JPH05140868A - Production of acrylic fiber having antimicrobial activity - Google Patents

Abstract

PURPOSE:To obtain the subject acrylic fibers of high safety by quaternizing the fibers from an acrylonitrile-amino group nitrogen-containing acrylic ester copolymer with an alkyl halide. CONSTITUTION:The acrylic fiber from a copolymer comprising acrylonitrile and an antifungal amino group nitrogen atom-containing acrylic ester of formula I [R1 is H, CH3; R2 is CH3, C2H5; R3 is CH3, C2H5; R4 is (CH2)n where n is 2 to 3 or CH2CH(OH)CH2] is coated with an emulsion of an alkyl halide of formula II (R5 is CnH2n+1 where n is 1 to 20 or C6H5CH2; X is Cl, Br, I), then heat-treated to quaternize the nitrogen atom of the amino group to give the subject acrylic fibers having effective antifungal activity against various kinds of fungi.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an antibacterial activity-immobilizing group introduced into a synthetic fiber composed of a polyacrylonitrile copolymer, which is highly safe for the human body and effective for a wide variety of bacterial species. It relates to a method for producing active fibers.

[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 such as our country, the reproduction of microorganisms such as bacteria and mold is particularly active.For example, bacteria and bacteria adversely affect the living environment of food, clothing and housing, such as the unpleasant odor caused by decay due to bacteria, and the required comfort. 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 of imparting antibacterial activity to the polyacrylonitrile fiber product, (1) a low molecular weight antibacterial agent is contained in the fiber during spinning. Alternatively, it is applied to the fiber together with a processing agent or the like. (2) An alkoxysilane quaternary ammonium salt compound having antibacterial activity is bonded on the fiber. (3)
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 addition, during the synthetic fiber manufacturing process, followed by textile processing, the additive may be a toxic by-product (e.g., dioxins) due to long-term heat treatment at extremely high temperatures, 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. Further, 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 those of the mobile 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 antibacterial activity is even more difficult. Further, the application of the processing agent may impair the product performance originally held in the final product, such as appearance, texture, color, and other important functions.

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 which bonds by a condensation reaction. Fibers, acrylic fibers, polyester fibers, and nylon fibers have the problem of poor durability because they cannot be bonded by a condensation reaction on the fiber surface. That is,
Lack of durability against repeated washing.

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. However, on the other hand, the amino groups, which are the antibacterial active sites, are distributed throughout the fiber, and the rate of effective use on the fiber surface in contact with microorganisms is roughly one tenth, which is extremely high. Antibacterial activity is weakened due to low activity. In order to reinforce this, when an amino group portion equivalent to ten times the required amount is introduced by copolymerizing a monomer, the content of the copolymerization component becomes too large and deviates from general fiber physical properties. In addition to the above acrylic fibers, the economical efficiency is significantly impaired by the use of a large amount of expensive monomers.

[0006]

The antibacterial activity of polyacrylonitrile fiber 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. Therefore, the amino group on the fiber is quaternized in order to enhance the stable and highly efficient scavenging activity of microorganisms. Alkylation reaction of amino compounds in a homogeneous system such as a liquid phase is generally known, but the reaction in a fiber solid phase is an unknown matter. Further, there are no cases or knowledge to carry out industrially, and there is no clue to undertake.

[0007]

In the present invention, a polyacrylonitrile copolymer fiber in which a copolymerization component of the following general formula (A) is introduced as an amino group having antibacterial activity is used. The most main feature is that the group is quaternized with an alkyl halide of the following general formula (B) to selectively enhance antibacterial activity. As a method for producing the same, as a result of diligent research, it was found that an amino group on the fiber can be alkyl-quaternized by a method of applying an emulsified alkyl halide on the fiber and then performing a heat treatment. By this method, the antibacterial activity can be reinforced and the purpose of imparting the antibacterial activity with high durability and safety is realized. Further, according to this method, it is not necessary to introduce many copolymerization components, so that the characteristics can be exhibited without deteriorating the fiber physical properties originally possessed by the acrylic fiber.

