JPH055947B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Field of the Invention The present invention relates to an antibacterial processing method for textile products, and more specifically, the present invention relates to an antibacterial processing method for textile products, and more specifically, an organosilicon quaternary ammonium salt having an antibacterial and antifungal effect against microorganisms such as bacteria and mold. By coexisting electrolyte salts in the treatment solution and then treating with a specific compound, there is no change in the texture of the fibers after treatment, there is less variation, and the washing durability is significantly improved. This relates to an antibacterial processing method for obtaining (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, putrefaction caused by bacteria, and unpleasant odors caused by fermentation. We are now faced with a situation that is having a negative impact on the living environment of clothing, food, and shelter, and threatening the comfortable and sanitary lifestyles and health that we desire. 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 It has been said that the important requirements for textile products that have undergone antibacterial sanitary processing are greater hygienic effects, durability, and high safety. There are also many processed products. In addition to these requirements, it is important to note that antibacterial and sanitary processing does not impair the original performance of the processed product, such as appearance, texture, color, and 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 robust film is formed on the surface of the treated fiber, and the alkyl quaternary ammonium salt as an organic functional group is applied to the surface of the treated fiber. It is believed that this method provides durable antibacterial effects to textile products. However, as in the case where the fiber substrate is cotton (cellulose), the above problem occurs. Synthetic fibers, such as acrylic fibers, do not contain functional groups (-OH) that can act as acceptors for reactive group residues (-OH) of oligomers in the reaction. If not, the solidity of the cured film formed between the organosilicon compounds,
We have encountered a phenomenon in which the durability seems to be significantly different and inferior, and when applying the compound to antibacterial treatment to synthetic fibers such as acrylic fibers, there is an urgent need to improve washing durability. In addition, regarding the method of treating textile products with the organosilicon compound, the optimum processing method depends on the form of the fiber, such as raw cotton, yarn (skein, cheese, etc.), fabrics such as knitted fabrics, and piece objects in the form of products. Generally speaking, (1) the textile product is impregnated with the treatment liquid, squeezed with a mangle, the required amount of processing agent is applied, and then dried and fixed; (2) the textile product is impregnated with the treatment liquid and then (3) Processing the textile product in a treatment bath containing a predetermined amount of the processing agent for a predetermined period of time to adsorb the processing agent, followed by dehydration and drying. Methods such as fixation are employed. However, in the treatment methods (1) and (2) above, the treatment liquid can be applied to 1 part of the fiber in the range of 0.3 to 2.0 parts in (1) and 0.2 to 0.5 parts in (2), but in both cases the treatment liquid is applied to 1 part of the fiber. The liquid exceeds the restricted moisture content of synthetic fibers such as acrylic fibers and is applied to the fibers in a floating state, and the amount of treatment liquid applied to the fibers is small, so a highly concentrated treatment liquid is inevitably used. As a result, 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 effective against fibers containing ordinary anionic groups. Selective adsorption is expected, but unlike on cotton, adsorption on fibers is unexpectedly poor.
Therefore, in order to impart the desired antibacterial performance to textile products, it is necessary to use a highly concentrated treatment solution in method (3), and due to poor adsorption properties, expensive processing agents remain in high concentrations. The company was faced with undesirable problems in terms of processing costs and wastewater pollution, such as disposing of residual liquid. (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 treating with electrolyte salts coexisting in the treatment bath, and then treating with a specific compound. , it is possible to apply organosilicon quaternary ammonium salts to textile products with high efficiency and uniformity from a low concentration treatment solution, there is no change in the texture of the fibers after treatment, and the washing durability is significantly improved. The present invention was achieved based on the discovery that the present invention can be obtained. (iv) Purpose of the invention The purpose of the present invention is to be able to uniformly and firmly apply organosilicon quaternary ammonium salt to textile products from a low-concentration treatment solution with high efficiency, so that there is no variation in antibacterial performance. It is an object of the present invention to provide an antibacterial processing method that has excellent whiteness and washing durability and does not change the texture of treated products. Another object of the invention is to
It is an object of the present invention 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. Different objects of the present invention are that the processing agent can be uniformly applied;
It is an object of the present invention to provide an antibacterial processing method that does not cause problems such as abnormal texture, yellowing, skin irritation, and spots such as mold growth associated with treatment spots. It will become clear from the detailed description of the invention. (e) Structure of the invention The above-mentioned object of the present invention is to provide textile products with
The following general formula in which electrolyte salts coexist (However, R ₁ is a C ₁₂ to ₁₈ long chain alkyl group, R ₂ , R ₃
and R ₄ is a lower alkyl group, X is Cl, Br, I or
Represents CH ₃ COO. ) This is achieved by treating with an organosilicon quaternary ammonium salt treatment solution shown in the following formula, and then treating with a _C8 to _C18 unsaturated fatty acid or a salt thereof. (F) Specific explanation of the structure Here, the textile product according to the present invention may be in any form such as short fibers, long fibers, yarns, knitted fabrics, etc., and may be natural, recycled, semi-synthetic, etc. Although it does not matter whether it is a single product or a mixed product of various types of fibers, such as synthetic fibers, it is preferable to use a single product of acrylic fiber or a mixed product of this fiber and other fibers because it can exhibit particularly remarkable effects. Furthermore, the organosilicon quaternary ammonium salts represented by the general formula used in the present invention include lauryl (C ₁₂ ^- ), myristyl (C ₁₄ ^- ), and cetyl (C ₁₆ ^- ).
