JPH0316423B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Field of the Invention The present invention relates to a method for antibacterial processing of acrylic fibers, and more specifically, the present invention relates to an antibacterial processing method for acrylic fibers.
By adding a specific compound to the treatment bath when treating with organosilicon quaternary ammonium salt, which has antibacterial and antifungal effects against microorganisms such as mold, there is no change in the texture of the fiber after treatment, and it is easy to wash. The present invention relates to an antibacterial processing method that can significantly improve durability. (b) Conventional technology In recent years, as society has matured and the population has aged, there has been a strong latent desire to maintain and improve health, and the need to develop cleaner and more comfortable clothing, bedding, home products, etc. has increased. It's coming. In addition, in a hot and humid environment like our country, microorganisms such as bacteria and mold are particularly active in breeding, such as athlete's foot, rot caused by bacteria, and unpleasant odors caused by fermentation. We are now facing a situation that is having a negative impact on our living environment, including food, clothing, and shelter, and threatening our desired comfortable and sanitary lifestyles and health. Under these circumstances, there is a social need for antibacterial processed products to help prevent the occurrence of microorganisms that have a negative impact on our living environment, suppress their growth and reproduction, and maintain a hygienic and clean living environment. Attempts are being made to develop the following. For textile products that have been treated with antibacterial sanitary treatment, it has been said that the important requirements are greater hygienic effects, durability, and high safety, and there are cases where these requirements are not met. There are many processed products that have been erased. In addition to these requirements, it is important to note that antibacterial and hygienic treatments do not impair the inherent performance of the treated product, such as appearance, texture, color, or other important functions. There is no such thing. Here, an organosilicon quaternary ammonium salt represented by the following formula is widely known as an antibacterial, antifungal, and antialgal agent, and is accepted as meeting the above three requirements. By the way, as shown in the diagram below, the organosilicon compound is treated in a processing bath (aqueous solution). Hydrolysis of three methoxy groups, . Formation of oligomers by condensation,
．． Formation of bonds between oligomers and fiber substrates (for example, formation of hydrogen bonds when the substrate is cellulose), . Through the reactions of drying, film formation, and curing (formation of covalent bonds due to dehydration), a strong film is formed on the surface of the treated fiber, and the alkyl group quaternary ammonium as an organic functional group is formed on the surface of the treated fiber. The introduction of salt is believed to provide durable antibacterial effects to textile products. However, compared to fiber substrates such as cotton (cellulose), which contain a functional group (-OH) that can serve as an acceptor for the reactive group residue (-OH) of the oligomer in the above reaction, it is difficult to synthesize. In the case of fibers, such as acrylic fibers, which do not contain such functional groups, the hardness and durability of the cured film formed between the organosilicon compounds is markedly different, resulting in an event that seems to be inferior. When antibacterial treatment is applied to acrylic fibers by applying the compound, there is a need to improve the washing durability of the effect. In addition, regarding the method of treating fibers with the organosilicon compound, the form of the fibers, such as raw cotton,
The optimal processing method is selected depending on the fabric such as yarn, skeins, cheese, etc., knitted fabrics, and the piece product that has become the product, but in general, (1) the fibers are impregnated with a processing solution and then squeezed with a mangle; A method of applying a required amount of a processing agent and then drying and fixing the material; (2) impregnating the fiber material with a treatment liquid and then centrifugally dehydrating it to apply a required amount of a processing agent;
(3) A method in which fibers are treated in a treatment bath containing a predetermined amount of a processing agent for a predetermined period of time to adsorb the processing agent, and then dehydrated and dried and fixed. By the way, in the treatment methods (1) and (2) above, in (1), the treatment liquid is added to 1 part of the fiber.
