JP2000328448A - Production of functional textile product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a functional textile product having excellent deodorant, antimicrobial, antiallergic and antioxidant properties and durability of still maintaining the properties even when brought into contact with water because an active component such as a tea extract, catechin or saponin can surely be supported even on a textile product comprising acrylic, polyester-based or polypropylene-based fibers. SOLUTION: (B) At least one kind of active component selected from the group consisting of a tea extract, catechin, saponin and tannin (tannic acid) is supported on (F) a textile product comprising acrylic, polyester-based or polypropylene-based fibers according to a dyeing method. At this time, the textile product (F) is simultaneously or successively treated in a bath containing two of (A) an auxiliary selected from the group consisting of a reducing agent, a carrier agent, a fixing agent and a cationizing agent and the active component (B) or three of the auxiliary (A), active component (B) and (C) a mordant together or separately therein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method in which an effective ingredient such as a tea extract, catechin or saponin is carried on a textile made of acrylic, polyester or polypropylene fibers by a dyeing method (meaning similar to dyeing). Deodorant,
The present invention relates to a method for obtaining a fiber product having functions such as antimicrobial, antiallergic, and antioxidant properties.

[0002]

2. Description of the Related Art Acrylic, polyester or polypropylene fibers are used for clothing, interior products (hot carpets, carpets, curtains, etc.), bedding (futon cotton, sheets, etc.), car interior goods, air conditioners and air purifiers. Widely used for various applications including filters. If these fibers can carry an effective ingredient such as tea extract, catechin, saponin, etc., an acrylic fiber product having antibacterial properties and deodorant properties can be obtained.

(1) Japanese Patent Application Laid-Open No. 7-148407 (Japanese Patent No. 2719088) discloses an antivirus in which a filter is impregnated with a virus inactivating agent containing tea extract as an active ingredient or kneaded into a filter material. Filters are shown. Tea extraction components are tea polyphenols such as catechins. Examples include (a) a tea extract component dissolved in water to form an aqueous solution and then impregnated and attached to an electret filter. (B) A tea extract component is mixed with polypropylene and melt-molded to form a film. Examples of forming, cutting, and forming a non-woven fabric are given.

(2) Japanese Patent Application Laid-Open No. Hei 8-266828 discloses an antivirus filter comprising a dust collecting filter and a filter to which a tea extraction component is attached. The tea extraction component is a tea polyphenol such as catechin. The filters impregnated with the tea extraction component include electret filters, HEPA filters, high-performance filters, medium-performance filters, and bag filters.

(3) Japanese Patent Application Laid-open No. Hei 6
No. 56656 discloses that a cloth-like material made of natural fibers is reacted with tannic acid by contact 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.

(4) Japanese Patent Laid-Open Publication No.
No. 173176 discloses a process of treating a textile product with tannic acid → fixing treatment with tartar → mordant reaction with a mordant containing a mordant → dyeing reaction with a stain containing an extract of tea. 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. It is described that the material of the fiber product is arbitrary, such as natural fibers such as cotton, hemp, silk, and wool, or a blended product of these natural fibers and a chemical fiber, a mixed woven product, a mixed knitted product, and the like. With respect to applications, applications that come into contact with the skin and applications that have fashionability are listed.

(5) Japanese Patent Application Laid-Open No. Hei 9-316786, also filed by the present applicant, discloses that (a) a fiber product is brought into contact with a dyeing solution containing catechins or an attribute thereof and then contains a mordant. A method for producing a dyed textile product that is brought into contact with a mordant liquid,
(b) There is disclosed a method for producing a dyed fiber product in which a dyeing reaction and a mordant reaction are simultaneously performed by bringing a textile product into contact with a dyeing / mordanting liquid containing both a catechin or an attribute thereof and a mordant. . 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]

However, as described in (1) and (2) above, even if an effective ingredient such as tea extract, catechin, or saponin is adhered and carried on the filter material, the target fiber is made of acrylic. In the case of system fibers, polyester fibers or polypropylene fibers, the amount of adhesion carried is extremely small, and when used in contact with water such as washing or wiping, most of the attached active ingredients are lost. There is a problem that. In addition, even if these active ingredients are kneaded into a filter material such as polypropylene, most of the kneaded active ingredients are eluted when used in contact with water.

On the other hand, according to the dyeing methods (3) to (5) (exactly a method similar to dyeing) proposed by the present applicant, the effective use of catechin or the like is achieved by a dyeing reaction and a mordant reaction. There is an advantage that the components can be chemically supported on the fiber product. However, the dyeing and carrying method by these dyeing means is effective when the fiber product is made of natural fiber such as cotton or silk or synthetic fiber having polarity, but is difficult to dye acrylic fiber, Polyester fibers or polypropylene fibers have a lower dyeing amount than natural fibers and the like, and have a limit that the above-mentioned active ingredient is easily lost when used in contact with water.

