JP2023097388A - Fiber structure and method for manufacturing the same - Google Patents

Abstract

To provide a fiber structure having high washing durability and antibacterial and antiviral functionality, capable of suppressing discoloration and excellent even in texture.SOLUTION: A fiber structure obtained by sticking silver chloride supported titanium oxide and quarternary ammonium salt to a fiber includes a polyurethane component. To the mass of the fiber structure, the silver chloride supported titanium oxide is 0.003-0.6 mass%, and the quarternary ammonium salt is 0.0005 to 0.5 mass %; the following (1) and/or (2) are satisfied; and an antiviral activity value after home washing of about 10 times is 2.0 or more by a JISL1922 plaque measurement method. (1) The polyurethane component is a polyurethane resin sticking to the fiber constituting the fiber structure as a binder, and the coating weight is 0.01-1.0 mass% to the mass of the fiber structure, and (2) the polyurethane component is a polyurethane fiber included as the fiber constituting the fiber structure.SELECTED DRAWING: None

Description

The present invention relates to a fiber structure and its manufacturing method.

In recent years, with the diversification of lifestyles and the spread of new coronavirus infections, awareness of health and hygiene has increased. As a result, products with antibacterial, deodorant, and antiviral functions have been put to practical use.

So far, methods for imparting functionality such as antibacterial and antiviral properties include methods using metal particles or quaternary ammonium salts (Patent Document 1), and methods of attaching fumaric acid to fibers (Patent Document 2). It is

Patent Document 1 describes a fiber having a quaternary ammonium salt and a metal salt or metal oxide, and states that it is preferable to use a polyurethane binder as the binder resin.

Patent Literature 2 describes a technique in which fumaric acid is used as an antibacterial agent in combination with a resin such as polyurethane for adhesion.

JP 2013-184906 A JP 2017-197853 A

With the spread of the new coronavirus infection, lifestyles have changed significantly, and various indoor and outdoor exercises are being actively carried out from the viewpoint of health promotion. There is a growing demand for textile goods made from

There is a demand for the development of various antiviral textiles, especially textiles that maintain high antiviral performance even after repeated washing in daily life.

The methods disclosed in Patent Literatures 1 and 2 have problems of poor washing durability, large amounts of antiviral agents and binders, and impairing the quality such as texture of the fiber structure.

In particular, in the technique described in Patent Document 2, a large amount of polyurethane resin is used as a binder in order to impart durability to washing, which may impair the texture of the fiber.

In addition, high virality can generally be imparted using an antibacterial agent, but the amount used for imparting antibacterial properties does not exhibit sufficient high virality. Therefore, it is necessary to use more antibacterial agents and binders in order to develop antiviral properties with high washing durability.

However, according to the studies of the present inventors, if the amount of binder used is increased compared to the antiviral agent in order to improve washing durability, the binder may inhibit the performance of the antiviral agent. It was found that the water absorption might be inhibited.

In addition, metal-based antiviral agents such as silver, copper, and zinc have been well known. was also found to be a problem.

An object of the present invention is to provide a fiber structure having functionality such as antibacterial properties and antiviral properties with high washing durability, suppressed discoloration, and excellent texture, and a method for producing the same.

In order to solve the above problems, the present inventors have found that by using a very small amount of silver chloride supported on titanium oxide and a quaternary ammonium salt as a silver component, there is no fear of discoloration and a high antiviral It was found that a fiber structure having properties can be obtained. Furthermore, by applying the high adhesion and high exhaustion capacity of polyurethane resins, we have found that high antiviral properties can be maintained even after washing by retaining the functional agent on the fiber surface.

Further, the inventors have found that the washing durability of the functional agent can be greatly improved by utilizing the high absorption capacity of the polyurethane fiber without using the polyurethane resin.

That is, the present invention employs the following configurations.
[1] A fibrous structure in which silver chloride-supported titanium oxide and a quaternary ammonium salt are attached to fibers, and further comprising a polyurethane component, wherein the mass of the fibrous structure is Silver chloride-supported titanium oxide is 0.003 to 0.6% by mass, the quaternary ammonium salt is 0.0005 to 0.5% by mass, satisfies the following (1) and / or (2), and meets JISL1922 : A fiber structure with an antiviral activity value of 2.0 or more after 10 washings at home according to the 2016 plaque assay method.
(1) The polyurethane component is a polyurethane resin adhered as a binder to the fibers constituting the fiber structure, and the adhered amount thereof is 0.01 to 1.0% by mass with respect to the mass of the fiber structure. .
(2) Polyurethane fibers in which the polyurethane component is included as fibers constituting the fiber structure.
[2] The fiber structure according to [1], wherein the polyurethane resin is a polycarbonate-based urethane resin.
[3] The fiber structure according to [1] or [2], which further satisfies the following (3) or (4).
(3) The ionicity of the polyurethane resin is cationic or nonionic.
(4) The ionicity of the polyurethane resin is anionic, and the polyurethane resin adheres to the fibers together with the compatibility improver.
[4] The fiber structure according to any one of [1] to [3], which has an antiviral activity value of 3.0 or more after 10 washings at home according to the JISL1922:2016 plaque assay method.
[5] The fibers are immersed in an aqueous solution of the silver chloride-supported titanium oxide and the quaternary ammonium salt, or an aqueous solution of the silver chloride-supported titanium oxide, the quaternary ammonium salt, and the polyurethane resin, and then heated to 130°C. The method for producing a fiber structure according to any one of [1] to [4], wherein drying and curing are performed at the above temperature.

