JP2000328469A - Production of functional nylon-based fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a functional nylon-based fiber product which has excellent deodorizing, antimicrobial, anti-allergic and antioxidizing properties, because even a fiber product comprising low water- absorbing nylon fibers can surely carry an active ingredient such as tea extract, catechin or saponin, can still maintain the properties, even when brought into contact with water, and does not change the dimension even on contact with the water. SOLUTION: This method for producing a functional nylon-based fiber product comprises carrying (A) at least one active ingredient selected from the group consisting tea extract, catechin, saponin and tannin(acid) on (F) a fiber product comprising low water-absorbing fibers having a water absorption of <=1% in water for 24 hr by ASTM D570 by an exhaustion method. Therein, the fiber product F is treated in a bath containing the active ingredient A in a high temperature condition of >100 deg.C in the bath containing the active ingredient. Therein, the fiber product is preferably treated in the bath containing the active ingredient A and further treated in a bath containing a dye mordant B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a functional product in which an effective ingredient such as a tea extract, catechin or saponin is carried on a textile made of low water-absorbing nylon fiber by a dyeing method (a method similar to dyeing). The present invention relates to a method for producing a nylon fiber product.

[0002]

2. Description of the Related Art Nylon fibers represented by nylon 6 and nylon 66 are used for various purposes including consumer use and industrial use. One notable application is in air conditioners and air purifier filters. If an active ingredient such as tea extract, catechin, saponin or the like can be attached and carried (and further carried by reaction) to the nylon-based fiber, a nylon-based fiber product having antibacterial properties and deodorant properties can be obtained.

[0003] There is no description about nylon-based fibers,
JP-A-7-148407 (Patent No. 2719088)
No. 2) discloses an anti-virus filter in which a virus inactivating agent containing an extracted component of tea as an active ingredient is impregnated into a filter or kneaded into a filter material. Tea extraction components are tea polyphenols such as catechins. Examples include (a) an example in which an extract component of tea is dissolved in water to form an aqueous solution and then impregnated and attached to an electret filter.
There is an example in which a tea extraction component is mixed with polypropylene, melted, formed into a film, cut, and formed into a nonwoven fabric.

Although there is no description about nylon-based fibers,
Japanese Patent Application Laid-Open No. 8-266828 discloses an anti-virus filter including a dust collecting filter and a filter to which a tea extraction component is attached. Tea extraction components are tea polyphenols such as catechins. The filters impregnated with the tea extraction component include electret filters, HEPA filters, high-performance filters, medium-performance filters, and bag filters.

Japanese Unexamined Patent Publication No. 6-566 filed by the present applicant.
No. 56 discloses that a cloth-like material made of natural fibers is reacted with tannic acid by contacting with a reaction solution containing tannic acid, and then further contacted with a reaction solution containing tartarite to form tartarite. A method for producing an external germicidal disinfecting cloth characterized by reacting is disclosed.

Japanese Patent Application Laid-Open No. Hei 6-173 filed by the present applicant
No. 176 discloses a process of treating a textile product with a tannic acid treatment → [fixing treatment with tartar] → [mordanting reaction with a mordant containing a mordant] → a dyeing reaction with a dyeing solution containing a tea extract. A method of producing a tea-dyed fiber product to be dyed through is disclosed. [] Indicates an optional step. In addition, there is also disclosed a method in which a mordant reaction and a dyeing reaction are simultaneously performed using a mordant-dyeing solution in the above step. For the material of textile products,
It is described that the fibers are arbitrary, such as natural fibers such as cotton, hemp, silk, and wool, or blends, cross-wovens, and cross-knits of these natural fibers and chemical fibers. With respect to applications, applications that come into contact with the skin and applications that have fashionability are listed.

[0007] Japanese Patent Application Laid-Open No.
No. 316,786 discloses a method for producing a dyed fiber product in which (a) a textile product is brought into contact with a dyeing liquid containing a catechin or an attribute thereof and then is contacted with a mordant liquid containing a mordant, A method for producing a dyed fiber product in which a dyeing reaction and a mordant reaction are simultaneously performed by contacting a dyeing liquid and a mordant containing both a catechin or an attribute thereof and a mordant is disclosed. The material of the textile product is arbitrary, such as natural fibers such as cotton, hemp, silk, and wool; chemical fibers such as polyamide fibers; or blended, woven, and knitted products of these natural fibers and chemical fibers. Among these, cotton, hemp and silk are described as being particularly important. Examples of the use include a contact with the skin, a use having fashionability, and a filter for an air purifier or an air conditioner.

[0008]

According to the dyeing method (exactly a method similar to dyeing) proposed by each of the above-mentioned publications, the nylon fiber is made of ordinary nylon 6 or nylon 66.
In this case, there is an advantage that an active ingredient such as catechin can be chemically supported on the fiber product by a dyeing reaction and a mordant reaction.

