JPH0814073B2 - Antibacterial processing method for textile products - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antibacterial processing method for textiles, and more particularly to an antibacterial / antifungal treatment of textiles against microorganisms such as bacteria and fungi. Organosilicon with effect 4th
When treating with a treatment liquid in which an electrolyte salt is allowed to coexist in a primary ammonium salt, by allowing a specific compound to coexist in the treatment liquid, or by further performing a specific treatment thereafter, there is no change in the texture of the treated fiber. The present invention relates to a processing method capable of providing an antibacterial product having little variation and excellent wash durability.

(B) Conventional technology With the maturity of society and the aging of society in recent years, there is a strong potential demand for maintaining and improving health, and there is an increasing need for development of cleaner and more comfortable clothing and home products for bedding. Is coming. In a hot and humid environment such as Japan, the reproduction of microorganisms such as bacteria and fungi is particularly active.
For example, it is injured by athlete's foot, has a bad odor caused by bacteria and bacteria, and has an unpleasant odor associated with fermentation. Facing the situation. Under such circumstances, there is a social need for antibacterial processed products to help prevent the generation of microorganisms that adversely affect our living environment, suppress their growth and reproduction, and maintain a hygienic and clean living environment. Development is being attempted.

It has been said that the important requirements for antibacterial sanitary processed textile products are greater hygiene effects, durability and higher safety than before, and these requirements are not met and disappear. There are many processed products that have gone down. In addition to these requirements, it is important that antibacterial and sanitary processing does not impair the product performance originally possessed by the processed product, such as appearance, texture, color and other important functions. Is.

Here, the organosilicon fourth represented by the following formula
Grade ammonium salt Is widely known as an antibacterial, antifungal, and antialgal agent, and is accepted as satisfying the above three requirements. By the way, the organosilicon compound is, in a processing bath (aqueous solution), I. hydrolysis of three methoxy groups, II. Formation of an oligomer by condensation, III. Bond formation between an oligomer and a fiber substrate (for example, when the substrate is In the case of cellulose, hydrogen bonds are formed), IV. Drying, film formation, and curing (formation of covalent bonds associated with dehydration) to form a robust film on the surface of the treated fiber, It is believed that by introducing an alkyl quaternary ammonium salt as an organic functional group into the product, a durable antibacterial effect is imparted to the textile product.

However, as compared with the case where the fiber substrate is cotton (cellulose), it has a functional group (-OH) that can be a receptor for the reactive group residue (-OH) of the oligomer in the reaction of the above III. , Such as synthetic fibers such as acrylic fibers, which do not contain such a functional group, the cured film formed between the above-mentioned organosilicon compounds has markedly different fastness and durability, and an event which seems to be inferior is encountered. However, when the compound is applied to synthetic fibers such as acrylic fibers and subjected to antibacterial treatment, it is necessary to improve washing durability and the like.

Further, regarding the method of treating a textile product with the organosilicon compound, the form of the fiber, for example, raw cotton, yarn (crepe,
The optimum processing means is selected depending on the type of product such as cheese), knitted fabric, and other pieces, and the piece that has become the product form. Generally, (1) impregnate a textile product with a processing liquid and then squeeze with a mangle to obtain the required amount of processing agent. (3) a method of applying and then dry-fixing, (2) a method of impregnating a textile product with a treatment liquid and then centrifugally dehydrating to apply a required amount of a processing agent, and dry-fixing.
A method in which a textile product is treated in a treatment bath containing a prescribed amount of a treating agent for a prescribed time to adsorb the treating agent, and then dehydrated and dried and fixed is used. However, in the treatment methods of (1) and (2), the treatment liquid can be applied to 1 part of the fiber in an amount of 0.3 to 2.0 parts in the case of (1) and 0.2 to 0.5 parts in the case of (2). The liquid exceeds the restrained water content of the synthetic fibers such as acrylic fibers and is applied on the fibers in a floating state, and since the amount of the processing liquid applied to the fibers is small, a high-concentration processing liquid is inevitably used. This means that the treatment liquid in the floating state causes treatment unevenness, and the processing agent migrates to the workpiece during drying, further promoting the treatment unevenness. Such treated spots cause an abnormal feeling of the product after treatment, and the excessively adhered portion is likely to turn yellow, which may cause abnormal irritation in terms of skin safety and hygiene. It is also considered to give spots for the development of mold and bacterial growth, and furthermore, the non-uniform adhesion causes asymmetric formation of the network between the organosilicon compounds, which is considered to cause deterioration of durability.