0.3 to 2.0 copies, 0.2 to 0.5 copies can be given in (2),
In both cases, the treatment liquid exceeds the restricted moisture content of synthetic fibers such as acrylic fibers and is applied to the fibers in a floating state, and because the amount of treatment liquid applied to the fibers is small, a high concentration of treatment liquid is inevitably required. The processing liquid in a floating state causes processing spots, and furthermore, when drying, the processing agent migrates to the workpiece, further promoting the processing spots. Such treatment spots give rise to an abnormal texture of the product after treatment, and areas with excessive adhesion tend to yellow, which may cause abnormal irritation in terms of skin safety and hygiene.Furthermore, areas with insufficient adhesion may lack antibacterial performance. It also provides spots for the growth of mold and bacteria, and furthermore, non-uniform adhesion is thought to lead to asymmetry in the formation of networks between organosilicon compounds, leading to deterioration in durability. On the other hand, in the treatment method (3) above, 5%
The treatment is carried out for a predetermined period of time in ~100 parts of the treatment solution, and the concentration of the treatment agent in the treatment solution is 20 to 400 times dilute compared to methods (1) and (2) above, so the treatment agent does not affect the fibers. It is generally considered desirable for homogeneous adsorption unless it exhibits selective adsorption properties. However, organosilicon compounds used as processing agents have poor adsorption properties from low-concentration processing solutions, and because the processing agents are cationic (quaternary ammonium salts), they are not suitable for ordinary acrylic fibers containing anionic groups. However, unlike on cotton, the adsorption on acrylic fibers is unexpectedly poor. Therefore, when the fibers to be treated are acrylic fibers, in order to impart the desired antibacterial properties to the fibers, it is necessary to use a highly concentrated treatment solution even in method (3), and the treatment solution has poor adsorption properties. Therefore, we were faced with an undesirable situation in terms of processing costs and wastewater pollution, which involved disposing of the processing residual liquid in which a high concentration of expensive processing agents remained. (c) Point of view As a result of intensive research in order to provide an antibacterial processing method that does not have the various drawbacks mentioned above, the present inventors have found that by adding a specific compound to the treatment bath, organosilicon quaternary The present invention was achieved by discovering that ammonium salts can be applied uniformly and with high efficiency from a low concentration treatment solution. (d) Purpose of the invention The purpose of the present invention is to be able to uniformly and firmly apply organosilicon quaternary ammonium salt to acrylic fibers from a low-concentration treatment solution with high efficiency, thereby providing excellent washing durability and reducing the The objective is to provide an antibacterial processing method that does not change the texture of treated products. Another object of the present invention is to provide an antibacterial processing method that can exhaust a low-concentration treatment liquid with high efficiency and is free from problems in terms of processing cost and wastewater pollution. A different object of the present invention is to provide an antibacterial processing method that can uniformly apply a processing agent and is free from problems such as abnormal texture, yellowing, skin irritation, and spots such as mold growth caused by processing spots. In particular, further objects of the invention will become apparent from the detailed description of the invention provided below. (E) Structure of the Invention The above object of the present invention is to prepare acrylic fibers by the following general formula. (However, R ₁ is a C ₁₂ to ₁₈ long chain alkyl group, R ₂ is
R ₃ and R ₄ represent a lower alkyl group, and X represents Cl, Br, I or CH ₃ COO. ) The treatment with the organosilicon quaternary ammonium salt shown in the following is achieved by adding electrolyte salts to the treatment bath. (f) Specific explanation of the composition Here, the acrylic fiber according to the present invention refers to acrylonitrile (hereinafter referred to as AN) alone or from 50% by weight or more of AN and another vinyl monomer that can be copolymerized with AN. This term refers to fibers formed from polymers, and the form of such fibers may be short fibers, long fibers, yarns, or knitted fabrics. synthesis,
It does not matter if it is a mixture with other types of fibers such as synthetic fibers. Furthermore, the organosilicon quaternary ammonium salts represented by the general formula used in the present invention include lauryl (C ₁₂ −), myristyl (C ₁₄ −), cetyl (C ₁₆
-) or stearyl (C ₁₈ -) dimethylamine by heating reaction with tertiary amine γ-halopropyl trialkoxysilane, such as dimethyl octadecyl (3-trimethoxysilyl)-propyl Ammonium chloride was manufactured by Shin-Etsu Chemical Co., Ltd., PETARCH in the United States,
It is commercially available from SYSTEM, and Dow Corning's product name DC5700 is also said to be this type of compound. Such compounds contain approximately 50% active ingredient
It is supplied as a methanol solution and is known to have excellent antibacterial and antibacterial effects against various molds and bacteria. It has been certified as meeting the requirements of the Japanese law, and is an extremely safe processing agent as long as it is used in appropriate amounts. Bacteria and molds for which the processing agent exhibits antibacterial effects include, for example, Gram-positive bacteria such as Staphylococcus aureus and Bacillus subtilis; Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, urea-degrading bacteria, and Klebsiella pneumoniae; and Ringworm interdigitalis. Examples include fungi such as fungi and black mold. The processing agent is added in an amount of 0.1 to 3 based on the weight of the fiber to be processed.
