JP2000073280A - Antimicrobial acrylic fiber and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial acrylic fiber capable of preventing the discoloration thereof in each finishing process, and having antimicrobial properties hardly reduced by dyeing and laundering by allowing the pores in the interior of the fiber to carry a chitosan, and further allowing a specific quarternary ammonium salt to bind to the anionic group of the fiber. SOLUTION: This antimicrobial acrylic fiber is obtained by dipping a porous acrylic gel fiber into a chitosan solution, subjecting the dipped fiber to a neutralizing treatment to insolubilize the chitosan, drying the obtained fiber to compact the fiber, imparting a quarternary ammonium salt-based agent of the formula [R1 is an 8-21C alkyl or alkenyl; R2 is a 2-5C alkylene; R3 and R4 are each a 1-5C alkyl; R5 is a 1-5C (hydroxy)alkyl; X is I, Cl, Br or the like], e.g. stearylamidopropyldimethylhydroxyethylammonium nitrate to allow the agent to bind with an anionic group of the acrylic fiber. The antimicrobial acrylic fiber has >=23 mmol/kg of the quarternary ammonium salt and the non-binding anionic group, and >=2.2 of a bacteriostatic activity value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cationic dyeable antibacterial acrylic fiber and a method for producing the same. More specifically, it has good anti-bacterial properties and good dyeing properties (dense dyeing properties), and there is no discoloration / coloring due to light, heat, processing chemicals, etc. in the process of processing into various products. Provided is a cationic dyeable antibacterial acrylic fiber having high practical performance which is not deteriorated by washing and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, with the maturation of society and the aging of society, and the tendency to seek a rich and comfortable living environment, maintaining and maintaining health
There is an increasing demand for promotion, and there is a demand for cleaner and more comfortable clothing, bedding, interior products, living materials, and the like. As one of the methods, various antibacterial fibers have been developed to prevent the generation of microorganisms that adversely affect our living environment, suppress their growth and reproduction, and maintain a sanitary and clean living environment. ing.

[0003] As an antibacterial agent to meet such demands, cationic surfactants are well known as inverted soaps, and are sterilized and disinfected in medical treatments such as disinfection of fingers and operating departments in hospitals or in food processing plants. It is used for sanitary areas such as. Also, among the cationic surfactants, quaternary ammonium salts have strong bactericidal activity, a typical example of which is lauryl dimethyl benzyl ammonium chloride (also known as benzalkonium chloride). Organosilicon quaternary ammonium salts are well known as antibacterial agents. Examples of the application of quaternary ammonium salts to acrylonitrile-based fibers include, as described in Japanese Patent Publication No. 3-16423, an organosilicon quaternary ammonium salt such as dimethyl octadecyl. (3-trimethoxysilyl). ) -Propyl ammonium chloride is generally immersed in, adsorbed to, and dried and fixed to the final textile product after dyeing and bleaching. Further, as described in Japanese Patent Publication No. 3-216743, it is described that a product treated with a quaternary ammonium salt generally has a problem that coloring by heat is large.

When a quaternary ammonium salt is treated in a step prior to a step of dyeing acrylonitrile-based fibers dyeable with a cationic dye having a sulfonic acid group, the sulfonic acid group serving as a dyeing seat becomes a quaternary ammonium salt (cation). And it becomes difficult to dye later. Lauryl dimethyl benzyl ammonium chloride and dimethyl octadecyl, which have particularly strong bactericidal and antibacterial properties,
When (3-trimethoxysilyl) -propylammonium chloride is pre-treated to acrylonitrile-based fibers dyeable with a cationic dye having a sulfonic acid group, the sulfonic acid group of the dyeing seat is firmly blocked and the dyeability is obtained later. The problem that it cannot be done arises.