However, when nylon fiber made of ordinary nylon 6 or nylon 66 is used as a filter for an air conditioner or an air purifier, it is stretched over a grid-like frame.
Warpage and distortion were unavoidable due to changes in the humidity in the atmosphere and contact with water during washing.
In order to overcome such a problem, an attempt was made to replace a part or one of the vertical and horizontal filaments of the filter with a polypropylene fiber having no water absorbency, but the warpage and distortion were reduced. Could not be resolved.

Further, when nylon fibers made of nylon 6 or nylon 66 are used, for example, for interlining or lining of clothing, there is a risk of deformation due to the absorption of sweat.

Therefore, the present inventors have thought that instead of nylon 6 and nylon 66, fibers of low water-absorbing nylon such as nylon 610, nylon 612, nylon 11, nylon 12, and nylon 1212 may be used. Reduces the amount of dyeing, so the desired deodorant, antimicrobial,
There was a problem that the antioxidant property was not obtained, and the above-mentioned active ingredient was easily lost when contacted with water.

[0012] Under the above-mentioned circumstances, the present invention is excellent in that an effective ingredient such as tea extract, catechin and saponin can be surely carried on a fiber product made of a low water-absorbing nylon fiber. It has deodorant, antimicrobial, antiallergic, and antioxidant properties, and maintains its properties even when in contact with water, and does not easily change its dimensions even when in contact with water. It is an object of the present invention to provide a method for producing a functional nylon-based fiber product.

[0013]

The process for producing a functional nylon fiber product of the present invention is directed to a fiber product (F) comprising a low water-absorbing nylon fiber having a water absorption of 1% or less in water for 24 hours by ASTM D570. At least one active ingredient (A) selected from the group consisting of tea extract, catechin, saponin, and tannin (acid) by a dyeing method. The treatment is carried out under a high temperature condition exceeding 100 ° C. in a bath containing the active ingredient (A). In this case, it is particularly preferable to treat in a bath containing the active ingredient (A) and then in a bath further containing the mordant (B).

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

In the present invention, "deodorant" is used to include deodorizing, odor eliminating and harmful gas component removing properties, and "antimicrobial" means bactericidal, bacteriostatic and antibacterial. It is used in the sense including mold and antiviral.

The fiber product (F) in the present invention is ASTM D57
0 has a water absorption of 1% or less in water for 24 hours (preferably
0.8% or less, more preferably 0.5% or less). A typical example of such a low water-absorbing nylon is nylon 610 (water absorption 0.4%).
%), Nylon 612 (water absorption 0.4%), nylon 11
(Water absorption 0.25%), nylon 12 (water absorption 0.25%), nylon 1212 (water absorption 0.2%) and the like. Incidentally, the water absorption of nylon 6 is 1.6%, and the water absorption of nylon 66 is 1.5%. For the water absorption of various nylons,
"Polyamide resin handbook, published by Nikkan Kogyo Shimbun,
Table 1.11 on page 27 of “January 30, 1988, First Edition, First Printing Issuance” and 3 of “Plastics, Vol. 41, No. 2”.
See the tables on pages 5-52. However, the value of the water absorption differs slightly depending on the literature because there is a difference depending on the grade.

The fiber product (F) includes raw fibers, yarns (monofilament, multifilament yarn, spun yarn, spun yarn, covering yarn, etc.), pile,
Cotton, woven, non-woven, knitted, flocked, etc.
In addition, blended products with other materials such as fibers and yarns, blended products, interwoven products,
It may be a knitted product, a aligned product, or the like. The low-water-absorbing nylon fiber may be a sheath-core or bimetallic conjugate fiber, or may be a fiber in which an appropriate amount of an active ingredient (A) described below has been previously added during the production thereof. .

As the active ingredient (A), at least one selected from the group consisting of tea extract, catechin, saponin and tannin (acid) is used. These are often used in combination of two or more.

As the tea extract, powdered teas such as Ichibancha, No.2 and No.3 teas, tea extracts such as deep-boiled and covered, and black tea and oolong tea extracts can be used.

As the catechin (including its attribute form), a monomer form or an oligomer form is used (including theaflavin). A particularly important catechin used in the present invention is a tea-derived catechin preparation having an increased catechin concentration. The main components of tea catechin are epigallocatechin, epigallocatechin gallate, epicatechin, epicatechin gallate, etc., but it is not necessary to isolate it into individual components, so it contains tea catechin consisting of a mixture of these richly Formulation (especially containing 20% or more, preferably 25% or more)
Can be suitably used as it is. Commercially available tea-derived catechin preparations include 30%, 50%, 60%, 70%
% Products, 80% products, 90% products, etc., so it is easy to obtain. Since catechin is contained in various plants other than tea, such as Asenyaku, catechins derived from those plants can also be used.