[0010] Under such a background, the present invention makes it possible to reliably carry active ingredients such as tea extract, catechin and saponin even on textiles made of acrylic, polyester or polypropylene fibers. Excellent deodorant, antimicrobial, antiallergic,
It is an object of the present invention to provide a method for producing a durable functional fiber product having antioxidant properties and maintaining these properties even when used in contact with water.

[0011]

Means for Solving the Problems The method for producing a functional fiber product of the present invention is a method for producing a fiber product (F) comprising acrylic, polyester or polypropylene fibers by adding tea extract, catechin, saponin and tannin (acid). A) carrying at least one active ingredient (B) selected from the group consisting of: a dyeing method, and at this time, selected from the group consisting of a reducing agent, a carrier agent, a fixing agent, and a cationizing agent. Auxiliary (A) and the above-mentioned active ingredient (B), or the above-mentioned auxiliary (A), the above-mentioned active ingredient (B) and mordant (C)
The above textile products in a bath containing, together or separately,
(F) is processed simultaneously or sequentially.

[0012]

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 antibacterial, bactericidal and bacteriostatic. sex,
It is used in a sense that includes antifungal and antiviral properties.

The present invention is directed to a fiber product (F) comprising acrylic, polyester or polypropylene fibers, and may be a combination of these fibers. Of these, acrylic fibers are fibers containing acrylonitrile as an essential component. Polyester fibers include biodegradable polyester (polylactic acid, aliphatic polyester, microbial polyester, etc.) in addition to ordinary polyester.
Is also included. As the polypropylene in the polypropylene fiber, ordinary polypropylene can be used, but it is particularly preferable to use modified polypropylene as exemplified below. Examples of the modified polypropylene include those obtained by graft copolymerizing polypropylene with a monomer composed of an unsaturated carboxylic acid or a derivative thereof (see, for example, Japanese Patent Publication No. 59-23098). At least one of a nonpolar polymer modified with an acid or a derivative thereof, a nonpolar polymer modified with an unsaturated epoxy monomer, and a nonpolar polymer modified with a silane monomer having an olefinically unsaturated bond is blended. Things (for example, 2-6
No. 3282). Such a modified polypropylene may be a mixture of polyethylene, poly-4-methyl-pentene-1, polyamide and the like. These acrylic, polyester or polypropylene (particularly modified polypropylene) fibers are sheath-
Core-type or bimetal-type conjugate fibers may be used, or fibers in which an active ingredient (B) described below is appropriately added in advance in the production of the fibers may be used.

The above fiber products (F) include raw fibers, yarns (monofilaments, multifilament yarns, spun yarns, woolen yarns, covering yarns, etc.), piles, cotton-like materials, woven fabrics, nonwoven fabrics, knitted fabrics, Any material such as a flocking cloth may be used, and a mixture of fibers and yarns of other materials, a blended product, a mixed woven product, a mixed knit product, a aligned product, or the like may be used.

As the active ingredient (B), 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 bean paste and caps, and black tea and oolong tea extracts can be used.

As the catechin (including its attributed product), a monomeric or oligomeric catechin (including theaflavin) is used. 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 component containing saponin 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 quintet or gallic, or a semi-purified product thereof is used as it is. It can also be used.

The auxiliary agent (A) includes a reducing agent, a carrier agent,
An auxiliary agent selected from the group consisting of a fixing agent and a cationizing agent is used. When the textile (F) is made of acrylic fiber, for example, a reducing agent such as a hydroxylamine salt (in this case, a copper mordant is usually used for the mordant (C)), a polyethylene polyamine resin, Fixing agents such as polyhydric phenol derivatives are preferably used. When the fiber product (F) is made of polyester fiber, for example, aromatic ester diphenyl type,
Carrier agents such as aromatic ester-based, aromatic diallyl oxide-based, aromatic ether-based, methyl naphthalene-based, phenylphenol-based, phthalic acid-based, chlorobenzene-based, and diphenyl derivatives are preferably used. Ester diphenyls are particularly preferred. When the fiber product (F) is made of polypropylene (particularly modified polypropylene) fiber, for example, a fixing agent such as a polyethylene polyamine resin or a polyhydric phenol derivative is preferably used. As the cationizing agent for the textile product (F), various commercially available cationizing agents can be used, and the cationization treatment is usually performed in the presence of an alkali. The role or action of these auxiliaries (A) differs depending on the type and target fiber, but in any case, the desired dyeing properties are sufficiently achieved without the use of these auxiliaries (A). Not done.