On the other hand, as an example of application to acrylonitrile fibers using a chemical other than a quaternary ammonium salt, silver ions or copper ions exhibit excellent antibacterial properties. Methods for imparting antibacterial properties to acrylonitrile fibers are known (JP-A-52-92000, JP-A-3-199418, etc.). However, they may be colored or discolored due to the influence of light, heat, chemicals used in various processing steps, or the like, and there is a problem that processing is restricted.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the problems of the prior art, and it is an object of the present invention to provide an antibacterial and good dyeing property (dark dyeing). Cation dyeable antibacterial acrylic fiber that does not discolor due to light, heat, processing chemicals, etc., and that the antibacterial performance is not reduced by dyeing and washing in the process of processing into various products. To provide.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Chitosan is supported in the pores inside the fiber, and a part of the anionic group of the polymer constituting the fiber has the following general formula [3]
Is bonded to at least one quaternary ammonium salt-based drug, more preferably 23 mmol / kg of an anionic group not bound to the quaternary ammonium salt-based drug.
The antibacterial acrylic fiber is characterized by having an antibacterial activity value of 2.2 or more and having an antibacterial property of at least 2.2.

[0008]

Embedded image

The antibacterial acrylic fiber is wet-spun from an acrylonitrile polymer, impregnated with an acidic solution of chitosan in the pores of the fiber before the densification step, neutralized and insolubilized, and then dried and densified. The chitosan is supported on the inner pores of the acrylic fiber, and one or more quaternary ammonium salt-based drugs represented by the following general formula [4] are imparted thereto. Is done.

[0010]

Embedded image

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The acrylic fiber used in the present invention is a fiber composed of an acrylonitrile-based polymer having an anionic group, and acrylonitrile is preferably 60% by weight or more, more preferably 80% by weight or more and a desired amount of anionic group capable of copolymerizing with acrylonitrile. Containing monomer and, if necessary, other vinyl monomer 1
Cationic dye-dyeable acrylonitrile-based fibers formed from acrylonitrile-based copolymers of at least one species are preferred. In addition, the cationic dye dyeability (or abbreviated as cationic dyeability) means that the polymer molecule constituting the acrylic fiber has an anionic group, and the cationic dye (dissociates by cationic dissociation) in an aqueous solution. ) And a property capable of ionic bonding.

Examples of the vinyl monomers copolymerizable with acrylonitrile include vinyl esters such as vinyl acetate, vinyl halides or vinylidenes such as vinyl chloride, vinyl bromide and vinylidene chloride, methyl acrylate, and the like.
(Meth) acrylic acid lower alkyl esters such as methyl methacrylate (hereinafter the description of (meth) acrylic acid shall represent both acrylic acid and methacrylic acid),
Acrylamide, styrene and the like can be mentioned.

In the present invention, the polymer constituting the fiber needs to have an anionic group. The anionic group referred to in the present invention is a sulfonic acid group, a carboxylic acid group, or the like, and in order to obtain a polymer containing these anionic groups, acrylonitrile and a monomer containing the anionic group, that is, an anion It is necessary to copolymerize with a monomer having a functional group. However, a redox catalyst used in the polymerization of acrylonitrile, particularly a sulfonic group introduced into the polymer terminal when an acidic sulfite is used as a reducing agent, is also applied to a part of a desired amount of anionic group. It goes without saying that it can be done.

However, unless the target fiber has a low level of antibacterial activity and a low level of dyeing even if it has a low antibacterial property, the anionic property of the amount of the introduced catalyst residue is not so large. The group is often unsatisfied. In such a case or when a catalyst system different from the above-described catalyst system and the like cannot expect an anionic group from the catalyst residue at all, the shortage with the required amount, or all of the required amount is an anionic group-containing simple amount It must be introduced from the body.

In any case, the amount of the anionic group to be contained in the polymer is not essentially limited. However, the anionic group partially binds to a quaternary ammonium salt-based drug (described later) to prevent the drug from being eluted or dropped off by washing or the like, thereby contributing to the maintenance of durable antibacterial performance, and the balance remaining. That is, the anionic group that is not bound to the drug is responsible for the dyeability of the polymer fiber with the cationic dye. As will be described later, the fiber of the present invention is also provided with antibacterial properties by chitosan carried by the pores of the fiber. That is, antimicrobial properties are provided by both the drug and chitosan. Therefore, the amount of the anionic group in the polymer varies depending on the cationic dyeability and antibacterial property required for the fiber. Even if the antibacterial level is the same, the antibacterial level is changed to quaternary ammonium. The required amount of anionic group varies depending on what percentage the salt drug and chitosan bear.