Saponin can be obtained by extracting a saponin-containing component from tea leaves or tea seeds using an organic solvent or water, and then repeatedly performing purification using a means such as column chromatography. Saponin is a variety of plants other than tea,
For example, it is also contained in carrots, carrots, soybeans, psycho, amachadul, loofah, onji, kikyo, senega, bakmondou, mokutsu, timo, gossip, licorice, sankirai and the like. However, tea saponins derived from tea described above are particularly suitable in terms of availability, small amount of contaminants, and dyeing properties. Saponins include steroidal saponins, triterpenoid saponins, and the like.Depending on the type of the starting plant, there are many saponins having a large amount of steroidal saponins and those having a large amount of triterpenoid saponins. Can be used.

As the tannin (acid), a commercially available purified tannic acid can be used, and an extract of a high tannic acid-containing natural plant containing a large amount of tannic acid such as pentaploid or gallic or a semi-purified product thereof is used as it is. It can also be used.

As the mordant (B), copper mordant (copper salt),
Iron mordants (iron salts such as iron acetate, ferrous sulfate, iron nitrate, ferrous acetate, iron acetate), calcium mordants (calcium acetate, calcium hydroxide, etc.), titanium mordants (titanium salts of organic acids) , Aluminum mordants (aluminum acetate, aluminum sulfate, aluminum chloride, alum, calcined alum, potassium alum, aluminum salts such as commercially available aluminum liquids), silver mordants (silver salts such as silver acetate and silver nitrate), tin mordants (tin salts) , Zinc mordant (zinc salt), chromium mordant (chromium salt), cobalt mordant (cobalt salt) and the like. Plant ash (wood ash or straw ash) such as camellia ash, Sawaftagi ash, Hisakaki ash, oak ash, Akaza ash, and Waseda straw ash can also be used. These plant ash contain aluminum ions as well as other metal ions and alkaline substances useful for dyeing.

Since the dyeing properties vary depending on the type of mordant, it is preferable to find out which mordant is appropriate by preliminary experiments. One example of a suitable mordant is a copper mordant (copper salt).

In the present invention, at least one of the above-mentioned active ingredients (A) is carried on the above-mentioned textile product (F) by a dyeing method (means similar to dyeing).
100 ° C. in the bath containing the active ingredient (A)
Treated under high temperature conditions exceeding In this case, textile products
It is particularly preferred that (F) is treated in a bath containing the active ingredient (A) under a high temperature condition exceeding 100 ° C., and then further treated in a bath containing the mordant (B). Prior to or simultaneously with the treatment of the textile product (F) in a bath containing the active ingredient (A) under a high temperature condition of more than 100 ° C., in a bath containing an auxiliary (C) comprising a fixing agent. It can also be processed.

At this time, the order of the baths can be variously varied as exemplified below. I. Bath containing (A). B. Bath containing (A) → Bath containing (A). C. Bath containing (A) → Bath containing (B). D. Bath containing (A) → bath containing (A) → bath containing (B). E. Bath containing (A) and (B) → Bath containing (B). F. Bath containing (A) → Bath containing (A) and (B). G. Bath containing (C) and (A). H. Bath containing (C) → Bath containing (A). Re. Bath containing (C) and (A) → Bath containing (B). Nu. Bath containing (C) → bath containing (A) → bath containing (B). Le. Bath containing (C), (A) and (B) → Bath containing (B).ヲ. Bath containing (C) → Bath containing (A) and (B).

In any of these methods, desizing, scouring, bleaching, etc., of the fiber product (F) can be carried out before the bath treatment, if necessary.

Active ingredient in bath containing active ingredient (A)
The amount of (A) is about 0.2% by weight or more (usually about 1 to 50% by weight) based on the weight of the textile (F), and the amount of the mordant (B) in the bath containing the mordant (B) is It is often about 0.2% by weight or more (usually about 1 to 20% by weight) based on the weight of (F). The amount of the auxiliary agent (C) in the bath containing the auxiliary agent (C) comprising a fixing agent is often not more than about 20% by weight based on the weight of the textile (F). However, the above amounts are for reference only.

The bath temperature of the bath containing the active ingredient (A) is 100 ° C.
, Preferably about 105 to 140 ° C, especially about 110 to 130 ° C. The bath temperature of the bath containing the mordant (B) is preferably about 40 to 140 ° C, particularly preferably about 70 to 130 ° C. The bath temperature of the bath containing the auxiliary agent (C) is 40
The temperature is preferably set to about 140 ° C, particularly about 70 to 130 ° C. In any of the baths, the bath ratio is often about 5 to 100 times the weight of the fiber, and the treatment time is often about 10 minutes to 3 hours (particularly about 15 minutes to 2 hours).