Alternatively, it is obtained by heating reaction of a tertiary amine such as stearyl (C ₁₈ ^- ) dimethylamine and γ-halopropyl trialkoxysilane, such as dimethyl octadecyl (3-trimethoxysilyl)-propylammonium. Chloride is manufactured by Shin-Etsu Chemical Co., Ltd. and PETRARCH 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 typically contain active ingredients of about
Supplied as a 50% methanol solution. Bacteria and molds for which the processing agent exhibits an antibacterial effect 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.
It is effective when applied within the range of %, 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. In addition, the concentration of the processing agent is 0.005 to 2.5
It is desirable to use a treatment solution of 0.01 to 1.5% by weight, more preferably 0.01 to 1.5% by weight, because effective processing can be carried out without causing problems such as processing costs and wastewater pollution. 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 unequivocally, a range of approximately 10 to 60 minutes is appropriate. Next, as electrolyte salts to be added to the treatment solution, cation components include alkali metals such as lithium, sodium, potassium, etc.; beryllium,
Alkaline earth metals such as magnesium, calcium, and barium; other metals such as copper, zinc, aluminum, manganese, iron, and nickel; ammonium ions, and anionic components such as hydrochloric acid, sulfuric acid, rhodanic acid, Examples include one type of salt or a mixture of two or more types of salts composed of acid radicals such as acetic acid, and among them, alkali metal, alkaline earth metal, or ammonium salts of sulfuric acid, rhodanic acid, and 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. By subsequently treating the textile product that has been antibacterially treated with a _C8 to _C18 unsaturated fatty acid or a salt thereof, the washing durability can be further improved. If the number of carbon atoms in the fatty acid is outside the recommended range of the present invention, the objectives and effects of the present invention cannot be achieved. In addition, examples of such fatty acids include decenoic acid, undecenoic acid, dodecenoic acid, tetradecenoic acid, and hexadecenoic acid, and examples of salts of such acids include salts of zinc, barium, potassium, calcium, etc. be able to. Such a compound is usually used as a solution in methanol, ethanol, etc., and the amount of the compound used is 0.05 to 10% based on the weight of the fiber to be treated.
As long as it is preferably within the range of 0.1 to 5%, it goes without saying that a new aqueous dispersion treatment liquid can be prepared and treated, and a predetermined amount can be added to the treatment bath after the antibacterial treatment for subsequent treatment. . The temperature for treatment with such a compound is 20 to 90°C, preferably 30 to 70°C, and the treatment time is approximately 10 to 60 minutes. (g) Effects It is not necessary to clearly explain the reason why the method recommended in the present invention enables highly durable and consistent antibacterial processing without causing any change in the texture of textile products after treatment. I haven't reached it yet, but
It is estimated as follows. That is, organosilicon quaternary ammonium salts have poor adsorption ability, especially in exhaust treatment methods that use low-concentration treatment baths that do not pose problems in terms of processing cost or wastewater pollution, but they do not have sufficient adsorption ability when electrolyte salts are added to the treatment baths. This is thought to cause the processing agent to aggregate, increase its affinity for the fibers, promote adsorption, increase the proximity of the processing agent molecules, and promote the formation of a thin, uniform, and strong network. The homogeneously applied organosilicon quaternary ammonium salt forms a type of complex with specific unsaturated fatty acids, resulting in consistent antibacterial performance, further improved washing durability, and even greater durability in the treated product. It is thought that it forms an antibacterial film that does not impair the texture of the product. A noteworthy effect of the present invention is that the above-described method of the present invention can impart antibacterial performance with uniform whiteness and excellent durability to textile products without any loss of texture. Further, since the present invention employs an exhaustion treatment method using a low concentration treatment bath, another advantage of the present invention is that there are no problems regarding processing costs or wastewater pollution. 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, percentages are expressed on a weight basis unless otherwise specified. In addition, the antibacterial property was calculated by calculating the number of Staphylococcus aureus based on AATCC-100 and using the following formula. Reduction rate (%) = X-Y/X×100 210 (manufactured by Nippon Oil & Fats Co., Ltd.), and was measured and calculated for a sample that had been washed 20 times in a household electric washing machine. Example 1 100% acrylic fiber (exlan K2.0d x 51mm, manufactured by Nippon Exlan Kogyo Co., Ltd.) yarn (1/52'S),
After cheese dyeing using a small package dyeing machine for 1 kg, 42% of dimethyl octadecyl (3-methoxysilyl)-propylammonium chloride was added to the processing solution adjusted to 50℃ at a bath ratio of 1:10 based on the yarn weight. The treatment was carried out for 30 minutes in a treatment bath into which methanol solution, 1.0% and rhodan soda 3.0% as salt was injected with good stirring, and then 10-
A 30% methanol solution of undecenoic acid was gradually added at 1.5% based on the yarn weight, and the sample was immersed for 20 minutes.
(A) was produced. In addition, sample (B) was prepared in the same manner as above except that the acid treatment (50° C. for 20 minutes) was performed in a separate bath. Furthermore, samples (C and D) were prepared in the same manner as described above except that mirabilite was used instead of Rodan soda as the salt, and comparative samples (E and F) were prepared in the same manner as described above except that no salt was used. Table 1 shows the results of evaluating the antibacterial properties of the six types of samples (A to F) obtained.