In general, the cationic dyeability depends on the amount of the above-mentioned non-bonded anionic group, but in order to dye a dark color such as black, dark blue or orange, the non-bonded anionic group is added in an amount of 20 mmol. / Kg or more, and more preferably 23 mmol / kg or more when deep color cationic dyeability is required. The anionic group-containing monomer for introducing an anionic group having such a role into the polymer is not particularly limited as long as it can be copolymerized with acrylonitrile, but is not limited to sodium methallyl sulfonate, 2-acrylamide-2-methylpropane sulfone. Examples thereof include sulfonic acid group-containing monomers such as acid soda, p-styrene sulfonic acid sodium, and vinyl sulfonic acid sodium, and carboxylic acid group-containing monomers such as sodium acrylate and sodium methacrylate.

The acrylonitrile-based polymer into which the anionic group has been introduced in this manner is dissolved in a usual polyacrylonitrile solvent to form a spinning solution, and is wet-spun. However, the fiber of the present invention needs to have pores inside the fiber. The pores referred to in the present invention are pores opened in the fiber surface and voids are formed in a portion deeper than the surface, that is, inside the fiber. To obtain such a special porous acrylic fiber, some measures were taken, for example, as disclosed in
Japanese Patent Application Laid-Open No. 63-145345, Japanese Patent Application Laid-Open No. 07-150470 filed by Japanese Patent Application Laid-Open No. 63-145345, discloses a method of forming macrovoids having holes in the fiber surface using a special spinning nozzle disclosed in Japanese Patent Application Laid-Open No. 161505. The method employing special spinning conditions and coagulation conditions described in (1) can be suitably adopted.

That is, when an inorganic salt such as sodium rhodanate is used as a solvent, the liquid fiber spun from the nozzle as described above is used at a temperature of -3 ° C to 15 ° C, preferably 0 ° C to 1 ° C.
Coagulation is performed under coagulation conditions of 0 ° C., and stretching is performed by washing with water, hot water or steaming to obtain a porous acrylic fiber. Also, when the solvent is an organic solvent, for example, dimethylacetamide, the target fiber can be obtained by using an aqueous solution having a concentration of preferably 40% or less as a coagulation condition. In each case, a condition in which the direction of the structure is somewhat sparser than that of the ordinary polymer concentration in the undiluted solution and the coagulation conditions aiming at a dense structure is adopted. Also, the important thing is
Until the fibers thus formed are impregnated with the following chitosan, the fibers must not be subjected to a densification treatment,
That's what it means. This is because the densification treatment crushes the pores of the fibers even if they are different in degree, and almost loses the opportunity to carry chitosan.

In the present invention, the fiber having pores inside the fiber is impregnated with an acidic solution of chitosan to neutralize and insolubilize the fiber. First, chitosan referred to in the present invention is a chitin obtained by removing contaminants such as calcium carbonate and protein from an chitin substance forming an exoskeleton of a crustacean such as a crab and a shrimp by an acid and alkali treatment, and removing chitin by a concentrated alkali treatment. It is an acetylated basic polysaccharide. The chitosan that can be used in the present invention is not particularly limited as long as it can be dissolved in an acidic solution such as acetic acid or formic acid to form a uniform solution, and it can be reversibly insolubilized by neutralization. The degree of deacetylation is 40% or more, preferably 60
% Is preferable. Here, the amount of chitosan applied is 2.8% by weight based on the weight of the fiber, indicating sufficient antibacterial activity (bacteriostatic activity value of 3 or more) even without the addition of another antibacterial agent. However, another antibacterial agent used in combination as in the present invention,
When a quaternary ammonium salt-based drug contributes, the amount of chitosan to be applied is determined by the required antibacterial performance and the amount of other antibacterial agents, but generally may be smaller than that of chitosan alone.