As the mordant (C), 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, a textile product (F) comprising the above-mentioned acrylic, polyester or polypropylene (particularly modified polypropylene) fibers is dyed with at least one of the above-mentioned active ingredients (B) by a dyeing method ( In this case, an auxiliary agent (A) selected from the group consisting of a reducing agent, a carrier agent, a fixing agent, and a cationizing agent and the above-mentioned active ingredient are used.
(B) or in the bath containing the auxiliary (A), the active ingredient (B) and the mordant (C) together or separately, in the above-mentioned textile product (F)
Are processed simultaneously or sequentially.

The order of the bath at this time will be exemplified below. Among these, the methods b, d, e, f, and g are particularly preferred. Various other variations are possible. I. Bath containing (A) → Bath containing (B). B. Bath containing (A) → bath containing (B) → bath containing (C). C. Bath containing (B) → bath containing (A) → bath containing (C). D. Bath containing (A) → Bath containing (B) and (C). E. Bath containing (A) and (C) → Bath containing (B). F. Bath containing (A) and (C) → Bath containing (B) → Bath containing (C). G. Bath containing (A) and (B) → Bath containing (C). H. Bath containing (A) and (B) → Bath containing (B) → Bath containing (C). Re. Bath containing (B) and (C) → bath containing (A) → bath containing (C). Nu. Bath containing (A), (B) and (C).

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

The amount of the auxiliary (A) in the bath containing the auxiliary (A) is about 0.2% by weight or more (usually about 1 to 20% by weight) based on the weight of the textile (F), and the amount of the active ingredient (B )), The amount of the active ingredient (B) is based on the weight of the textile (F).
The amount of the mordant (C) in the bath containing the mordant (C) is about 0.2% by weight or more (usually about 1 to 50% by weight).
0.2% by weight or more based on the weight of (F)
% By weight). However, the above amounts are for reference only. Also, (A), (B), and (C) can be contained in two or more baths, such as a part in one bath and the rest in another bath.

In any of the baths, the bath ratio is a fiber product.
5 to 100 times the weight of (F), bath temperature 30 to 14
The treatment time is often about 0 ° C. and about 10 minutes to 3 hours (particularly about 15 minutes to 2 hours), but is not necessarily limited to this range.

Then, at least one of the bath treatments (preferably a bath treatment containing the active ingredient (B)) is carried out for 100 times.
It is particularly preferable to carry out the reaction under a high temperature condition exceeding ℃. At this time, since the bath treatment is performed under pressure, a pressure-type closed dyeing machine is usually used. The temperature during the bath treatment is 105
About 140 ° C, particularly about 115 to 130 ° C. However, when using a fiber having insufficient heat resistance such as a biodegradable polyester, care should be taken to keep the upper limit of the bath temperature at, for example, about 110 ° C. In addition to the above method, a method of performing a dry heat treatment under a high temperature condition exceeding 100 ° C. after the bath treatment (or padding treatment) may be adopted depending on the case. At this time, after performing the bath treatment containing the active ingredient (B) in the bath treatment, preferably the temperature is about 150 to 240 ° C., and more preferably 1 to 240 ° C.
Under high temperature conditions (about 60 to 230 ° C) for a short time (30 seconds to
(About 2 minutes) Dry heat treatment is often used.

The textile product (F) after the above-mentioned treatment is subjected to post-treatment such as acid washing, alkali washing, soaping or water washing, if necessary, followed by natural drying or hot-air drying.

Thus, acrylic, polyester or polypropylene (especially modified polypropylene)
A functional fiber product in which the active ingredient (B) is dyed and carried on the fiber product (F) made of fibers is obtained. The functional fiber products include, for example, filter materials (filters for air conditioners, air purifiers, vacuum cleaners, clean rooms, water purification filters, etc.), clothing (clothes, interlining, lining, apron, 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 kitchenware (toothbrushes, clothes brushes) , Hair brushes, 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 carpets, carpets, curtains, chair upholstery, screen doors, bath mats, etc.), VOCs such as formalin and 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. In addition, "% owf" means weight% with respect to fiber weight. The treatment under high temperature and pressure was performed using a pressurized closed dyeing machine.

<Preparation of Materials> Textile (F) (F ₁ ): Commercially available acrylic fiber (F ₂ ): Commercially available polyester fiber net

Auxiliaries (A) (A ₁ ): hydroxylamine sulfate (reducing agent) (A ₂ ): polyethylene polyamine resin-based fixing agent (A ₃ ): polyhydric phenol derivative-based fixing agent ( A ₄ ): Oil-based emulsified nonionic aromatic ester / diphenyl-based carrier agent (A ₅ ): Oil-based emulsified anionic methylnaphthalene-based carrier agent (A ₆ ): cationizing agent (manufactured by Yatsuo Yushi Kogyo Co., Ltd.) "U
k ")

