.7 / 3.7 [Composition F], Same = 85.6 / 9.2 / 5.2
A copolymer comprising [Composition G] was dissolved in a 50% aqueous solution of rhodanese so as to have a polymer concentration of 10% to prepare a spinning dope. The spinning dope was spun through a spinneret with a hole diameter of 0.06 mm and 50 holes in a coagulation bath of a 10% aqueous solution of rodan soda at -3 ° C to form a fiber by coagulation, which was washed with water and then boiled to 10 times the original length in boiling water. It was stretched. Next, after constant humidity drying at 105% relative humidity 60%, the temperature at which the fiber length shrinks 30% with respect to the length after constant humidity drying is selected in the range of 105 to 120 ° C, and steam is selected. Heat treatment was performed to obtain fibers A to G from the polymers having the respective compositions. The weight ratio of the copolymer of composition E is 24
% Dissolved in dimethylacetamide, dimethylacetamide / water (70/30 weight ratio) from a discharge port with a diameter of 60 microns
After coagulation in the solution and stretching at a total stretch ratio of 5 times, after drying 13
Steam heat treatment was performed at 0 ° C. to obtain fiber e. 80% or more AN,
If necessary, for example, sodium methallyl sulfonate (M
AS), p-styrene sulfonate, 2-acrylamide
-2-Methylpropane sulfonic acid and other cationic dyes, and other monomers such as vinyl acetate, vinylidene chloride, and (meth) acrylic acid ester, etc. AN / as a typical example of
A copolymer H having a composition of MA / MAS = 91.0 / 8.7 / 0.3
Fiber [fiber H] was obtained by the above method. 1.5-fold amount (molar ratio) of 1-chlorooctane was added to DADM using ether as a solvent, and the reaction was continued at the boiling point of ether in a glass flask equipped with a reflux condenser. Methacryloethyldimethyloctyl ammonium chloride (O
Copolymer I obtained by adding 2.9% of DMEM) to the composition of AN / VA = 85.8 / 11.3 was used as a fiber [fiber I] by the above method.

Example 2 Hereinafter, a copolymer containing a copolymerization component of the general formula (A) will be referred to as component A, and a copolymer containing no copolymerization component of the general formula (A) will be referred to as component B. Copolymer of Composition B (Component A) or Copolymer I (Component A) and Copolymer H (Component B)
Alternatively, the copolymer of composition E (component B) is subjected to composite spinning by the above-mentioned acrylic fiber production method. Component A is unevenly distributed particularly on the surface that comes into contact with microorganisms so that the component A is in the range of 5 to 50%, preferably 10 to 35% per fiber cross-sectional area. As the uneven distribution method, a sheath-core type composite spinning with component (a) as the sheath side and component (b) as the core is the most preferable, but a sandwich type or side-by-side type composite spinning method is also applicable. Can be reached That is, in the composite spinning method, by adjusting the polymer concentration and viscosity of the spinning dope for both components, the two components are attached so that component A is concave (three months) and component A surrounds component B. Can be matched. By this method, a sandwich type (surface area ratio A / B = 7/3) fiber [fiber J] composed of copolymer I (component A) / copolymer of composition E (component B) and copolymer of composition B Side-by-side type consisting of (component a) / copolymer H (component b) (composite ratio a / b = 3
5/65 (3) Cover fiber (fiber K) was produced in 3 months.

Example 3 Fiber E was quaternary alkylated with halides of different alkyl chain lengths. In a 1 liter flask equipped with a reflux condenser, 5 g of the fiber E was placed, methanol was used as a solvent, and 100 times equivalent of an alkyl halide of amino nitrogen group in the fiber was injected, and the boiling point of methanol was 65 ° C. Heating was carried out for 2 hours. The alkyl halide used for the alkylation is ethyl iodide (MW 158) fiber L], butyl chloride.
(MW 92.2) [Fiber M], hexyl chloride (MW 120.6) [Fiber N], octyl chloride (MW 148.7) [Fiber O], lauryl chloride (MW 205) [Fiber P], cetyl chloride (MW 261) [Fiber Q], stearyl chloride (MW289) [fiber R] and benzyl chloride (MW126.6) [fiber S] were washed with methanol and dried to obtain sample fibers L to S. Further, the fiber e was quaternized with octyl chloride in the same manner as above to obtain a fiber T.