On the other hand, the treatment method of the above (3) is 5 to 1 part of fiber.
Processing is performed in 100 parts of the processing liquid for a predetermined time, and the concentration of the processing agent in the processing liquid is 20 compared with the above methods (1) and (2)
Since it is ~ 400 times less dilute, it is generally considered desirable for uniform adsorption unless the processing agent exhibits selective adsorption to the fibers. However, the organosilicon compound, which is a processing agent, has poor adsorption from the low-concentration processing liquid,
In addition, since the processing agent is cationic (quaternary ammonium salt), selective adsorption to fibers containing ordinary anionic groups is expected, but unlike cotton, the fibers are unexpectedly adsorbed. It has poor adsorptivity for. Therefore, in order to impart the expected antibacterial performance to textiles, it is necessary to use a high-concentration treatment liquid also in the method (3), and an expensive processing agent remains at a high concentration due to poor adsorption. We faced an unfavorable situation in terms of wastewater pollution due to processing costs such as disposal of residual liquid.

(C) Problems to be Solved by the Invention There is no problem of treatment unevenness in the above (1) and (2), and in the above method (3), a high-concentration treatment liquid must be used to compensate for poor adsorption. There is no problem in terms of wastewater pollution due to the processing cost of the residual liquid due to the absence, and the organosilicon compounds are almost completely and uniformly exhausted, and the antibacterial properties are excellent in washing durability without damaging the feeling and the like. It is to provide a processing method capable of providing a textile product.

That is, the object of the present invention is to enable the organosilicon quaternary ammonium salt to be applied to a textile product evenly and firmly from a low-concentration treatment liquid with high efficiency, so that there is no variation in antibacterial performance, whiteness and washing durability. An object of the present invention is to provide an antibacterial processing method which has excellent properties and does not change the feeling of the product to be treated. Another object of the present invention is to provide an antibacterial processing method capable of exhausting a low-concentration treatment liquid with high efficiency, and thus having no problems in processing cost and wastewater pollution. Another object of the present invention is to provide an antibacterial processing method capable of uniformly applying a processing agent and having no problems such as abnormal feeling associated with treated spots, yellowing, skin irritation, spots such as mold development. In view of the above, other objects of the present invention will be apparent from the detailed description of the present invention given below.

(D) Means for Solving the Problems The above-mentioned object of the present invention is as follows. (However, R ₁ is a C _12-18 long-chain alkyl group, R ₂ , R ₃ and R ₄
Is a C ₁ -C ₃ lower alkyl group, X is Cl, Br, I or CH ₃ COO
Represents ) In the treatment with the organosilicon quaternary ammonium salt treatment solution represented by the following, the treatment solution is allowed to coexist with a C _{8 to} C ₁₈ saturated fatty acid or a salt thereof, or the treatment is followed by a cation treatment. Achieved by

Here, the fiber product according to the present invention may be in any form such as short fibers, long fibers, yarns, knitted fabrics, etc., and is a single product of various fibers such as natural, regenerated, semi-synthetic and synthetic, It may be either a mixed product or a mixed product, but a single product of acrylic fiber or a mixed product of the fiber and another fiber is preferable because a particularly remarkable effect can be exhibited.

Further, the organosilicon quaternary ammonium salt represented by the general formula for use in the present invention, lauryl (C ₁₂ ^-),
Myristyl (C ₁₄ ^-) cetyl (C ₁₆ ^-) or steryl (C ₁₈ ^-) are those obtained by heating the reaction of the tertiary amine and γ- halopropyl-trialkoxysilane of dimethyl amine and the like, for example, dimethyl Octadecyl ((3
-Trimethoxysilyl) -propylammonium chloride is commercially available from Shin-Etsu Chemical Co., Ltd., PETRARCH SYSTEM, USA, trade name DC of Dow Corning.
5700 is also said to be this type of compound. Such compounds are usually supplied as a solution of about 50% active ingredient in methanol. Examples of bacteria and fungi which have antibacterial activity are the gram-positive bacteria such as Staphylococcus aureus and Bacillus subtilis; Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Urea-degrading bacteria, Klebsiella pneumoniae, and Trichophyton interdigitale. Molds such as fungi and black mold are listed.