By applying the high adhesion and high exhaustion capacity of polyurethane, it has become possible to obtain fiber structures with excellent washing durability and antibacterial and antiviral properties. This processing technology is highly safe in that the chemicals used are highly safe and effective even when the amount of chemicals used is small. For the same reason, it has little effect on the human body, such as skin irritation. In addition, the amount of the metal-based antiviral agent used is extremely small, so discoloration of the fiber structure is suppressed.

In addition, even when a polyurethane resin is used as a binder in the present invention, the content is small, the performance of the antiviral agent is not impaired, and the texture of the obtained fiber structure is hardly spoiled.

The present invention will be described in detail below.

[Silver chloride-supported titanium oxide]
The silver chloride-supported titanium oxide in the present invention is silver chloride supported on titanium oxide, and the titanium oxide is preferably titanium dioxide. Silver chloride is highly stable, and when it is carried on titanium oxide, it leads to further improvement in stability, and the washing durability of the silver component is improved.

The quaternary ammonium salt in the present invention is not particularly limited, but preferably has one alkyl group and three methyl groups, and more preferably the alkyl group has 8 to 20 carbon atoms.

[Quaternary ammonium salt]
The quaternary ammonium salt is a salt of a quaternary ammonium ion and various anions (anions), and is not particularly limited as long as the desired antibacterial and antiviral finishing agents, etc., of the present invention can be obtained. Anions that form salts with quaternary ammonium ions include chloride, bromide, fluoride, iodide, hydroxide, nitrate and sulfate ions, as well as molecular ions (polyatomic ions). It's okay. Preferably the anion is a chloride ion. Preferably, the quaternary ammonium salt is a quaternary ammonium chloride.

Quaternary ammonium salts include didecyldimethylammonium chloride, cetrimonium chloride, dialkyldimethylammonium chloride, dialkyldimethylammonium bromide, hexadecyltrimethylammonium bromide, tetrabutylammonium acetate, benzalkonium chloride, tetramethylammonium iodide, trimethyldecylammonium bromide, alkyltrimethylammonium bromide, alkyltrimethylammonium chloride, trimethyloctadecylammonium chloride, didecylmonomethylhydroxyethylammonium bromide, alkyldimethylhydroxyethylammonium chloride, alkyltrimethylammonium bromide, dioctyldimethylammonium chloride, dioctyldimethylammonium bromide, octyldecyldimethylammonium chloride and the like.

In addition, "HeiQ Viroblock NPJ03" manufactured by HeiQ (silver chloride-supported titanium oxide: 0.3% by mass, quaternary Ammonium salt component: 0.3% by mass) has low skin irritation and can be used very preferably in the present invention. And it can be said that the fiber structure obtained by processing it is highly safe.

[Polyurethane component]
The polyurethane component is not particularly limited. The form of the polyurethane component may be a form of a so-called binder resin that is used by adhering it to fibers constituting a fiber structure, or a form of a polyurethane fiber described later.

When the polyurethane component is a polyurethane resin that is used as a so-called binder resin by attaching it to fibers as a binder, it is preferably a polyester-based or polycarbonate-based polyurethane resin. Since polycarbonate has a benzene ring in its structure, it can suppress the shedding of the antiviral agent compared to other resins and binders. Moreover, the synthesis method thereof is not particularly limited.

In addition, when a processing liquid is prepared by adding a polyurethane resin together with silver chloride-supported titanium oxide and a quaternary ammonium salt used in combination as an antiviral agent and used for processing a fiber compound, the scale of implementation is an industrial scale. In some cases, or when the processing liquid is stored for a long time after preparation, complex-like aggregates may be formed depending on the ionicity of the polyurethane resin used. That is, when the polyurethane resin is cationic or nonionic, complexes are not normally formed. They tend to form a complex inside. Therefore, when using an anionic polyurethane resin, it is preferable to further add a compatibility improver to improve compatibility. If processing is performed in the presence of aggregates in the processing liquid, there is a concern that the functional agent (antiviral agent) may become uneven during processing, and processing equipment may become dirty. Therefore, when the working fluid is stored for a long period of time, aggregation may occur when it is carried out on an industrial scale. This is a preferred embodiment in that it is possible to prevent unevenness in printing and to prevent contamination of the processing apparatus.