After the completion of the above bath treatment, post-treatments such as acid washing, alkali washing, soaping and water washing are performed, if necessary, followed by natural drying or hot air drying.

Thus, the active ingredient (A) is added to the textile product (F).
To obtain a functional fiber product having dyed and carried thereon. This fiber product is used, for example, for filter materials (filters for air conditioners, air purifiers, vacuum cleaners, clean rooms, water filters, etc.), clothing (clothes, interlining, lining, aprons, socks, socks, etc.), footwear (shoes). , Slippers, insoles, etc.), personal belongings (towels, scarves, mufflers, belts, hats, gloves, tablecloths, umbrellas, bags, bags, wallets, etc.), daily necessities and kitchen utensils (toothbrush, clothes brush, hairbrush) , Makeup brushes, scourers, dishwashing, rags, fukins, rubs, etc.), medical supplies, welfare-related products, sanitary products (surgical gowns, white coats, bed mats, masks, bandages, diapers, various sanitary products, etc.), interior products・ Interior goods / furniture (hot carpet, carpet, curtain, chair upholstery, screen door, bath mat, etc.), VOC such as formalin / acetaldehyde
(Volatile organic compounds) for prevention of sick house syndrome, MCS (multiple chemical sensitivities) prevention materials (wall covering, fiberboard, cloth, etc.), bedding (futon cotton, sheets, duvet cover, blanket) , Mats, pillowcases, cushions, etc.), sporting goods (sports clothes, fishing lines, etc.), car interior parts (car cover sheets, etc.), packaging materials, and other industrial and consumer uses (tents, conveyor belts, hoses, ropes, Cover, canvas, fishing net, longline, insect net, seaweed net, bird net,
It is useful for various applications including filter cloth, dry canvas for paper machine, sweat for helmet, attachment brush for vacuum cleaner, mop, stuffed toy, polishing brush, sewing thread, mosquito net, etc.).

[0032]

The present invention will be further described with reference to the following examples. Hereinafter, “parts” and “%” are expressed on a weight basis. "% Owf" means percent by weight based on fiber weight. The treatment under high temperature and pressure was performed using a pressurized closed dyeing machine.

<Preparation of Materials> Textile (F) (F ₁ ): Nylon 610 fiber (monofilament yarn) (F ₂ ): Nylon 612 fiber (monofilament yarn) (F ₃ ): Nylon 11 fiber (monofilament yarn) (F ₄ ): Nylon 12 fiber (monofilament yarn) (F ₅ ): Nylon 1212 fiber (monofilament yarn)

Active ingredient (A) (A ₁ ): tea extract (10 g of powdered tea powder of the first tea in 200 ml of water, immersed for about 5 minutes, and then dried at a temperature of 20 to 25 ° C. for 5 to 5 minutes)
Stir for 15 minutes and leave overnight. The following day, filtration was performed to obtain 160 to 190 ml of a tea leaf extract, which was evaporated to dryness and used. (A ₂ ): catechin (epigallocatechin, epigallocatechin gallate, catechin preparation derived from tea having a total amount of epicatechin and epicatechin gallate of about 30%) (A ₃ ): saponin (saponin content of about 50%) Saponin preparation derived from tea) (A ₄ ): tannic acid (tannic acid having a tannic acid content of about 80%)

Mordant (B) (B ₁ ): Copper mordant (copper sulfate) (B ₂ ): Copper mordant (copper acetate)

<Preliminary treatment> The above fiber product (F) was put into water, heated to 80 ° C with stirring, stirred at this temperature for about 10 minutes, washed with water and dehydrated.

<Method 1, 1 ′> One or two kinds of active ingredients (A) were added to water so as to have a concentration of 20% owf, and a small amount of water was further added to make a total of 1200 parts (bath ratio 1:12). ), A treatment bath is prepared, 100 parts of the fiber product (F) is added to the treatment liquid, and the mixture is heated to 120 ° C. (method 1) or 80 ° C. (method 1 ′) and stirred for 60 minutes. After the temperature was turned off, stirring was continued for 60 minutes, followed by washing and dehydration.