Active ingredient (B) (B ₁ ): Tea extract (10 g of powdered first tea in 200 ml of water, immersed for about 5 minutes, and 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. (B ₂ ): Catechin (epigallocatechin, epigallocatechin gallate, a catechin preparation derived from tea having a total amount of epicatechin and epicatechin gallate of about 30%) (B ₁₂ ): The above (B ₁ ) and (B ₂ ) (B ₃ ): saponin (a saponin preparation derived from tea having a saponin content of about 50%) (B ₄ ): tannic acid (tannic acid having a tannic acid content of about 80%)

Mordant (C) (C ₁ ): Copper mordant (copper sulfate) (C ₂ ): Iron mordant (iron 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> 5% owf and 5% owf of hydroxylamine sulfate (A ₁ ) and copper mordant (C ₁ ) in water, respectively.
And add a little more water to make the whole 12
A treatment bath was prepared at a rate of 00 parts (bath ratio 1:12), and 100 parts of the acrylic fiber (F ₁ ) washed with water as described above was added to the treatment solution, and heated to 120 ° C. for 60 minutes. After the stirring treatment, and then the temperature control was stopped, the stirring treatment was continued for 60 minutes, followed by washing and dehydration.

An active ingredient (B) was 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) to prepare a treatment bath. 100 parts of the acrylic fiber (F ₁ ) which has been subjected to the above treatment is added, and the mixture is heated to 120 ° C., and then stirred for 60 minutes. And dehydration. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Method 2> A polyethylene polyamine resin-based fixing agent (A ₂ ) was added to water so as to have a concentration of 10% owf, and a small amount of water was further added to make the whole 1200 parts (bath ratio 1:12). A treatment bath was prepared, and 100 parts of the acrylic fiber (F ₁ ) that had been washed as described above was added to the treatment liquid.
After heating to 20 ° 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.

The active ingredient (B) was added to water at 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) to prepare a treatment bath. 100 parts of the acrylic fiber (F ₁ ) which has been subjected to the above treatment is added, and the mixture is heated to 120 ° C., and then stirred for 60 minutes. And dehydration.

A treatment bath was prepared by adding a copper mordant (C ₁ ) to water so as to have a concentration of 5% owf, and further adding a little water to make a total of 1200 parts (bath ratio 1:12). 100 parts of the acrylic fiber (F ₁ ) that has been subjected to the above treatment
After heating to 120 ° C., the mixture was stirred for 30 minutes, and then stirred for 60 minutes after the temperature was turned off.
Dehydration was performed. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Method 3> Method 2 was repeated except that a polyhydric phenol derivative-based fixing agent (A ₃ ) was used in place of the polyethylene polyamine resin-based fixing agent (A ₂ ). As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Method 4> An aromatic ester / diphenyl type carrier agent (A ₄ ) was added to water so as to be 6% owf,
Also, the active ingredient (B) was added to 15% owf, and a little more water was added to make the whole 1200 parts (bath ratio 1:12).
A treatment bath was prepared, and 100 parts of the polyester-based fiber (F ₂ ) which had been subjected to the above-mentioned water washing was added to the treatment solution, and the mixture was heated at 120 ° C.
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.

A treatment bath was prepared by adding a copper mordant (C ₁ ) to water so as to have a concentration of 5% owf, and further adding a small amount of water to a total of 1200 parts (bath ratio 1:12). After 100 parts of the polyester fiber (F ₂ ) that had been subjected to the above treatment was added thereto, the mixture was heated to 90 ° C., stirred for 30 minutes, and then stirred for 60 minutes after turning off the temperature control. Washing and dehydration were performed. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Method 5> Method ₄ was repeated except that an oily emulsified anionic methylnaphthalene-based carrier agent (A ₅ ) was used in place of the aromatic ester-diphenyl carrier agent (A ₄ ).
Was repeated. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Method 6> 5 g of the acrylic fiber (F ₁ ) washed as described above was put into 250 ml of water, 25 ml of cationizing agent (uk) (A ₆ ) (uk 100 g / l) was added, and the mixture was brought to room temperature. After infiltrating for 5 minutes, slowly heat to about 80 ° C over about 30 minutes. Then NaOH 3.75 g (N
(aOH 15f / liter) was added at first 3/10, then 7/10 and heated for about 1 hour. Next, acrylic fiber
(F ₁ ) was taken out and washed with water, 1.25 ml of acetic acid was added to the solution for neutralization, and the solution was permeated at 40 ° C. for 5 minutes. Finally, it was washed with water and dehydrated to obtain a cationized acrylic fiber (F ₁ ).

The active ingredient (B) was added to water at 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) to prepare a treatment bath. Acrylic fiber (F ₁ ) 10 subjected to the above cationization treatment
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.