General formula (A):

[Chemical 3]

General formula (B):

[Chemical 4]

Generally, the reaction rate of quaternization of amines is affected by many factors such as basicity of amine, reactivity of halide and polarity of reaction solvent. The alkyl halide used for quaternization is insoluble in water and has a limit of solubility even in a highly polar reaction solvent. On the other hand, it is also known that the longer the alkyl chain length of the halide, the poorer the reactivity. The reaction temperature is accelerated as the temperature increases, but under normal pressure it is limited by the boiling point of the solvent. Although water is a reaction medium having a high boiling point and high polarity, an alkyl halide is insoluble in water regardless of the length of the chain. On the other hand, there is no case of reacting a long-chain alkyl halide having poor reactivity with an amino group on the fiber, and it has been extremely difficult by the existing technical means. When carrying out the reaction between the amino group and the alkyl halide on this solid phase, it is necessary to select a temperature above the glass transition temperature of the fiber to be reacted and to avoid the temperature at which the fiber is deteriorated and the fiber characteristics are significantly deteriorated. Considering the necessity, when water is used as a medium, paying attention to the fact that high temperature conditions effective for the reaction can be set, and by solubilizing the alkyl halide in water, emulsifying, or in other words, forming a suspension, Forming a reaction medium,
The method of applying the alkyl halide contained in the suspended particles together with the suspension onto the fiber to be reacted, adhering to or contacting the fiber to be reacted, and selecting a temperature within the above range to cause the reaction was found out through repeated trial and error. It was. The suspension of an alkyl halide is prepared by the general formula (C): RO (C ₂ H ₄ O) nHR =
-C ₁₂ -C _18, polyoxyethylene alkyl ethers represented by n = 5 to 30, Formula _{(D): RC 6 H 4} O (C 2 H 4 O) nH R =
-C ₈ H _17, polyoxyethylene alkyl phenol ethers represented by _{-C 9 H 19, n = 5~30} , the general formula _{(E): RCOO (C 2} H 4 O) nH R =
-C ₁₂ ~C _18, n = polyoxyethylene alkyl ester represented by 3 to 45, sorbitan alkyl esters, or polyoxyethylene sorbitan one or the above-described alkyl halide in more mixtures of alkyl esters After solubilizing by mixing and kneading, it can be achieved by pouring the necessary amount into water and stirring well, usually an emulsion (emulsion)
Obtained as. After applying an alkyl halide emulsion adjusted to a predetermined concentration to a fiber bundle having an amino group,
Pick up at a specified squeezing ratio and 130 ℃ in the pressure pot
Heat to a temperature of up to. As a result, it became clear that the reaction proceeded at a high rate mainly on the surface portion of the fiber, and the present invention reached the present invention in which an amino group on the fiber was alkyl-quaternized from an aqueous system. This method is different from the reaction system using a non-aqueous polar solvent,
It is excellent in industrial practicality because it allows a reaction in an aqueous system that is relatively easy to handle.

The present invention includes improvements in the effective contact of antimicrobial active groups with microorganisms, which is an essential prerequisite for antimicrobial action. The first is the quaternization of the amino group, the second is the selection of the alkyl chain length that quaternizes the amino group, and the third is the activity effective for a specific bacterial species based on the observation of the antibacterial spectrum in the antibacterial activity. Which is characterized by selecting and combining alkyl chain lengths having a selective activity for the bacterial species specified for removal and removal of alkyl chain lengths (complexing of selective activity). According to the method, the temperature at which the reaction temperature at which the reactivity associated with the alkyl chain length is sufficiently satisfied can be set can be selected because it is an aqueous system as described above. 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 relating to the metabolism,
There is no definite theory, and the action and effect are the active agent concentration, pH, electrolyte,
It is extremely complicated in relation to the solvent and 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 it becomes positively charged is determined. It is strongly affected by the medium conditions such as pH and temperature. On the other hand, the quaternized amino group is positively charged and negatively charged against microorganisms that have a negative charge regardless of the conditions of the medium such as pH, electrolyte and temperature that act on the microorganisms. Can be reliably captured.

The alkyl chain length of the alkyl halide which quaternizes the amino group on the fiber is such that the contact between the antimicrobial active group and the microorganism causes the growth of the microorganism by the action of the protein or lipid forming its cytoplasmic membrane or outer membrane. It has a deep relevance with respect to the inhibition of erythrocyte, and the destruction of the wall membrane to kill the microorganism by its action with the proteins and lipids forming the cytoplasmic membrane and outer membrane. 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. There is also a theory that it is also related to the accessibility to work. It is believed that, in conjunction with what is described here, the methods of the present invention result in alkyl groups of different chain lengths being introduced that exhibit selective activity in the antimicrobial activity of different bacterial species.

The characteristic effect of the long-chain alkyl group introduced in the present invention is that it is difficult to deactivate 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.

According to the method of the present invention, the antibacterial activity can be enhanced. By selecting alkyl quaternized fibers with different chain lengths as described above, the bacterial species showing selective antibacterial activity is determined,
It is based on the method of selecting a combination of fibers that show selective antibacterial activity against multiple species of bacteria and compounding it.
Combines selective antibacterial activity to cover and enhance a broad spectrum of antibacterial properties. The present invention provides alkyl quaternized fibers of different chain lengths therefor.