A mordant (B) was added to water at a concentration of 5% owf, and a small amount of water was further added to make a total of 1200 parts (bath ratio 1:12) to prepare a treatment bath. 100 parts of the textile product (F) which has been subjected to the above treatment is added, and the mixture is heated to 90 ° C., stirred for 30 minutes, and then stirred for 60 minutes after turning off the temperature control. went. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Methods 2 and 2 ′> Tannic acid (A ₄ ) of the active ingredient (A) was added to water so as to have a concentration of 10% owf, and a small amount of water was further added to make a total of 1200 parts (bath ratio). 1: 1
2) to prepare a treatment bath, and add a fiber product (F)
100 parts were added, and the mixture was heated to 80 ° C. and stirred for 60 minutes. After the temperature was turned off, the stirring treatment was continued for 60 minutes, followed by washing and dehydration.

A treatment bath was prepared by adding 15% owf of the active ingredient (A) in water and further adding a small amount of water to make the whole 1200 parts (bath ratio 1:12). 100 parts of the textile product (F) treated
The mixture was heated to 80 ° C. (method 2) or 80 ° C. (method 2 ′) and stirred for 60 minutes. After the temperature was turned off, stirring was continued for 60 minutes, followed by washing and dehydration.

The mordant (B) was added to water at a concentration of 5% owf, and a small amount of water was added to make a total of 1200 parts (bath ratio 1: 1).
2) to prepare a treatment bath, 100 parts of the fiber product (F) subjected to the above treatment is added to the treatment liquid, and the mixture is heated to 90 ° C., stirred for 30 minutes, and then the temperature is cut off. After the stirring treatment was continued for 60 minutes, washing and dehydration were performed. As a result, dyed fibers of relatively dark color (functional fiber products)
Was obtained and used for the test described below.

<Method 3> In method 2, only the treatment with the mordant (B) was omitted.

<Summary of Processing Conditions> The processing conditions are shown in Table 1. The symbols in Table 1 are: Textile (F): (F ₁ ), (F ₂ ), (F ₃ ), (F ₄ ), (F ₅ ), Active ingredient (A): (A ₁ ) , (A ₂ ), (A ₃ ), (A ₄ ), mordant (B): (B ₁ ), (B ₂ ). “(A) Amount” is the amount of dyeing (loading) of the active ingredient (A), and the amount of dyeing is determined by the heat balance (heat absorption) when heating and heating at a constant rate using a differential thermal analyzer. / Heat generation) and the accompanying weight increase / decrease.
“−” Omits the corresponding bath treatment.

[0044]

[Table 1]  (F) (A) Quantity Method First bath Second bath Third bath  Comparative Example 1 (F₁) 0.0 Blank − − − Comparative Example 2 (F₁) 1.1 1 '− (A_Two) (B₁)Comparative Example 3 (F ₁ ) 1.3 2 '(A ₄ ) (A ₂ ) (B ₁ )  Example 1 (F₁) 15.9 1 − (A_Two) (B₁) Example 2 (F₁) 16.6 2 (A_Four) (A_Two) (B₁) Example 3 (F₁) 7.3 3 (A_Four) (A_Two)-Example 4 (F₁) 15.5 1 − (A_Three) (B₁) Example 5 (F₁) 16.5 1 − (A_Two) + (A_Four) (B₁)Example 6 (F ₁ ) 16.4 2 (A ₄ ) (A ₁ ) + (A ₂ ) (B ₁ )  Comparative Example 4 (F_Two) 0.0 Blank − − − Comparative Example 5 (F_Two) 1.1 1 '− (A_Two) (B₁)Comparative Example 6 (F ₂ ) 1.4 2 ′ (A ₄ ) (A ₂ ) (B ₁ )  Example 7 (F_Two) 15.8 1 − (A_Two) (B₁)Example 8 (F ₂ ) 16.2 2 (A ₄ ) (A ₁ ) + (A ₂ ) (B ₁ )  Comparative Example 7 (F_Three) 0.0 Blank − − −Comparative Example 8 (F ₃ ) 0.8 2 ′ (A ₄ ) (A ₂ ) (B ₁ )  Example 9 (F ₃ ) 13.4 2 (A ₄ ) (A ₁ ) + (A ₂ ) (B ₁ )  Comparative Example 9 (F_Four) 0.0 Blank − − − Comparative Example 10 (F_Four) 0.7 1 '− (A_Two) (B₁)Comparative Example 11 (F ₄ ) 0.9 2 ′ (A ₄ ) (A ₂ ) (B ₂ )  Example 10 (F_Four) 12.3 1 − (A_Two) (B₁)Example 11 (F ₄ ) 13.1 2 (A ₄ ) (A ₁ ) + (A ₂ ) (B ₂ )  Comparative Example 12 (F ₅ ) 0.0 Blank − − −  Example 12 (F ₅ ) 10.7 1 − (A ₂ ) (B ₁ )