Means for impregnating, neutralizing and insolubilizing the porous acrylic fiber with the acidic solution of chitosan is not particularly limited,
For example, there is the following method. That is, the fiber bundle that has undergone the hot water drawing process of wet spinning is immersed in a solution in which chitosan is dissolved in 2% by weight of acetic acid so that the chitosan concentration is 5% by weight, and the chitosan solution is impregnated into the pores of the fibers. Let it. Next, the fiber bundle that has exited the chitosan bath is introduced into an aqueous sodium hydroxide solution adjusted to pH 10, and the chitosan solution is neutralized to make it in a solid state, that is, water-insoluble from the solution state.
As a result, chitosan exists in a solid state in the pores in the fiber.

Further, the structure of the fiber bundle is densified in a dry densification step. In this step, the pores in the fibers shrink somewhat, so that the solid chitosan held inside is firmly supported. Without going through this step, it is impossible to prevent the chitosan from easily falling off from the fiber due to the action of water or the like, even though it is solid. By this step, the fiber is given sufficient physical properties of the surface with high elongation and strong support of chitosan. The conditions of the densification process are not significantly different from those for ordinary clothing, for example, drying under humidity control in a relaxed state is adopted, but of course, a drum type dryer in a tension state is also used it can.

The fiber of the present invention is obtained by further imparting one or more quaternary ammonium salt-based drugs represented by the above general formula [3] to the fiber having chitosan supported in the pores through the densification step. It is. Specifically, a predetermined agent is applied to the fiber bundle that has undergone the above-described densification step by a dipping method, a spray method, or the like.For example, as an example using crimper preheating, the specific agent of the present invention is applied to the treatment tank solution. During the addition, a target amount to be adsorbed to the fiber bundle is added, and then the agent is applied to the fiber bundle by squeezing it to a constant amount by a crimper. To complete the binding. The steam is not limited to saturated steam, superheated steam and the like, but it is preferable to perform the treatment at 105 ° C. to 140 ° C. in saturated steam. 5 to 30 for relaxing
% Is preferred. Thus, the drug binds to the anionic group present in the polymer constituting the fiber and takes a chemical structure that cannot be easily removed. This bond appears to be an ionic bond,
Under the environmental conditions in which the fiber is used as a final product, it does not debond. This, combined with the strength of the above-described chitosan-carrying form, ensures the durable antibacterial properties of the fiber of the present invention.

As described above, the quaternary ammonium salt-based drug binds to the anionic group of the fiber, in other words, blocks the ionic group. Since the ionic group is, of course, a dyeing site of the cationic dye, the cationic dyeability of the fiber depends on the amount of the non-bonded or free anionic group with the drug. Therefore, the amount of the quaternary ammonium salt-based drug to be applied is determined in consideration of the required antibacterial level, cationic dyeing level, and anionic group abundance, which will be described later. The step of applying the agent to the fibers must be after the above-described densification step. That is, when the drug is applied before the densification step, the drug does not stay on the fiber surface but also penetrates into the fiber and binds to the anionic group inside because the fiber structure is still sparse. This is because the amount of drug present on the fiber surface is reduced, and the manifestation of antibacterial performance is as poor as possible.

As such a quaternary ammonium salt-based drug, the carbon number of R1 in the general formula [3] is preferably from 8 to 21, and if it is less than 8, the antibacterial performance is reduced. Further, when the carbon number of R1 exceeds 21, the antibacterial performance is reduced and the dyeability is significantly reduced. R2 preferably has 2 to 5 carbon atoms,
If it exceeds 5, the dyeability deteriorates. Further, R3, R4,
The carbon number of R5 is preferably from 1 to 5, and if it exceeds 5, the dyeability will be reduced.