[Table] From the above table, the effect of the antibacterial processing method according to the present invention can be clearly understood. Example 2 After washing a knitted fabric (1/48'S24G jersey) consisting of acrylic fiber/polyester fiber = 50/50 in hot water,
Six types of samples (GL) were prepared in the same manner as in Example 1 except as shown in Table 2 below. The antibacterial evaluation results of the six types of samples (GL) obtained are also listed in Table 2.

[Table] From the above table, it is understood that the processing method of the present invention imparts antibacterial properties with improved durability. Example 3 50 pairs of sports socks (2.5 kg) knitted from cotton yarn (bleached), nylon textured yarn, and polyurethane filament yarn were dyed using a paddle dyeing machine in the same manner as in Example 1 (however, dyeing was carried out at 40°C for 20 minutes). , methanol solution amount of acid: 1.0%), four types of samples (M to P) were prepared and antibacterial properties were evaluated. The results are shown in Table 3.

[Table] From the above table, the excellent effects of the processing method of the present invention can be clearly understood. Comparative Example 1 Using the same cheese-dyed yarn as in Example 1, the following three samples (Q, R, S) were prepared using a conventional processing method or a method considered to be an improvement thereof. That is, the treatment liquid was a 42% methanol solution of dimethyl octadecyl (3-methoxysilyl)-propylammonium chloride, 1.0% based on the yarn weight.
and 30% methanol solution of 10-undecenoic acid.
Sample Q was immersed for 50 minutes. The treatment solution appeared cloudy due to the formed complex. This turbidity is thought to be the cause of non-uniform adhesion, so when preparing the above treatment liquid, before mixing the acid, add Neugen HC (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), a nonionic surfactant, to the acid. Sample R was prepared by adding the same amount of the acid, mixing with the acid, and then treating it. Note that the treatment liquid was considerably less turbid than the treatment liquid prepared for sample Q. Prepare the same treatment solution as that used to prepare sample Q,
Furthermore, a treatment liquid was prepared by stirring and adding 3.0% Rodan soda based on the weight of the yarn as salt. Although the liquid exhibited a non-uniform dispersion with further turbidity and agglomeration, Sample S was obtained by processing this liquid. The antibacterial evaluation results of the obtained samples (Q to S) are shown in Table 4.

[Table] It can be seen that the antibacterial properties are all at a low level, and the washing durability is extremely poor. In particular, in sample S, large agglomerates have already formed in the treatment solution, making it lumpy and having a hard texture. Sample R is somewhat better, but clearly cannot withstand washing.

Claims (1)

[Claims] 1. A textile product is treated with an organosilicon quaternary ammonium salt treatment solution in which electrolyte salts coexist, and then treated with a C ₈ to _{C 18} unsaturated fatty acid or a salt thereof. Antibacterial processing method for textile products. 2 Electrolyte salts 0.1 to 20% of the weight of the textile product
% of the antibacterial processing method according to claim 1. 3. The antibacterial processing method according to claim 1, wherein the concentration of the organosilicon quaternary ammonium salt in the treatment liquid is 0.005 to 2.5% by weight.