<Deodorizing test> 1 m ³ having a substantially cubic shape
Prepare a space, install a small vacuum cleaner in which all the interior parts such as dust collection bags have been removed, and wrap the fiber of the test sample around each of the processed suction ports so that the length becomes a certain length. A circulating device capable of circulating air in the space was prepared by adjusting and installing. First 5 cigarettes (Seven Star)
The test was ignited at the same time, placed in the center of the floor of the test space, immediately closed and almost closed, and left for 5 minutes. The circulation device was set so that the air volume became 0.5 m ³ / min, and the tobacco was installed so that it could be sucked by an automatic suction machine. . Smell measurement is 5
After 3 minutes, start (measurement time 0).
0 minutes later, the odor, ammonia concentration, and acetaldehyde (CH ₃ CHO) concentration of the tobacco were measured. The measurement was performed using a general-purpose odor sensor “XP-32” manufactured by Shin Cosmos Electric Co., Ltd.
9 "and gas detection tubes for ammonia and acetaldehyde. Table 2 shows the results.

The same sample as above was immersed in water at a temperature of 60 ° C. for 48 hours, dried, and subjected to the same deodorizing test as above. The results are shown in Table 2. According to Table 2,
In the examples, despite the use of the low water-absorbing nylon fiber as the fiber product (F), the deodorizing property is good, and the good deodorizing property is still maintained after immersion in water. Understand. Comparative Example 12 is almost the same as Comparative Example 11.

[0047]

[Table 2]  Tobacco odor deodorization rate NH ₃ concentration decrease rate CH ₃ CHO concentration reduction rate  Before water immersion After water immersion Before water immersion After water immersion Before water immersion After water immersion  Comparative Example 1 22.0 21.9 40.3 40.2 15.1 15.1 Comparative Example 2 25.3 22.4 45.7 42.0 18.3 16.3Comparative Example 3 26.3 23.5 46.6 44.1 18.9 17.2  Example 1 68.2 67.2 70.5 69.6 62.2 61.7 Example 2 70.3 69.0 72.8 72.0 63.8 63.2 Example 3 50.1 47.0 49.5 46.8 42.1 40.5 Example 4 67.8 66.7 69.5 69.6 62.2 61.7 Example 5 70.0 69.6 70.1 69.5 63.8 63.0Example 6 69.6 69.3 69.7 69.2 63.4 62.9  Comparative Example 4 22.2 22.1 40.2 40.1 14.9 14.8 Comparative Example 5 25.5 22.4 45.5 41.9 18.2 16.0Comparative Example 6 26.9 24.0 46.9 44.2 19.4 17.4  Example 7 67.7 67.1 70.1 69.4 61.5 61.3Example 8 69.2 68.8 69.6 69.2 62.6 62.4  Comparative Example 7 22.0 21.9 40.3 40.2 15.1 15.1Comparative Example 8 23.9 22.9 44.1 41.7 16.5 15.6  Example 9 63.2 62.8 64.4 64.0 58.0 57.7  Comparative Example 9 21.7 21.6 38.8 38.5 14.3 14.0 Comparative Example 10 23.5 22.6 43.3 41.1 15.7 14.4Comparative Example 11 24.4 23.4 44.7 42.1 17.5 16.0  Example 10 61.7 61.4 62.0 61.5 56.7 56.5Example 11 62.6 62.5 63.8 63.1 57.6 57.0  Example 12 58.4 58.1 59.5 59.2 52.9 52.9

<Antimicrobial test 1> As a mold cultivation solution, a commercially available modified GAM agar medium was used, which was heated and dissolved in a flask and allowed to cool naturally. For the mold, 0.5 ml of a previously prepared black mold solution (100 mg / 500 ml) was inoculated in 1000 ml of the medium solution. The growth promotion of mold was observed by using a thermo-hygrostat at 35 ° C. and 95% RH for 14 days. The test evaluation was carried out on an artificial medium planted with black mold. The occurrence frequency is observed by visual observation and photography, and the antifungal effect is-, +, ++, +++, ++
Judgment was made in five stages of ++. Table 3 shows the results.

[0049]

[Table 3]

<Antimicrobial test 2> Examples 1, 2, 4,
5,8,9,11,12 functional fiber products before and after water immersion, Staphylococcus aureus St
The antibacterial activity against aphylococcus aureus ATCC6538P was examined. That is, a bouillon suspension of the test bacterium was poured into a sterilized sample, and the number of viable cells after culturing at 37 ° C. for 18 hours in a closed container was measured to obtain an increase / decrease value with respect to the number of inoculated cells. The unprocessed cloth used was a standard cotton cloth. The results are shown below and in Table 4.・ Number of inoculated bacteria (A) is 1.9 × 10 ⁴ , log A is 4.3 ・ Number of unprocessed bacteria (B) is 1.3 × 10 ⁷ , log B is 7.1 ・ log B-log A = 2.8> 1.5 (Test is valid )-Increase / decrease value = log C-log A-Difference value = (log B-log A)-(log C-log A)