The quaternary ammonium salt-based drug according to the present invention is preferably stearyl amido propyl
Dimethyl hydroxyethyl ammonium nitrate, cetyl amide propyl dimethyl hydroxyethyl ammonium nitrate, stearyl amide propyl dimethyl hydroxyethyl ammonium chloride, cetyl amide propyl dimethyl dimethyl hydroxyethyl ammonium Chloride, stearyl amide propyl dimethyl hydroxyethyl ammonium bromide, stearyl amide ethyl diethyl hydroxyethyl ammonium acetate, stearyl amide ethyl diethyl diethyl hydroxyethyl ammonium phosphate, stearyl
Amido propyl dimethyl ethyl ammonium ethyl sulfate, cetyl amide propyl dimethyl ethyl ammonium ethyl sulfate, stearyl amide propyl diethyl methyl ammonium methyl sulfate, cetyl amide propyl diethyl diethyl methyl ammonium Examples include methyl sulfate, stearyl amide propyl trimethyl ammonium methyl sulfate, cetyl amide ethyl diethyl methyl ammonium methyl sulfate, stearyl amide ethyl trimethyl ammonium methyl sulfate, and the like.

The amount of the agent to be applied to the acrylic fiber is generally preferably from 0.2 to 2.0% owf, and more preferably from 0.2 to 1.0% owf. As described above, the determination should be made in consideration of the sharing of the antibacterial performance with chitosan and the dyeability, and one of the above-mentioned drugs or a mixture of several drugs may be used. If the applied amount is less than 0.2% owf, it is necessary to increase the amount of chitosan supported necessary for developing antibacterial properties. Therefore, it is necessary to prepare a concentrated solution of chitosan, and the viscosity becomes high. It is difficult to penetrate inside. Also, 2.0
When the content exceeds% owf, the amount of free anionic groups decreases, so that the amount of saturated dyeing of malachite green, which is a cationic dye, decreases, and it becomes difficult to perform dark color dyeing. Although there is no means to increase the anionic group introduced into the acrylonitrile-based polymer by copolymerization, it is generally expensive and cannot be increased without limitation. Here, in order to exhibit cationic dyeability that enables deep color dyeing, the amount of anionic group that is not bound to the quaternary ammonium salt-based drug in the fiber is 23 mmol.
l / kg or more, preferably 25 mmol / kg or more. Black when less than 23 mmol / kg,
It becomes difficult to dye dark colors such as navy blue and orange, and there may be a problem with dyeing fastness, especially wet fastness. However, this is not always the case unless a deep color is intended.

The amount of anionic group not bound to the quaternary ammonium salt-based drug in the present invention means that the molecular weight of malachite green is 46 based on the amount of saturated dyeing of malachite green.
3 is a value calculated by the following equation (3), and the amount of malachite green saturated dyeing (weight% to fiber weight,% ow)
f) Staining is carried out under the following conditions, absorbance is measured by a residual liquid colorimetric method according to a conventional method, the degree of dyeing is determined by the equation (1), and calculated by the equation (2). Dyeing solution: Malachite green, 3.5% owf pH adjuster: 1.5% owf, acetic acid Bath ratio: 1/100 Temperature: 100 ° C Time: 150 minutes Measuring method: U-2000, manufactured by Hitachi, Ltd. Using a mold, the absorbance for light at 620 nm is measured. If the degree of dyeing determined by this method exceeds 70%,
Malachite green in the dyeing liquor is 5.0% owf and remeasured.

[0028]

(Equation 1)

[0029]

(Equation 2)

[0030]

(Equation 3)

[0031]

The fiber of the present invention is a quaternary ammonium salt-based drug bonded to chitosan supported on pores opened on the fiber surface and an anionic group of a polymer constituting the fiber as having antibacterial properties. And has a non-bonded anionic group to carry out cationic dyeability. Therefore, since the chitosan and the drug express antibacterial properties in cooperation with each other, the amount of binding of the drug can be reduced as compared with a case where chitosan is not used in combination to express a certain antibacterial property. This means that the number of bound anionic groups is small and, at the same time, the number of non-bonded anionic groups is large, so that high cationic dyeability can be obtained. Although the mechanism of the antibacterial action of chitosan is unclear, the cationic amino group of quaternized chitosan attracts anionic constituents in the cell wall of the bacterium in the same manner as the quaternary ammonium salt-based drug. It is presumed that the biosynthesis of the cell wall is inhibited, so that antibacterial properties are expressed.