The processing agent exerts an effect when it is applied within a range of 0.1 to 3% with respect to the weight of the fiber to be processed, but when it exceeds the upper limit, the feeling becomes abnormal, and also from the viewpoint of skin safety and hygiene. May cause unpleasant stimuli. The concentration of the processing agent is 0.005 to 2.5% by weight, more preferably 0.01 to 1.
It is desirable to use a treatment liquid of 5% by weight, because the treatment can be effectively performed without causing problems such as processing cost and wastewater pollution.

A suitable treatment temperature with the processing agent is 20 to 90 ° C., preferably 30 to 70 ° C. When the temperature exceeds 70 ° C., the adsorption amount decreases, and when the temperature exceeds 90 ° C., the temperature decreases remarkably. Although it is difficult to unambiguously define the treatment time, it is appropriate that the treatment time is generally within the range of 10 to 60 minutes.

Next, as electrolyte salts to be added to the treatment liquid, cation components include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium and barium; copper, zinc and aluminum. , Other metals such as manganese, iron and nickel; ammonium ions and the like, and the anion component is composed of acid radicals such as hydrochloric acid, sulfuric acid, rhodanic acid and acetic acid 1
Mention may be made of one salt or a mixture of two or more salts,
Among them, alkali metal salts of sulfuric acid, rhodanic acid, acetic acid, alkaline earth metals or ammonium salts are preferable.

The amount of the salt added is 0.1 to 20 relative to the weight of the fiber.
%, More preferably in the range of 0.5 to 10%, and use of a high concentration exceeding the upper limit is not desirable because it hardens during the dry heat treatment after the treatment and impairs the feel of the fiber.

Examples of the method for adding such a salt include adding the fiber to be processed with a processing agent in advance before adding the fiber to be processed into the processing bath, adding the fiber after processing the fiber for a required time in the processing bath, and adding the fiber in the processing bath. Any means such as gradual addition while treating with a processing agent can be adopted, and in each case, the electrolyte salt can be added in several times if necessary.

As the saturated fatty acid or a salt thereof used is added into the treating solution, it is necessary to use within the scope of C ₈ -C _18, if the carbon number of the fatty acid is out of the recommended range of the present invention Therefore, the object and effect of the present invention cannot be exhibited.

Examples of such saturated fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like, and examples of salts of such acids include potassium, sodium, zinc, barium,
Mention may be made of salts such as calcium. Such compounds are usually used as an aqueous solution or a solution of methanol, ethanol or the like, and the amount of the compound used is preferably set within the range of 0.05 to 10% based on the weight of the fiber to be treated. As for the addition method for allowing the compound to coexist in the treatment liquid, the same means as the addition method of the electrolyte salt can be adopted.

The treated fiber product is then optionally subjected to a cation treatment to further improve the durability of the finally obtained antibacterial product.

As such cations, various cationic surfactants such as amine salts, quaternary ammonium salts, phosphonium salts and sulfonium salts can be used in a wide range. Especially, if a polyamide polyamine type amine salt is used, It is preferable from the viewpoint of exhibiting an excellent effect of improving durability and also in terms of flexibility and feel of the final fiber product. In addition,
As a polyamide polyamine type cationic surfactant,
Zontes 603A, TC-816, Zontes TA460-15 manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., Tafflon ACH manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
320A, S-15, AS, Tafflon Sur, Marubishi Yuka Co., Ltd.
Bevinar 715, -801 made by Yakusha Yushi Co., Ltd., Vicron 90, Long size VK-103, Bel made by Henkel Hakusui Co., Ltd.
Examples thereof include those marketed under the trade names of fasin 615, Safanol AC manufactured by Sanyo Kasei Co., Ltd., and Softlon FC-28 and FC-136 manufactured by Yoshimura Oil Chemical Co., Ltd.