Example 4 SF for the fiber samples prepared in Examples 1-3
The antibacterial effect was tested by the method. For the evaluation, the sterilization rate% is obtained from the following equation based on the viable cell count A before shaking and the fiber sample of the test sample, and the viable cell count B measured after shaking. Sterilization rate = 100 X (AB) / B (%) [Fiber E] having N, N-dimethylmethacryloxyethylamino group (tertiary amine) and the fiber obtained in Example 3 were octyl chloride or SF for fibers quaternized with benzyl chloride, [fiber O], [fiber S] and [meth] acrylooxyglycidyl trimethylammonium chloride (quaternary salt), respectively
The sterilization rate was determined by the method. The results are shown in Table 1.

[0027]

[Table 1]

Table 1 shows that although a decrease in the number of bacteria was observed in all the fiber samples, it was scarce in the fiber E, and in the alkyl quaternized fibers O, S and B, the bacteria were extremely remarkable up to 3 digits. Had a decrease. It was also shown that the fiber e, which has a low bacterial reduction rate, has a significantly increased bacterial reduction rate in the alkyl quaternized fiber T.

Example 5 By the method of preparing [Fiber J] and [Fiber K] prepared in Example 2 and [Fiber K] in Example 2, a copolymer (composition A) / copolymer of composition B was prepared. The composite ratio of the combined H (component B) was changed to prepare three samples shown in Table 2. In each sample, component A was spun so that component A covered a large amount of component B in three months. Basic nitrogen groups (active amino groups), which are thought to exist on the fiber surface, were quantified and the relationship with antibacterial properties was examined. A solution in which a predetermined amount of Acid Orange II was dissolved (Solution 1; pH of dyeing bath with sodium hydrogen carbonate)
Is maintained at 8.5 or higher) (Solution 2; pH of dyeing bath is adjusted to 3 with sulfuric acid) at 70 ° C for 30 minutes, washed thoroughly with water, and then dyed on the dried fiber. The amount of immobilized amino (antibacterial) active group is determined from. The dyed amount on the surface of the fiber was estimated from a calibration curve prepared from fibers dyed with a known amount in advance. The results are shown in Table 2.

[0030]

[Table 2] Samples containing fibers having an amount of cation groups that are cationized on the fiber surface exceeding 5 mmol / Kg regardless of the pH of the system, fibers J, K, 5-
Good antibacterial activity was shown in 1 and 5-2.

Example 6 [Fiber D] and [Fiber E] were prepared by the method shown in Example 3.
Was tried to quaternary alkylate with octyl chloride under the following conditions. The amount of alkylated amino groups was calibrated by the Orange II surface dyeing method described in Example 5 (with solution 1). The antibacterial test is SF method, Staphylococcus aureus, and the results are shown in Table 3.

[0032]

[Table 3]

Fibers E and D were dyed at 19 and 15 mmol / Kg according to the surface dyeing method with solution 2, respectively, but the degree of alkylation obtained here was extremely low and activated regardless of the pH of the system. The number of activated amino groups on the fiber surface is 5
The two samples No. 6-1 and 6-3, which exceeded mmol / Kg, showed excellent antibacterial performance.

Example 7 [Fiber B], [Fiber C], [Fiber K], [Fiber M], [Fiber O], [Fiber P] and [Fiber S] produced in Examples 1 to 3 were used as anions. A washing test with an active detergent was conducted to examine changes in antibacterial activity due to washing. The prescription and procedure of the washing test were based on JIS-L-0217 103 (detergent; Monogen Uni). The results are shown in Table 4.

[0035]

[Table 4] Although the fibers C and M show a slight decrease in antibacterial property, they are still at a level showing antibacterial activity. The other samples show high sterilization rate even after washing.

It is revealed that the polymer forming the fiber itself possesses an antibacterial active ingredient and exhibits robustness. The functional deterioration due to washing, which has been a problem in processed products using alkoxysilane quaternary ammonium salt compounds, is said to be masking by anion-active detergent molecules in addition to desorption of the processing agent. Since no functional deterioration was observed, it is considered that a characteristic group introduced into the fiber molecule in an appropriate amount, a hydrophilic OH group or an alkyl group plays a role of inhibiting it.