[0032]

The following examples are provided to facilitate understanding of the present invention, but are merely illustrative, and the gist of the present invention is not limited thereto. Parts and percentages in the examples are shown on a weight basis unless otherwise specified. The antibacterial performance evaluation and washing conditions described in the examples were carried out by the following methods.

(1) Antibacterial performance Test strain: Staphylococcus aureus ATC
C 6538P Test method: According to the method specified by the Textile Sanitary Processing Council (SEK), pour a bouillon suspension of the test bacterium on a sterile sample cloth, and culture in a closed container at 37 ° C for 18 hours. The number was counted, and the bacteriostatic activity value = (logB-logA)-(logC-1)
ogA) is used. Generally, if the bacteriostatic activity value is 2.2 or more, it is considered to have antibacterial performance,
3.0 or more is preferable.

(2) Washing conditions According to the method 103 of JIS-L-0213 (for household washing machines), washing is repeated using a monogenyuni manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a detergent. (10 times, 20 times)

(3) Evaluation of Pore of Gel Fiber The weight (W1) of the fiber after freeze-drying the gel fiber, the immersion of the dried fiber in water for 1 hour, and the dehydration at 1000 G acceleration for 2 minutes. from the weight (W2) is a value calculated by the following equation, the specific gravity of water 1.00 g / cm ^3, was determined specific gravity of the acrylic fiber as 1.17 g / cm ^3, the pores are opened in the surface It is a volume ratio. Pore volume ratio = [{(W2) − (W1)} / 1.00] / [(W1) /1.17]
× 100 (%)

Example 1 91% of acrylonitrile, 8% of methyl acrylate and 1% of sodium methallyl sulfonate were polymerized according to a conventional method.
An acrylonitrile-based polymer having a total sulfonic acid group content of 30 mmol / kg was synthesized and dissolved in a 46% aqueous sodium rhodanate solution to prepare a stock solution for spinning having a polymer concentration of 12%. The stock solution is extruded into a 10% aqueous solution of sodium rhodanate at 5 ° C. using a well-known 3d die, and then subjected to cold drawing, washing with water, and hot drawing to form a porous acrylic gel fiber having a porosity of 216%. I got The porous acrylic gel fiber is immersed in a chitosan / 2% by weight acetic acid solution adjusted to a chitosan concentration of 0 to 10% by weight at 30 ° C. for 1 hour, and then neutralized with a sodium hydroxide aqueous solution adjusted to pH 10. Chitosan was insolubilized. The fiber after neutralization was washed with water and dried and densified (relaxed state, 90 ° C.).

Then, using a crimper preheating tank,
At 0 ° C, stearyl-amide-propyl-dimethyl-hydroxyethyl-ammonium nitrate is added as a quaternary ammonium salt-based drug in an amount of 0 to 1% owf as a pure component to the weight of the traveling fiber bundle, and then a crimper is used. The fiber bundle after squeezing and crimper was subjected to a relaxation wet heat treatment at 127 ° C. for 7 minutes. The oil was applied, dried and cut by a conventional method. 1 to 6 fibers were obtained. Each sample was evaluated for the amount of unbound sulfonic acid group, the amount of the quaternary ammonium salt-based drug, the amount of chitosan carried, the antibacterial property, and the deep color staining property. In addition, the dark color dyeability is a product of Cat Black, manufactured by Hodogaya Chemical Co., Ltd.
Using SBH 5.0% owf, heating at a bath ratio of 1/100 to a boil at an initial temperature of 60 ° C. to a boil at a rate of temperature increase of 2 ° C./min. Was evaluated. The results are shown in Table 1.

[0038]

[Table 1]

Sample No. 1 of the present invention shown in Table 1 was used. 3, 5, 6
By having 23 mmol / kg or more of anionic groups that are not bound to the quaternary ammonium salt-based drug, it has excellent dark-coloring properties, and furthermore, chitosan is supported in the pores of the fiber,
In addition, since a quaternary ammonium salt-based drug is also provided, all of them show sufficient antibacterial activity with a bacteriostatic activity value of 2.2 or more. In addition, it was also confirmed that these samples had durability such that the antibacterial performance did not decrease even after repeated washing 10 times and 20 times.