[0051]

[Table 4]  Sample before water immersion Sample after water immersion  Number of bacteria log C Increase / decrease value Difference of bacteria log C Increase / decrease value Difference  Control 7.1 2.7 0.0 7.1 2.7 0.0  Example 1 2.3 -2.0 4.8 2.4 -1.9 4.7 Example 2 2.1 -2.2 5.0 2.2 -2.1 4.9 Example 4 2.4 -1.9 4.7 2.5 -1.8 4.6 Example 5 2.2 -2.1 4.9 2.3 -2.0 4.8 Example 8 2.2 -2.1 4.9 2.3 -2.0 4.8 Example 9 2.5 -1.8 4.6 2.6 -1.7 4.5 Example 11 2.5 -1.8 4.6 2.5 -1.8 4.6Example 12 2.6 -1.7 4.5 2.7 -1.6 4.4

<Application to Air-Conditioner Filter> The dyed monofilament yarns of Examples 1, 2, 4, 5, 8, 9, 11, and 12 before immersion in water were applied to a polypropylene grid frame. The filter was stretched in the vertical and horizontal directions to produce a filter for an air conditioner.
Further, the dyed monofilament yarns before immersion in water and the polypropylene monofilament yarns of Examples 1, 2, 4, 5, 8, 9, 11, 12 and the polypropylene monofilament yarns were arranged in a polypropylene lattice so as to be in the transverse direction and the warp direction, respectively. A filter for an air conditioner was manufactured by attaching the filter to a frame. In any of these cases, it was confirmed that when the filter was washed with water after being used for a certain period of time, no warping or distortion of the filter was observed, and the deodorizing power and antimicrobial power hardly decreased.

<Sweat odor test> T-shirts made of nylon 610 fiber (F ₁ ) and nylon 612 fiber (F ₂ ) were prepared as fiber products (F) (Comparative Example 1, Comparative Example 4), respectively. Functional fiber products were produced in the same manner as in Example 2 (Method 2) and Example 8 (Method 2).

Six men and women belonging to a tennis club (24 years old,
28-year-old and 35-year-old men and 22-year-old, 29-year-old, and 38-year-old women) wore these T-shirts, played tennis games for 1 hour each, and measured sweat odor before and after wearing. . The sweat odor was measured by placing each T-shirt sample in a thermostatic chamber (35 ° C., 85% RH), one bag at a time, in a plastic bag, and two hours later, the odor sensor (New Cosmos The measurement was performed by inserting an XP-329 manufactured by Denki Co., Ltd.) and measuring. Table 5 shows the results. The odor frequency is the sensor reading (no unit). From Table 5, it can be seen that the examples have the effect of suppressing sweat odor.

[0055]

[Table 5]

<Antioxidant Test> The functional fiber products of Examples 2, 8 and Comparative Examples 1 and 4 produced for the above-mentioned sweat odor test were cut into pieces, and further dried using a ball mill. A crushed 325 mesh pass powder was prepared. In addition, castor oil having polyunsaturated fatty acid units and lard in weight of 5 as fat components for checking antioxidant power.
A mixed fat of 0:50 was prepared, and 5% of the above fine powder was mixed with the mixed fat with the aid of an emulsifier. This was left for a predetermined number of days.

1 g of the sample thus prepared was placed in an Erlenmeyer flask equipped with a stopper and added with 30 ml of a mixed solvent of chloroform and acetic acid at a weight ratio of 2: 3, and the fats and oils of the sample were dissolved while gently shaking. . Next, nitrogen gas was introduced into the flask to replace the air inside with nitrogen, and 0.5 ml of a saturated solution of potassium iodide was added while constantly flowing nitrogen gas.
Immediately stoppered. Then, after shaking for 1 minute, the flask was allowed to stand on a cardboard (normal temperature, dark place) for 5 minutes. After 5 minutes, add 30 ml of water, stopper again, vigorously stir, titrate with 1/100 standard sodium thiosulfate standard solution using starch as an indicator. Was quantified. The reaction at this time is -OOH + KI → -OH + I ₂ + KOH.