An iron mordant (C ₂ ) 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 acrylic fiber (F ₁ ) that has been subjected to the above treatment
After heating to 120 ° C., the mixture was stirred for 30 minutes, and then stirred for 60 minutes after the temperature was turned off.
Dehydration was performed. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Method 7> Method 6 was repeated except that the bath treatment with the mordant was omitted. As a result, a dyed fiber (functional fiber product) was obtained, and this was used in a test described later.

<Deodorizing Test 1> 1 m in a substantially cubic shape
Prepare space ³ and install a small vacuum cleaner in which all interior components such as dust collection bags have been removed, wrap the fiber to be tested into each of the processed suction ports, and adjust it to a certain length A circulating device was set up so that air in the space could be circulated. First, five cigarettes (Seven Stars) were ignited at the same time, placed at the center of the floor of the test space, and immediately closed with a lid to make them almost airtight and left for 5 minutes. Air volume
The circulation device was set to 0.5 m ³ / min, and the tobacco was installed so that it could be sucked by an automatic suction machine. . The measurement of the odor was started 5 minutes after the suction (measurement time 0).
After a minute, the internal odor was measured. The measurement of odor is performed by the general-purpose odor sensor “XP-
329 "and a gas detector tube.

Table 1 shows the conditions and Table 2 shows the results. Symbols in Table 1, and textile products _{(F): (F 1)} , (F 2), · aid _{(A): (A 1)} , (A 2), (A 3), (A 4) , (A ₅ ), (A ₆ ), ・ Active ingredient (B): (B ₁ ), (B ₂ ), (B ₁₂ ), (B ₃ ), (B ₄ ), ・ Mordant (C): ( C ₁ ) and (C ₂ ). "(B) Amount" is the active ingredient for textiles (F)
(B) is the amount of dyeing (loading), and the amount of dyeing is the heat balance (heat absorption / heat generation) when heating and heating at a constant rate using a differential thermal analyzer and the accompanying weight increase / decrease. Was determined by analyzing.

[0053]

[Table 1]  (F) (B) Quantity Method First bath Second bath Third bath  Comparative Example 1 (F₁) 0.0 Blank − − − Comparative Example 2 (F₁) 1.7 − (B₁) (C₁)Comparative Example 3 (F ₁ ) 1.6 − (B ₃ ) (C ₁ )  Example 1 (F₁) 10.1 1 (A₁) + (C₁) (B_Two) (C₁) Example 2 (F₁) 9.4 1 (A₁) + (C₁) (B_Three) (C₁) Example 3 (F₁) 10.1 1 (A₁) + (C₁) (B₁) (C₁Example 4 (F₁) 9.0 1 (A₁) + (C₁) (B_Four) (C₁) Example 5 (F₁) 8.8 1 (A₁) + (C₁) (B_Five) (C₁Example 6 (F₁) 9.6 2 (A_Two) (B₁₂) (C₁) Example 7 (F₁) 9.2 2 (A_Two) (B_Three) (C₁Example 8 (F₁) 8.2 3 (A_Three) (B₁₂) (C₁)Example 9 (F ₁ ) 8.0 3 (A ₃ ) (B ₃ ) (C ₁ )  Comparative Example 4 (F_Two) 0.0 Blank − − − Comparative Example 5 (F_Two) 1.4 − (B₁₂) (C_Two) Comparative Example 6 (F_Two) 1.5 − (B₁₂) (C₁)Comparative Example 7 (F ₂ ) 1.4 − (B ₃ ) (C ₁ )  Example 10 (F_Two) 9.7 4 − (A_Four) + (B_Two) (C₁Example 11 (F_Two) 8.2 5 − (A_Five) + (B_Two) (C₁)Example 12 (F ₂ ) 8.7 4 − (A ₄ ) + (B ₃ ) (C ₁ )  Example 13 (F₁) 8.0 6 (A₆) (B_Two) (C_Two)Example 14 (F ₁ ) 3.7 7 (A ₆ ) (B ₂ ) −  “-” Indicates that the bath treatment is omitted

[0054]