The amount of such cations used is 0.05-based on the fiber weight.
2.0%, more preferably 0.1 to 1.0% is suitable. The application method is not limited at all, and any method such as a spray method, a pad method, or a dipping method may be used as long as a predetermined amount of cations is applied to the fiber. The Pat method and the dipping method are preferable.

(E) Action The reason why the means recommended in the present invention enables the antibacterial treatment treatment which is excellent in durability and does not cause a change in the texture of the treated textile product, will be explained clearly. However, it is estimated as follows.

That is, although the organosilicon quaternary ammonium salt has a poor adsorption ability in the exhaust treatment method using a low-concentration treatment bath which does not cause a problem of wastewater pollution, especially in terms of processing cost.
By adding electrolyte salts to the treatment bath, the compounding agent is agglomerated to increase the affinity and adsorption to the fiber and enhance the proximity of the processing agent molecules to promote the formation of a thin, uniform and strong network. It is thought that the thin and evenly applied organosilicon quaternary ammonium salt, the specific saturated fatty acid, and the cation interact with each other (for example, form a kind of complex), resulting in variations in antibacterial performance. It is considered that the antibacterial film is further improved in washing durability and does not impair the texture of the product to be treated.

(F) Effect of the Invention According to the method of the present invention described above, the antibacterial performance excellent in whiteness and durability with no variation in the texture of the fiber product can be obtained by combining the silicon quaternary ammonium salt with the saturated fatty acid. The point that can be applied in the step of the one-step treatment in the same bath is a remarkable effect of the present invention.

Further, since the present invention adopts the exhaustion treatment method using a low-concentration treatment bath, there is no problem in processing cost or wastewater pollution, which is another advantage of the present invention.

(G) Examples The present invention will be described in more detail below with reference to Examples, but the scope of the present invention is not limited by the description of these Examples. In the examples, percentages are by weight unless otherwise specified.

Example 1 A jersey (1 / 64'S22G ponchiroma) made of 100% yarn of acrylic fiber (manufactured by Japan Exlan Kogyo Co., Ltd., trade name Exlan K8 1.5d x 51 mm) was washed with hot water, and then the weight of the jersey was measured. In contrast, dimethyl. Octadecyl.
42% methanol solution of (3-methoxysilyl) -propylammonium chloride in 1.1%, salts shown in Table 1 below.
3.0% and 1.5% of 10% methanol solution of lauric acid were poured into 30 times the weight of the jersey cloth in water with good stirring for 20 minutes in a treatment bath at 50 ° C.
~ D) were prepared.

On the other hand, a comparative sample (E) was prepared in the same manner as above except that salt and acid were not used.

Table 1 shows the results of evaluating the antibacterial properties of the obtained five types of samples (AE).

 As for the antibacterial property after washing,
Sannonion NS-210 (Manufactured by Nippon Oil & Fat Co., Ltd.),
Test sample after 20 washing cycles in a household electric washing machine
Is measured and calculated.

From the above table, it is clearly understood that the antibacterial processing method according to the present invention imparts antibacterial properties with excellent washing durability by using a low concentration treatment liquid.

Next, the finished sample jerseys (A to E) of this example were dipped in Sontes 603A 3.0% (bath ratio 1:30), treated at 45 ° C. for 15 minutes, and dried to obtain 5 kinds of cation-treated samples. It was The results of the same antibacterial evaluation as described above are shown in Table 2.

From the above table, it is clearly understood that the cation treatment of the present invention can provide an antibacterial textile product with significantly improved durability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location D06M 13/20

Claims (3)

[Claims] 1. When a textile product is treated with an organosilicon quaternary ammonium salt treatment liquid in the presence of electrolyte salts, the treatment liquid is treated with a C _{8 to} C ₁₈ saturated fatty acid or a salt thereof. An antibacterial processing method for textile products, which is characterized in that 2. An antibacterial processing method for a textile product, which comprises a cation treatment subsequent to the treatment according to claim 1. Wherein C ₈ -C ₁₈ saturated fatty acid or range first of the claims from 0.05 to 10% using a salt thereof relative to the textile weight of
Item 2. The antibacterial processing method according to Item 2 or Item 2.