On the other hand, the sample No. In the cases of Nos. 1 and 2, dark color staining is possible because the quaternary ammonium salt-based drug is lacked only by carrying chitosan, but antibacterial activity is not obtained because the bacteriostatic activity value is 2.0 or less. Sample No. In sample No. 4, sample No. Compared with No. 3, antibacterial activity with a bacteriostatic activity value of 1.6 was not obtained because chitosan was not carried in spite of providing the same amount of quaternary ammonium salt antibacterial agent. These are not "antimicrobial" fibers. On the other hand, sample N
o. 7 is a quaternary ammonium salt-based drug 1.0% owf
While giving extremely good antibacterial performance when used in combination with chitosan, the amount of anionic groups not bound to the quaternary ammonium salt-based drug is as small as 20 mmol / kg, so that the deep color staining is inferior. . However, the antibacterial acrylic fiber has a wide variety of uses, and this fiber is sufficiently applicable to fields where high antibacterial properties are required and light colors are allowed.

[0041]

The antibacterial acrylic fiber according to the present invention has sufficient antibacterial properties and deep-color dyeing properties. This is originally the fourth
If an antibacterial property is to be imparted using only a quaternary ammonium salt-based agent, the quaternary ammonium salt-based agent blocks the dyeing seat made of an anionic group represented by the sulfonic acid group or the like of the acrylic fiber. It becomes impossible to dye dark colors such as blue, navy blue and red. Therefore, the application amount of the quaternary ammonium salt-based drug is suppressed to a level that does not impair the deep color dyeability of the fiber,
That is, while maintaining the non-bonded anionic group capable of deep color dyeing, the insufficient antibacterial performance was achieved by loading chitosan which hardly affected the dyeing property. In addition, in the case of a request that it is only necessary to dye in a light color, if there is an anionic group of about the amount introduced into the acrylic polymer terminal of the redox polymerization catalyst residue, the necessary dyeability is satisfied, And high antibacterial property by chitosan can be obtained. Thus, in general, compared to conventional fibers,
A notable effect is the provision of acrylic fibers having high antibacterial properties at various levels of cationic dyeability. Further, the fiber of the present invention has an advantageous effect that it has a durable antibacterial property because it does not easily fall off due to sweat, washing or the like since the antibacterial agent is chemically bonded or supported on pores. The fiber of the present invention having such excellent advantages is a yarn,
It can be processed into knitted fabrics, blankets, bores, non-woven fabrics, etc., and is widely used in applications such as comfortable clothing, bedding, interior products, living materials and industrial materials.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) D06M 13/463 D06M 13/463 // D01F 6/18 D01F 6/18 Z F term (reference) 4C058 AA03 AA05 BB07 JJ02 JJ04 4H011 AA02 BA06 BB06 BB19 BC19 DE17 DH10 4L033 AA05 AB01 AC10 AC15 BA85 CA02 DA07 4L035 BB03 BB13 EE11 EE20 JJ14 KK09 MB06 MB12 4L038 AA11 AB10 BA18 BA48 CA01 CA06 CA08 DA08

Claims (3)

[Claims] The present invention relates to a quaternary ammonium salt-based drug represented by the following general formula [1], wherein chitosan is supported in pores inside a fiber, and a part of an anionic group of a polymer constituting the fiber is partially An antibacterial acrylic fiber characterized by being combined with at least one species. Embedded image 2. An antibacterial bacteriostatic activity value of 2.2 or more, having at least 23 mmol / kg of anionic groups unbound to a quaternary ammonium salt drug. The antibacterial acrylic fiber as described. 3. An acrylonitrile polymer is wet-spun and impregnated with an acidic solution of chitosan into the pores of the fiber before the densification step, neutralized and insolubilized, and then subjected to a dry densification treatment to carry out a dry densification treatment. A method for producing an antibacterial acrylic fiber, wherein chitosan is supported on a substrate, and one or more quaternary ammonium salt-based drugs represented by the following general formula [2] are further provided. Embedded image