When given within the range of %, it shows results, but
If the upper limit is exceeded, the texture may become abnormal and may cause irritation that is undesirable from the standpoint of skin safety and hygiene. The processing temperature with the processing agent is 20 to 90°C;
Preferably, a temperature of 30 to 70°C is appropriate; if the temperature exceeds 70°C, the amount of adsorption will decrease, and if it exceeds 90°C, it will decrease significantly. Further, although it is difficult to define the processing time unambiguously, a range of approximately 10 to 60 minutes is appropriate. Next, regarding the electrolyte salts added to the treatment bath, which can be said to be the central component of the present invention, cationic components include, for example, alkali metals such as lithium, natrium, and potassium; alkaline earths such as beryllium, magnesium, calcium, and barium. Metals:
Other metals such as copper, zinc, aluminum, manganese, iron, and nickel; ammonium ions, and a type of salt in which the anion component is composed of an acid group such as hydrochloric acid, sulfuric acid, rhodanic acid, acetic acid, etc. Mixtures of two or more types of salts may be mentioned, among which alkali metal, alkaline earth metal or ammonium salts of sulfuric acid, rhodanic acid, acetic acid are preferred. The amount of salts added is based on the weight of the fiber.
It is desirable to set the concentration within the range of 0.1 to 20%, more preferably 0.5 to 10%; use of a high concentration exceeding the upper limit is not desirable because it will harden during the dry heat treatment after treatment and impair the texture of the fiber. do not have. Such salts can be added in advance together with the processing agent before the fibers to be processed are put into the processing bath, added after the fibers have been treated with the processing agent for the required time in the processing bath, or added after the fibers are treated with the processing agent in the processing bath. Any means such as gradual addition during treatment with a processing agent can be adopted, and in any case, if necessary, electrolyte salts can be added in several portions. (g) Effects The reason why the method recommended in the present invention enables highly durable antibacterial processing without causing any change in the texture of the fibers after treatment has not yet been clearly explained. is estimated as follows. In other words, since organosilicon quaternary ammonium salts are cationic, they have some adsorption properties to ordinary acrylic fibers, but unexpectedly, their adsorption capacity is poor, especially in terms of processing costs and wastewater pollution. However, by adding electrolyte salts to the treatment bath, the processing agent is coagulated and the affinity for acrylic fibers is increased.