[Table 2]  Tobacco smell Ammonia smell CH ₃ CHO concentration  Odor frequency Deodorization rate NH_ThreeConcentration reduction rate CH_ThreeCHO concentration reduction rate30min / 0min (%) 30min / 0min (%) 30min / 0min (%)  Comparative Example 1 1050/1242 15.5 32/55 41.8 14/16 14.3 Comparative Example 2 975/1235 21.1 28/54 48.1 11/16 31.3Comparative Example 3 983/1239 20.7 28/54 48.1 11/16 31.3  Example 1 812/1235 34.3 20/55 63.6 7/16 56.3 Example 2 815/1240 34.3 20/55 63.6 7/16 56.3 Example 3 813/1228 33.8 22/58 62.1 7/16 56.3 Example 4 860 / 1233 30.3 24/58 58.6 8/17 52.9 Example 5 866/1239 30.1 24/58 58.6 8/17 52.9 Example 6 847/1240 31.7 23/56 58.7 8/17 52.9 Example 7 829/1220 32.0 23/57 59.6 8/17 52.9 Example 8 832/1228 32.2 24/60 60.0 8/17 52.9Example 9 852/1236 31.1 25/60 58.3 8/17 52.9  Comparative Example 4 1070/1240 13.7 35/55 36.4 14/16 14.3 Comparative Example 5 1011/1245 18.8 29/55 47.3 11/16 31.3 Comparative Example 6 999/1234 19.9 30/58 48.3 12/17 29.4Comparative Example 7 1003/1230 18.5 30/56 46.6 12/17 29.4  Example 10 700/1240 43.5 7/58 87.9 6/17 64.7 Example 11 792/1238 36.0 11/58 81.0 7/16 56.3Example 12 755/1238 39.0 11/60 81.7 6/16 62.5  Example 13 878/1227 28.4 25/56 55.4 8/16 50.0Example 14 934/1230 24.1 27/56 51.8 10/16 37.5

<Deodorizing Test 2> Comparative Examples 1 to 3, Examples 1 to 9, Comparative Examples 4 to 7, Examples 10 to 12, and Example 1 described above.
The same sample as in Nos. 3 to 14 was subjected to a cycle of immersion in water for 4 hours, squeezing, and drying three times, and then the same deodorizing test was performed again. Table 3 shows the results. According to Table 3, it can be seen that even after the repetition of the above cycle, good deodorizing properties are still maintained.

[0056]

[Table 3]  Tobacco smell Ammonia smell CH ₃ CHO concentration  Odor frequency Deodorization rate NH_ThreeConcentration reduction rate CH_ThreeCHO concentration reduction rate30min / 0min (%) 30min / 0min (%) 30min / 0min (%)  Comparative Example 1 1049/1238 15.3 33/56 41.1 14/16 14.3 Comparative Example 2 978/1236 20.8 30/54 44.4 12/17 29.4Comparative Example 3 983/1236 20.4 30/54 44.4 12/17 29.4  Example 1 815/1235 34.0 21/57 63.2 8/18 55.6 Example 2 815/1235 34.0 21/57 63.2 8/18 55.6 Example 3 812/1222 33.5 22/57 61.4 8/18 55.6 Example 4 860 / 1230 30.1 24/56 57.1 8/16 50.0 Example 5 867/1237 29.9 24/57 57.9 8/16 50.0 Example 6 848/1237 31.4 24/57 57.9 8/17 52.9 Example 7 832/1220 31.8 24/59 59.3 8/16 50.0 Example 8 834/1227 32.0 24/59 59.3 8/17 52.9Example 9 855/1236 30.8 24/57 57.9 8/16 50.0  Comparative Example 4 1070/1233 13.2 36/55 34.5 14/16 14.3 Comparative Example 5 1012/1242 18.5 31/55 43.7 13/18 27.8 Comparative Example 6 1001/1237 19.1 31/56 44.6 13/18 27.8Comparative Example 7 1005/1228 18.2 30/54 44.4 13/18 27.8  Example 10 698/1226 43.1 8/60 86.7 6/17 64.7 Example 11 795/1237 35.7 11/57 80.7 7/16 56.3Example 12 760/1238 38.6 11/58 81.0 6/16 62.5  Example 13 878/1225 28.2 26/58 55.2 8/15 46.7Example 14 938/1230 23.7 28/56 50.0 11/17 35.3

<Antimicrobial test 1> As a fungus culture 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 4 shows the results.

[0058]

[Table 4]

<Antimicrobial Test 2> The functional fiber products before and after the water immersion tests of Examples 1, 6, and 10 were subjected to a bacterial cell count reduction test to determine Staphylococcus aureu.
s Antibacterial activity against ATCC 6538P was investigated. That is,
A bouillon suspension of the test bacterium was poured into the sterilized sample, and the number of viable cells after culturing at 37 ° C. for 18 hours in a closed container was measured to determine the rate of increase / decrease relative to the number of inoculated cells. The unprocessed cloth used was a standard cotton cloth. The results are shown below and in Table 5.・ Number of inoculated A is 1.9 × 10 ⁴ , log A is 4.3 ・ Number of unprocessed cloth B is 1.3 × 10 ⁷ , log B is 7.1 ・ log B-log A = 2.8> 1.5 (Test is valid) ・ Change = log C-log A ・ Difference in change = (log B-log A)-(log C-log A)

[0060]

[Table 5]  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 3.3 -1.0 3.8 3.4 -0.9 3.7 Example 2 3.1 -1.2 4.0 3.2 -1.1 3.9 Example 6 3.6 -0.7 3.5 3.8 -0.5 3.3Example 10 2.6 -1.7 4.5 2.6 -1.7 4.5