Example 8 Seven samples obtained by quaternary alkylating the [fiber E] prepared in Example 3 with halides having different alkyl chain lengths [fiber L,
M, N, O, P, Q, R] and [fiber A] containing glycidyl trimethyl ammonium chloride, [fiber E] having a dimethylaminoethyl group, N
An antibacterial activity evaluation test by the AP method was carried out by selecting Staphylococcus aureus IFO12732 as the test bacterium and setting the initial number of bacteria to 1.4 × 10 ⁴ . At this time, a normal acrylic fiber [fiber H] was used as a comparative control fiber. N
Regarding the AP method, the procedures for measuring and evaluating SA and CA by measuring the numbers a, b and c of the bacteria as described in paragraph 0020 above are described. The results are shown in Table 5.

[0038]

[Table 5] In the fiber E before the quaternization of alkyl, the ordinary acrylic fiber H
Although the number of bacteria is increased and growth is observed, the introduction of an alkyl group having 4 to 12 carbon atoms (hereinafter abbreviated as C4 to C12) shows remarkable bactericidal activity. The bactericidal activity of the fiber A is also remarkable. The bactericidal activity is also exhibited by increasing the chain length from C16 to C18.

Example 9 Six samples obtained by quaternary alkylating the [fiber E] prepared in Example 3 with halides having different alkyl chain lengths [fiber M,
N, O, P, Q, R] and [fiber A] containing glycidyl trimethylammonium chloride, and [fiber E] having a dimethylaminoethyl group, the test strains were tested as gram-negative bacteria / Pseudomonas aeruginosa IFO.
10145) was selected and an antibacterial activity evaluation test was carried out by the NAP method. At this time, ordinary acrylic fiber [fiber H] was used as a comparative control fiber. The results are shown in Table 6.

[0040]

[Table 6]

Fibers P and Q show excellent bacteriostatic activity against Pseudomonas aeruginosa. The bacteriostatic action generally means capturing microorganisms such as bacteria and inhibiting their growth and proliferation.
It has a mild and safe antibacterial effect. When the alkyl chain length is C8 or less and C18, the SA value is also small and C12-
It is noted that the chain length of C16 shows a high SA value, and that the antibacterial property has selectivity by the alkyl chain length. This selective activity was shown by the outstandingly superior alkyl chain length of C4 to C12 in the antibacterial activity of S. aureus of Example 8. As is clear from these two cases, there is an optimum range for the alkyl chain length of the active group that exhibits a higher antibacterial effect depending on the bacterial species. That is, it is considered that there is selective activity. Note that Fiber A shows bactericidal activity against P. aeruginosa. The bacteriostatic activity SA value of the fiber E having a non-quaternized amino group is very small. The third of fiber E
The pKb value of the primary amino group is around 5 to 6, and it is considered that it has a positive charge due to H + ion addition by pretreatment.

Example 10 Three samples obtained by quaternary alkylating the [fiber E] prepared in Example 3 with halides having different alkyl chain lengths [fiber M,
O, P] and [fiber E] with dimethylaminoethyl groups, for Gram-negative bacteria / Escherichia coli
i K12 OUT 8401) was selected as a test bacterium, and an antibacterial activity evaluation test by the NAP method was performed. At this time, ordinary acrylic fiber [fiber H] was used as a comparative control fiber. The results are shown in Table 7.

[0043]

[Table 7] For E. coli, a generally good bactericidal activity is shown. C4 having a short alkyl chain length shows a high CA value. The high CA value of fiber E is also noted.

Example 11 Three samples [fiber M, O, P] prepared by quaternary alkylation of [fiber E] with chlorides having different alkyl chain lengths in Example 3 and [fiber E] having a dimethylaminoethyl group. For this, an antibacterial activity evaluation test by the NAP method was carried out using the following test bacteria. At this time, ordinary acrylic fiber [fiber H] was used as a comparative control fiber. Also,
The amino group of the fiber E seems to be in a state of being positively charged by the H + ion addition. The results are shown in Table 8.