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 the microorganism. The amount should be at least 5 to 30 mmol per fiber weight (Kg).
This is achieved by a method of quaternizing an amino group nitrogen existing in the surface layer portion of the fiber with an alkyl halide.

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 the fiber is exposed to a harsh chemical reaction, the fiber itself has an antibacterial active ingredient that is not detached from the fiber.

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, when 0 <CA <100, the closer the CA is to 100, the higher the bactericidal activity. These evaluation test methods are not limited to processed products, and various copolymer fibers according to the present invention, amino groups quaternized with an alkyl chain by various methods, fibers into which a quaternary ammonium salt is introduced, For the products made of fiber and the intermediate products, the effective evaluation results on the relative antibacterial activity and antimicrobial activity against a wide range of bacterial species and microorganisms were presented. Regarding these evaluation test methods, the SF method is described in the above-mentioned "Condition Evaluation Test for Antibacterial and Deodorant Products" manual of the same conference, and the NAP method is Hironori Komali and Takayo Nakagawa, Journal of Antibacterial and Antifungal Society, Volume 16 1988. February 49-57.

[0019]

EFFECT OF THE INVENTION The acrylic fiber with antibacterial activity according to the present invention is used in a product field requiring antibacterial and deodorant functions, 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 sanitary napkins, medical clothes for preventing pathogen infection in hospitals, materials such as bandages, wound protection cloths, therapeutic clothes, surgical gowns, barrier cloths, outerwear for doctors and nurses, sweaters , Antibacterial water and air filters for gowns, tights, socks, sterilization, separation and purification, freshness and long shelf life of fruits and vegetables It is effectively used in the antimicrobial packaging material in many other contact applications because and microorganisms.

Example 1 Acrylonitrile (AN) / vinyl acetate (VAc) / 2-methyl-
5-vinylpyridine (MVP) = 85.0 / 7.5 / 7.5 [composition A],
AN / VAc / N, N-dimethylaminoethyl methacrylic acid ester (MADM) = 85.6 / 12.1 / 2.3 [Composition B], same as the left = 85.6 / 1
1.4 / 3.0 [composition C], same as the left = 85.6 / 9.2 / 5.2 [composition D]
The copolymer consisting of was dissolved in a 50% aqueous solution of rodan soda to a polymer concentration of 10% to prepare a spinning dope. The spinning dope is spun through a spinneret having a hole diameter of 0.06 mm and a number of holes of 50 in a coagulation bath of a 10% aqueous solution of rodan soda at -3 ° C to form a fiber by coagulating, and after washing with water, it is 10 times the original length in boiling water. It was stretched. Then, it was dried under constant humidity at a relative humidity of 60% and 105 ° C. Here, the respective fibers are referred to as original samples A to D. For the original samples A to D, the temperature at which each fiber length shrinks by 30% with respect to the length after constant humidity drying is selected in the range of 105 to 120 ° C., and steam heat treatment is performed to obtain a polymer of each composition. Fibers a to d were obtained from

Example 2 Copolymer of composition D (component A) and AN / methyl acrylate (MA) / sodium methallyl sulfonate (MAS) = 91.0 / 8.7 / 0.
The copolymer E having the composition of 3 (component B) is subjected to composite spinning by the above-mentioned acrylic fiber production method. Ingredient A
Is distributed in the range of 5 to 50%, preferably 10 to 35% per fiber cross-sectional area, especially component A on the surface which comes into contact with microorganisms. As the uneven distribution method, the component A is on the sheath side,
Although the sheath-core type composite spinning using the component B as the core is the most preferable, the intended point can be reached also by the sandwich type or the side-by-side type composite spinning method. That is, in the composite spinning method, by adjusting the polymer concentration and viscosity of the stock solution of both components AB,
The two components can be laminated so that the component A is concave (three-month shape) and the component A surrounds the component B. Side-by-side type (composite ratio A / B = 35/65, A covers 3 month type) consisting of copolymer D (component A) / copolymer of composition E (component B) (fiber) f) was produced.