<Preparation of Materials> Textiles (F) (F ₃ ): fibers of modified polypropylene obtained by graft-copolymerizing 7% of acrylic acid with polypropylene Auxiliary (A) (A ₂ ): polyethylene polyamine resin Fixing agent (A ₃ ): Fixing agent of polyhydric phenol type derivative ・ Active ingredient (B) (B ₂ ): Catechin (epigallocatechin, epigallocatechin gallate, epicatechin and epicatechin gallate having a total amount of about (B ₃ ): Saponin (saponin preparation derived from tea having a saponin content of about 50%)-Mordant (C) (C ₁ ): Copper mordant (copper sulfate)

<Pretreatment> The above fiber product (F) (modified polypropylene fiber (F ₃ )) was put into water, heated to 80 ° C. with stirring, and stirred at this temperature for about 10 minutes. , Washing and dehydration.

<Method 8> A polyethylene polyamine resin-based fixing agent (A ₂ ) was added to water at a concentration of 10% owf, and a small amount of water was further added to make a total of 1200 parts (bath ratio 1:12). A treatment bath was prepared, and 100 parts of the modified polypropylene fiber (F ₃ ) that had been washed with water was added to the treatment liquid, and the mixture was heated to 90 ° C. and stirred for 60 minutes.
Then, after turning off the temperature control, the stirring process was continued for 60 minutes.
Washing and dehydration were performed.

15% owf of the active ingredient (B) and acetic acid in water
1.5% owf was added, and a little water was further added to make a total of 1200 parts (bath ratio 1:12) to prepare a treatment bath, and this treated solution was treated with the modified polypropylene fiber ( F ₃ ) 100 parts were added, and the mixture was heated to 120 ° C., stirred for 60 minutes, and then cooled to 60 ° C.
After continuing the stirring treatment for minutes, washing and dehydration were performed.

A treatment bath was prepared by adding a copper mordant (C ₁ ) to water so as to have a concentration of 5% owf, and further adding a small amount of water to a total of 1200 parts (bath ratio 1:12). After 100 parts of the polypropylene fiber (F ₃ ) that had been subjected to the above treatment was added, the mixture was heated to 90 ° C., stirred for 30 minutes, and then stirred for 60 minutes after turning off the temperature control. Washing and dehydration were performed. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Method 9> A polyhydric phenol derivative-based fixing agent (A ₃ ) was used in place of the polyethylene polyamine resin-based fixing agent (A ₂ ), and acetic acid was added to the treatment bath of the active ingredient (B). Was repeated except that the addition of was omitted. As a result, a relatively dark-colored dyed fiber (functional fiber product) was obtained, and this was used for the test described later.

<Deodorizing Test 3> A test similar to the above-described deodorizing test 1 was performed on the functional fiber product obtained above.
For this functional fiber product, immerse in water for 4 hours → squeeze →
After repeating the drying cycle three times, the same deodorizing test as above was performed again.

Table 6 shows the conditions, and Table 7 shows the results. The symbols in Table 6 are: Textile (F): (F ₃ ), Auxiliary (A): (A ₂ ), (A ₃ ), Active ingredient (B): (B ₂ ), (B ₃ ), mordant (C): (C ₁ ).

[0069]

[Table 6]  (F) (B) Quantity Method First bath Second bath Third bath  Comparative Example 8 (F_Three) 0.0 Blank − − − Comparative Example 9 (F_Three) 1.9 − (B_Two) (C₁)Comparative Example 10 (F ₃ ) 1.9 − (B ₃ ) (C ₁ )  Example 15 (F_Three) 13.5 8 (A_Two) (B_Two) (C₁) Example 16 (F_Three) 9.4 9 (A_Three) (B_Two) (C₁)Example 17 (F ₃ ) 12.29 (A ₃ ) (B ₃ ) (C ₁ )

[0070]

[Table 7] Odor deodorization rate (%) NH ₃ concentration reduction rate (%) CH ₃ CHO concentration reduction rate (%) Before water immersion Before water immersion Before water immersion After water immersion Before water immersion Comparative Example 8 14.3 14.2 40.0 39.2 14.3 14.3 Comparative Example 9 22.2 20.7 48.5 44.6 31.3 29.4 Comparative Example 10 22.0 20.7 48.8 44.6 31.3 31.3 Example 15 47.4 47.0 88.6 88.1 70.1 68.8 Example 16 41.8 41.6 82.9 82.5 64.7 64.7 Example 17 46.5 46.2 87.0 86.7 70.1 68.8

<Antimicrobial Test 3> Examples 15 to 1
With respect to the functional fiber product of No. 7 and the fiber products of Comparative Examples 8 to 10, the propagation status of fungi was observed under the same conditions as in the antimicrobial test 2. Table 8 shows the results.