[0045]

[Table 8]

◆ Display of the number of bacteria; 3.0E5 in the example table means 3.0 × 10 ⁵ . ◆ Test bacteria; abbreviation Gram-positive bacterium Bacillus cereus IFO 3001 / spore-forming bacterium BC Bacillus magaterium IFO 3003 / Giant bacterium BM gram-negative bacterium Klebsiella pneumoniae ATCC 4352 / Klebsiella pneumoniae KP Proteus vulgaricus Ox19 RIMD / Urea degrading bacterium PM

In the test bacteria PV and BM, the fiber M of C4 shows an excellent bactericidal activity, and C8 has a good bactericidal activity against PV, but the bacteriostatic activity decreases as the chain length increases. Indicates. It shows that the antibacterial activity of the fiber E is inferior to that of the alkylated fiber. Among the BC and KP strains, C12 showed the highest antibacterial activity. For BC, alkyl quaternization has a great effect of enhancing the bactericidal activity, and the bactericidal activity of the fiber E is weak.
The antibacterial activity of KP is lowest at C4. In the test bacterium PM, the fiber E, which had the lowest antibacterial activity against the other four bacterial species, has the highest antibacterial activity. The SA value was 82%, indicating good bactericidal activity, and the SA% bacteriostatic activity tended to decrease as the alkyl chain length increased. Here again, there is an optimum range for the alkyl chain length of the active group that exhibits a higher antibacterial effect for each bacterial species. That is, it is considered that there is selective activity.

Example 12 In Examples 8 to 11, an evaluation test of the antibacterial activity of each fiber sample was carried out for each bacterial species. The results are classified according to the criteria shown below and summarized in Table 9. From this table, the antibacterial selective activity (antibacterial spectrum) against various bacteria for each fiber sample can be read.

[0049]

[Table 9] Abbreviation of bacterial species SA: Staphylococcus aureus IFO PA: Pseudomonas aeruginosa IFO EC: Escherichia coli K12

[Fiber P] has a remarkable bactericidal activity for SA and BC and a good bactericidal activity for EC. PA, P
It exhibits excellent bacteriostatic activity against V. [Fiber A]
Shows a remarkable bactericidal activity against SA, and the bactericidal activity against PA is characteristic. [Fiber E] has a lower antibacterial activity than that of the quaternary alkylated fiber sample, and shows good bactericidal activity for EC and PM. It was clear that each fiber exhibited selective activity, but the mixture (complexation) of fibers having selective activity was diluted according to the mixing ratio, and the selectively exhibited antibacterial activity was also revealed. , Common sense is expected to deteriorate. The possibility of expanding and enhancing the antibacterial selective activity characteristic of each fiber sample was sought by expanding the antibacterial effect against a wide range of bacterial species by mixing the fibers. The results are shown in Table 10
Shown in.

[0051]

[Table 10]

The selective activity exhibited by each fiber is not diluted and deteriorated by the mixing (complexing) of the fibers, and the antibacterial selective activity characteristic of each fiber sample is By mixing, spread to a wide range of bacterial species,
Table 10 shows that the antibacterial effect is enhanced. Furthermore, synergistic and amplification results exceeding the antibacterial effect of any of the combined fibers are also seen. Each of the combined fibers exerts a bacteriostatic action in a piecewise manner and plays a role of trapping bacteria in a charged manner, while sharing the action of sterilization with an optimal mechanism for contact of each bacterial species. Such a mechanism is inferred. The non-migrating antibacterial action of the immobilized antibacterial active group is extremely mild and highly safe, but by combining the selective activities shown here with proper combination of multiple types, high safety is maintained. However, it is clear that it can provide a wide range of advanced antibacterial activities.

Claims (2)

[Claims] 1. A surface layer portion of a fiber comprising a polyacrylonitrile copolymer into which a copolymerization component represented by the following general formula (A) is introduced is formed from amino nitrogen quaternized with an alkyl halide represented by the general formula (B). An antibacterial active acrylic fiber, which is covered with a fixed antibacterial active group. General formula (A): General formula (B): 2. An antibacterial active acrylic fiber characterized by having a surface layer part comprising a polyacrylonitrile copolymer introduced with immobilized antibacterial active groups as a copolymerization component of the following general formula (C). General formula (C):