Example 3 Original sample fiber C was quaternary alkylated with halides having different alkyl chain lengths. Butyl chloride (MW 92.2), octyl chloride (MW 148.7), lauryl chloride (MW 205) and benzyl chloride (MW 126.6), 82 parts (weight ratio) of polyoxyethylene castor oil ester 10 parts / polyoxyethylene It was solubilized by thoroughly kneading it with a mixture of 5 parts of nonylphenyl ether / 3 parts of lauric acid glyceride. Alkyl chloride and benzyl chloride each 1% pure concentration
(Weight) was poured into a 2 g / 1 aqueous solution of sodium bicarbonate with good stirring to dip the fibers into each emulsion as an emulsion and then squeezed to 60-70% (weight). 60
Each fiber to which ˜70% emulsion was attached was put in a pressure cooker and subjected to steam heat treatment at 115 ° C. for 10 minutes. as a result,
Alkyl quaternized fibers were obtained with butyl chloride (fiber G), octyl chloride (fiber H), lauryl chloride (fiber I) and benzyl chloride (fiber J), respectively.

Example 4 Fibers a, b and d of compositions A, B and D and side-by-side type fiber f of copolymer D / copolymer of composition E were alkyl quaternized with octyl chloride. Make a change. 40/20/40 (weight ratio) of polyoxyethylene (5) lauryl ether / polyoxyethylene (15) lauryl ether / polyoxyethylene (5) sorbitan monooleate
90 parts (by weight) of octyl chloride was solubilized in 10 parts (by weight) of the mixture. This was added dropwise to a 0.10% aqueous sodium carbonate solution so as to be 2% in terms of octyl chloride weight pure content while being well stirred to prepare an emulsion suspension.
The fibers a, b, d and f were immersed in the emulsified suspension and then dehydrated to a squeezing ratio of 30 to 50%. The fibers a, b, and d to which the emulsified suspension is attached are 105 ° C., and the fibers f are 127 ° C. in a pressure cooker by steam heat treatment to obtain a quaternary alkylated fiber A,
B, D and F were obtained.

Example 5 The fiber samples prepared in Examples 1 and 3 were tested for antibacterial effect by SF 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 (%) N, N-dimethylmethacryloxyethylamino group (tertiary amine) having (fiber C) and the fiber obtained in Example 3 with butyl chloride ( Fiber G), octyl chloride (fiber H), lauryl chloride (fiber I) or benzyl chloride (fiber J)
The sterilization rate by the SF method was obtained for the quaternized fiber. The results are shown in Table 1. Table 1 shows that although a decrease in the number of bacteria was observed in all the fiber samples, it was poor in the fiber c, and in the quaternized fibers G, H, I and J, all the bacteria were extremely remarkable exceeding 90%. Result in a reduction rate of.

Example 6 Regarding the (fiber G) and H prepared in Example 3, the numbers of bacteria a, b, and b were measured by the NAP method described in paragraph No. 17.
The antibacterial activity was evaluated by measuring c. The results are shown in Table 2. Fiber c before quaternization of alkyl shows growth from the initial number of bacteria, but growth is usually suppressed compared to acrylic. The antibacterial activity was increased by the introduction of the alkyl group, and the octylated fiber H showed remarkable bactericidal activity.

Example 7 Quaternary alkylated fibers A, B, D and F from Example 4
The basic nitrogen groups (active amino groups) that are thought to exist on the fiber surface were quantified, and the relationship with the antibacterial property was examined. A solution in which a predetermined amount of Acid Orange II is dissolved (Solution 1;
Use sodium hydrogen carbonate to keep the pH of the dyeing bath at 8.5 or higher) (Solution 2; adjust the pH of the dyeing bath to 3 with sulfuric acid), dye at 70 ° C for 30 minutes, and wash thoroughly with water. Determine the amount of immobilized amino (antibacterial) active groups from the amount of dyed dry fiber. 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 3. Good antibacterial activity was shown in all of the samples, in which the amount of activating groups cationized on the fiber surface exceeds 5 mmol / Kg, regardless of the pH of the system, and fibers A, B, D and F.

Example 8 Lauryl chloride was solubilized by the same method as described in Example 4, and lauryl groups were introduced into fibers c and d by the same method to obtain quaternized fibers CL and DL. The fibers CL and DL prepared here were subjected to a washing test with an anion-active neutral detergent (Monogen Uni) to examine changes in antibacterial activity due to washing. Washing test prescription and procedure are JIS
According to L 0217, 103. The results are shown in Table 4. The fibers CL and DL show a high sterilization rate even after washing.
It demonstrates the robustness of the fiber-forming polymer itself, which possesses antibacterial components. 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 is seen, a characteristic group introduced into the fiber molecule in an appropriate amount,
It seems that the alkyl group plays a role of inhibiting it.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

Claims (1)

[Claims] 1. An amino group nitrogen of a fiber made of a polyacrylonitrile copolymer into which a copolymerization component of the following general formula (A) is introduced is quaternized with an alkyl halide of the general formula (B). A method for producing an antibacterial active acrylic fiber. General formula (A): General formula (B):