It is believed that this adsorption increases the proximity of processing agent molecules and promotes the formation of a thin, uniform, and strong network.In particular, when using Rodan salt, during drying and fixation heat treatment, Rodan salt Concentrated in the fiber surface layer, it swells and dissolves the fiber matrix and promotes the penetration and adhesion of processing agents into the matrix layer to form a robust network or film, or at that time, it swells and dissolves the fiber matrix. It is believed that the durability is further improved because some chemical change occurs to provide a reaction receptor for the organosilicon compound, thereby firmly bonding the compound to the fiber matrix. A noteworthy effect of the present invention is that the above-described method of the present invention can impart antibacterial performance with excellent durability to acrylic fibers without any loss in texture. In addition, since the present invention employs an exhaustion treatment method using a low concentration treatment bath, there are no problems with processing costs or wastewater pollution, and in addition, in the same dyeing bath, subsequent to dyeing, or using a softener. Another advantage of the present invention is that it can be processed and processed at the same time. EXAMPLES The present invention will be described below in more detail with reference to Examples, but the scope of the present invention is not limited in any way by the description of these Examples. In the examples, parts and percentages are expressed on a weight basis unless otherwise specified. Example 1 A woven fabric (1/52′S, plain weave) made of 100% yarn of acrylic fiber (manufactured by Nippon Exlan Kogyo Co., Ltd., trade name Exlan K2.0 ^d × 51 mm) was desized and placed in a treatment solution. Four types of samples (A to D) were prepared by immersion treatment at 50° C. for 30 minutes. The treatment liquid is a 42% methanol solution of dimethyl octadecyl (3-methoxysilyl)-propylammonium chloride at 2.0% based on the weight of the fabric (0.84% pure).
and 3.0% of the salt shown in Table 1 below were each weighed out and poured into water in an amount 30 times the weight of the fabric with thorough stirring. On the other hand, a comparative sample (E) was prepared in the same manner as above except that no salt was used. Table 1 shows the results of evaluating the antibacterial properties of the five types of samples (A to E) obtained.

[Table] The antibacterial properties after washing were measured using Nitsusan Nonion NS-210 (manufactured by Nippon Oil & Fats Co., Ltd.) as a detergent, and the samples were washed a specified number of times in a household electric washing machine. This is what I did. From Table 1, it is understood that the processing method of the present invention imparts antibacterial properties with significantly improved durability. Example 2 After washing the jersey fabric (1/64′S 22G punch roll) made of 100% acrylic fiber used in Example 1 in hot water, it was immersed in a treatment solution at 60°C for 40 minutes to produce four types of fabrics. Samples (F to I) were prepared. The treatment solution was prepared by pouring 2.0% of the quaternary ammonium salt used in Example 1 and 5.0% of the salt shown in Table 2 below into water in an amount 50 times the weight of jersey fabric while stirring well. On the other hand, a comparative sample (J) was prepared without using salt. Table 2 shows the results of evaluating the antibacterial properties of the five types of samples (F to J) obtained. In addition, the antibacterial property was determined by soaking 1 g of the sample in 75 ml of test bacteria solution prepared according to AATCC-100-1974.
After being immersed for a period of time with stirring, the number of bacteria after culturing for 0 and 2 hours was determined and the reduction rate (%) was calculated.

[Table] As is clear from Table 2, the processing method of the present invention imparts antibacterial properties with improved durability. Example 3 200 pairs of sports socks (10kg) knitted from acrylic, cotton blend yarn, nylon textured yarn, and polycarethane filament yarn were bleached using a paddle dyeing machine and then heated at 45°C in a processing solution. Four types of samples (K to N) were prepared by immersion treatment for 15 minutes. The treatment liquid used was the same as in Example 2, except that 0.8% of quaternary ammonium salt was used based on the weight of the socks, and 40 times the volume of water was used. Table 3 shows the results of evaluating the antibacterial properties of five types of samples (K to O), including a comparative sample (O) in which no salt was used, in the same manner as in Example 1.

[Table] From the above table, the excellent effects of the processing method of the present invention can be clearly understood.

Claims (1)

[Scope of Claims] 1. Acrylic fibers with the following general formula: (However, R ₁ is a C ₁₂ to ₁₈ long chain alkyl group, R ₂ is
R ₃ and R ₄ represent a lower alkyl group, and X represents Cl, Br, I or CH ₃ COO. ) An antibacterial processing method for acrylic fibers, characterized in that electrolyte salts are added to the treatment bath during treatment with an organosilicon quaternary ammonium salt. 2. The antibacterial processing method according to claim 1, wherein electrolyte salts are added in an amount of 0.1 to 20% based on the weight of the fiber.