The peroxide value was determined by the following equation based on the measurement result by titration. Table 6 shows the results. The blank is the case of only fat. From Table 6, it can be seen that the antioxidant power is exhibited in the examples. Peroxide value (meq / kg) = 10 x (A + F) / B A: 1/100 standard sodium thiosulfate standard solution consumption (m
l) F: Factor of 1/100 standard sodium thiosulfate standard solution B: Sampling amount (g)

[0059]

[Table 6]  (F) (A) QuantityPeroxide value (meq / kg)  Type (%) Initial value After 3 days After 7 days After 14 days  Blank--0.0 0.53 0.72 1.38  Comparative Example 1 (F₁) 0.0 0.0 0.53 0.70 1.37Comparative Example 4 (F ₂ ) 0.0 0.0 0.54 0.72 1.39  Example 2 (F₁) 16.6 0.0 0.33 0.49 0.77Example 8 (F ₂ ) 16.2 0.0 0.32 0.47 0.75

<Antiviral test> An air conditioner in which the dyed monofilament yarn before immersion in water in Example 2, Example 8, Comparative Example 1, and Comparative Example 4 was in the horizontal direction and the polypropylene monofilament yarn was in the vertical direction. An influenza virus suspension (0.2 ml) was added dropwise to a sample (3 cm × 3 cm) composed of a filter for use and stored at 25 ° C. After 24 hours of storage, the virus on the specimen is washed out, and the virus infectivity in the wash solution (50% tissue culture infectious dose per 1 ml (TCID ₅₀ ))
Was measured. Table 7 shows the results. Control is a plastic petri dish.

[0061]

[Table 7]

<Method 4> This method 4 is a method in which an anionic fixing agent (C ₁ ) is used in combination as an auxiliary agent (C).

In water, 10 anionic fixing agent (C ₁ ) was added.
% Owf, and a little more water was added to make the whole 1200 parts (bath ratio 1:12) to prepare a treatment bath.
100 parts of the fiber product (F) is put into this treatment liquid,
After the mixture was heated to 60 ° C, the mixture was stirred for 60 minutes. After the temperature was turned off, the stirring was continued for 60 minutes, followed by washing and dehydration.

One or two kinds of catechins (A ₂ ) are added in water.
0% owf, and a little more water was added to make a total of 1200 parts (bath ratio 1:12) to prepare a treatment bath. 10
0 parts were added, the mixture was heated to 120 ° C., stirred for 60 minutes, and then stirred for 60 minutes after the temperature was adjusted, followed by washing and dehydration.

A mordant (B) was added to water at a concentration of 5% owf, and a little water was further added to make a total of 1200 parts (bath ratio 1:12) to prepare a treatment bath. 100 parts of the textile product (F) which has been subjected to the above treatment is added, and the mixture is heated to 90 ° C., stirred for 30 minutes, and then stirred for 60 minutes after turning off the temperature control. went.

Thus, the amount of catechin (A ₂ ) carried was 18.5.
% Of dyed fiber (functional fiber product) was obtained and used for the same deodorizing test and antimicrobial test 1 as described above. The results were as follows.・ Deodorization test Tobacco odor deodorization rate: 73.7% before water immersion, 73.3% after water immersion NH ₃ concentration reduction rate: 76.0% before water immersion, 75.5% after water immersion CH ₃ CHO concentration reduction rate: 66.1% before water immersion , 65.7% after water immersion ・ Antimicrobial test 1 Frequency before water immersion: “−”, frequency after water immersion: “−”

[0067]

The functional nylon fiber product obtained by the method of the present invention includes tea extract, catechin, saponin and the like, regardless of whether the fiber product (F) is a low-absorbing, low water-absorbing nylon fiber. Has an excellent deodorant, antimicrobial, antiallergic, and antioxidant properties, and retains these properties even when used in contact with water. Have maintained.

Since the low water-absorbing nylon fiber is used, for example, the functional nylon-based fiber product of the present invention is stretched over a frame to be used as a filter for an air conditioner or an air cleaner, or to be used for interlining, etc. Even in this case, occurrence of warpage and distortion can be effectively prevented.

Claims (4)

[Claims] 1. A textile product (F) comprising a low water-absorbing nylon fiber having a water absorption of 1% or less in water for 24 hours according to ASTM D570.
At least one active ingredient (A) selected from the group consisting of tea extract, catechin, saponin and tannin (acid) by a dyeing method, and at that time, the fiber product (F) In a bath containing the active ingredient (A)
A process for producing a functional nylon-based fiber product, wherein the process is performed under a high temperature condition exceeding 0 ° C. 2. The low water-absorbing nylon fiber is nylon 61.
The method according to claim 1, wherein the fibers are fibers of 0, nylon 612, nylon 11, nylon 12, or nylon 1212. 3. After treating the textile product (F) in a bath containing the active ingredient (A) under a high temperature condition exceeding 100 ° C., the mordant (B)
The method according to claim 1, wherein the treatment is performed in a bath containing: 4. An auxiliary agent (C) comprising a fixing agent prior to or simultaneously with the treatment of the textile (F) in a bath containing the active ingredient (A) under a high temperature condition exceeding 100 ° C. The method according to claim 1, wherein the treatment is performed in a bath.