[0072]

[Table 8]

<Application to Filter for Air Conditioner> Embodiment 1
5, 16 and 17 dyed monofilament yarns before water immersion were stretched in a vertical and horizontal direction on a polypropylene frame to produce a filter for an air conditioner. It was confirmed that even when these filters were washed with water after being used for a certain period of time, the deodorizing power and antimicrobial power hardly decreased. Also, by washing with water,
No warping or distortion of the filter was observed.

<Sweat Odor Test> T-shirts made of acrylic fiber (F ₁ ) and polyester fiber (F ₂ ) were prepared as fiber products (F) (Comparative Examples 1 and 4). 1
(Method 1) A functional fiber product was produced in the same manner as in Example 10 (Method 4).

[0075] Six men and women were asked to wear these T-shirts, a tennis game was played for one hour each, and the sweat odor before and after wearing was measured. 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 Electric Corporation, XP-32
9) was inserted and measured. Table 9 shows the results. The odor frequency is the sensor reading (no unit). From Table 9, it can be seen that the examples have the effect of suppressing sweat odor.

[0076]

[Table 9]

<Antioxidant Test> The functional fiber products of Examples 1, 10 and Comparative Examples 1 and 4 produced for the above-mentioned sweat odor test were shredded and further dried using a ball mill. A crushed 325 mesh pass powder was prepared. Also, as an oil component for checking the antioxidant power, a 50:50 mixed oil and fat by weight of castor oil having polyunsaturated fatty acid units and lard is prepared, and the above-mentioned fine powder is added to the mixed oil and fat to help an emulsifier. Borrowed and mixed 5%. 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 stoppered stopper, 30 ml of a mixed solvent of chloroform and acetic acid in a weight ratio of 2: 3 was added, and the fat and oil of the sample was 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 10 shows the results. The blank is the case of only fat. From Table 10, 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)

[0080]

[Table 10]  (F) (B) 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 0.73 1.39Comparative Example 4 (F ₂ ) 0.0 0.0 0.54 0.72 1.40  Example 1 (F₁) 10.1 0.0 0.42 0.57 0.85Example 10 (F ₂ ) 9.7 0.0 0.45 0.61 0.89

<Antiviral Test> The dyed monofilament yarn before immersion in Example 1, Example 10, Comparative Example 1, and Comparative Example 4 was set to the horizontal direction, and the dyeing before Example 15 was immersed in water. Specimen (3 cm x 3) consisting of a filter for an air conditioner with a denatured polypropylene monofilament yarn in the longitudinal direction
cm), 0.2 ml of the influenza virus suspension was added dropwise and stored at 25 ° C. After 24 hours of storage, the virus on the sample is washed out, and the virus infectivity (1
The logarithmic value of 50% tissue culture infectious dose per ml (TCID ₅₀ ) was measured. Table 11 shows the results. Control is a plastic petri dish.

[0082]

[Table 11]

[0083]

The functional fiber product obtained by the method of the present invention is a tea extract, regardless of whether the fiber product (F) is a difficult-to-dye acrylic, polyester or polypropylene fiber product. Because the active ingredients such as catechin and saponin are securely carried, it has excellent deodorant, antimicrobial, antiallergic and antioxidant properties, and even when used in contact with water These properties are maintained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) D06P 1/46 D06P 1/46 3/52 3/52 3/64 3/64 5/20 5/20 A 5/22 5/22 // D06M 101: 32 F term (reference) 4H011 AA02 BA04 BB08 BB22 BC19 DA10 DH02 DH04 4H057 BA05 BA22 BA32 CA03 CA08 CB18 CB33 CB35 CB38 CB39 CB40 CB43 CB90 CC01 DA01 DA17 DA18 DA19 HA03 A07A07 GA02 AC10 BA08 BA13 BA21 BA45 BA53 BA99 CA57

Claims (2)

[Claims] 1. A textile product (F) comprising acrylic, polyester or polypropylene fibers, comprising at least one active ingredient (B) selected from the group consisting of tea extract, catechin, saponin and tannin (acid). ) By the dyeing method, and at that time, an auxiliary agent (A) selected from the group consisting of a reducing agent, a carrier agent, a fixing agent and a cationizing agent, and the above active ingredient
(B) or the above-mentioned auxiliary (A), the above-mentioned active ingredient (B) and the mordant (C)
A method for producing a functional fiber product, wherein the fiber product (F) is treated simultaneously or sequentially in a bath containing the ingredients together or separately. 2. The method of claim 1, wherein at least one of the bath treatments is performed by
2. The method according to claim 1, wherein the heat treatment is carried out under a high temperature condition exceeding 00 ° C. or a dry heat treatment is carried out under a high temperature condition exceeding 100 ° C. after the bath treatment.