In addition, as another method when aggregates are generated when a polyurethane resin is used together with an antiviral agent in the same bath, a cationic polyurethane resin and / or a nonionic polyurethane resin can be used in combination, or a more compatible By adding an improver, the complex can be suppressed while maintaining high performance.

When the polyurethane resin is used in the present invention, its particle size is preferably 0.01 to 0.1 μm, more preferably 0.03 to 0.05 μm. By having the above particle size, the antiviral properties of the silver-based component and the quaternary ammonium salt are not inhibited, and they can be fixed to the fiber. The above particle size is an average particle size measured by a light scattering method using Nanotrac particle size distribution analyzer UPA-EX150; manufactured by Nikkiso Co., Ltd.

[Compatibility improver]
The compatibility improver is not particularly limited as long as the desired improvement in liquid stability is obtained in the present invention. By adding it to the processing liquid used when manufacturing the fiber structure, it has the effect of suppressing the generation of aggregates and improving compatibility. Examples include those commonly used as dispersants, which form ionic bonds with ionic components and disperse the components to suppress the generation of aggregates. As the compatibility improver, anionic surfactants and the like are generally used, and examples thereof include anionic surfactants such as sodium naphthalenesulfonate formalin condensate. Commercially available products can be used as such anionic surfactants, and specific examples include "Labelin (registered trademark)" FC-45M manufactured by K&D Fine Chemicals. Also, an amphoteric surfactant may be used in order not to deactivate the cationic properties of the antiviral agent. Carboxybetaine-type amphoteric surfactants and the like can be used as such amphoteric surfactants, and commercially available products thereof include, for example, "Enagicol (registered trademark)" L-30B manufactured by Lion Specialty Chemicals Co., Ltd. , “Enagicol (registered trademark)” C-40H, and the like.

The presence or absence of agglomeration should be confirmed by the following method. A working fluid of 300 ml is prepared, stirred at 3000 rpm for 5 minutes, and left to stand for 1 hour to check the state. When aggregates are generated, the working fluid is separated into two layers or semi-solid aggregates are generated. By observing the occurrence of this occurrence, the occurrence of aggregates can be confirmed.

The content of the compatibility improver is preferably 0.1 to 1.0% by mass relative to the mass of the fiber structure in order to obtain a sufficient effect, and is preferably 0.2 to 0.8% by mass. is more preferable.

Moreover, in addition to the above components, a water absorbing agent may be used in combination. By using a water-absorbing agent together, water absorption can be obtained without impairing the antiviral performance. Examples of water absorbing agents used in combination include polyester resin-based, silicone-based, and polyacrylic-based water absorbing agents.

[Fibers Constituting Fiber Structure]
The fibers constituting the fiber structure are not particularly limited, and may be synthetic fibers, natural fibers, or mixtures thereof. Synthetic fibers include polyalkylene terephthalates such as polyethylene terephthalate, polyester fibers made of copolymers thereof (which may be cationic dyeable polyesters), nylon fibers, acrylic fibers, polyurethane fibers, and the like. Examples of natural fibers include cotton, wool, rayon, and cupra. These can be used singly or in combination of two or more.

In the present invention, polyester fibers are preferably included from the viewpoint of functionality. Polyester fibers can be used alone or in combination with other fibers. As polyester fibers, cationic dyeable polyester fibers and other polyester fibers may be used in combination. It is preferable that the fibers constituting the fiber structure contain polyester fibers in an amount of 45% by mass or more.

Fibers other than polyester fibers may be synthetic fibers, natural fibers, or mixtures thereof. Examples of synthetic fibers other than polyester fibers include nylon fibers and acrylic fibers. Examples of natural fibers include cotton, wool, rayon, and cupra. These may be contained in any form such as spun yarn, mixed yarn, mixed weave, mixed knit, and mixed cotton.

Moreover, the use of polyurethane fibers is preferable in that they can function as the polyurethane component in the present invention.

When polyurethane fibers are used as the polyurethane component, fibers other than polyurethane include synthetic fibers and natural fibers, and mixed products thereof may be used. Synthetic fibers include, for example, polyester fibers, cationic dyeable polyester fibers, nylon fibers, and acrylic fibers. Examples of natural fibers include cotton, wool, rayon, and cupra. These may be contained in any form such as spun yarn, mixed yarn, mixed weave, mixed knit, and mixed cotton.

Both of the above polyester fibers and polyurethane fibers can be used in combination, and can also be used together with other fibers. As other fibers, synthetic fibers and natural fibers other than the polyester fibers and polyurethane fibers used can be used. Among the above other fibers, synthetic fibers include, for example, nylon fibers and acrylic fibers. Examples of natural fibers include cotton, wool, rayon, and cupra. One or more of these other fibers can be used.

When two or more types of fibers are used in combination in the fiber structure, the form of use may be any form such as blended yarn, composite spun yarn, mixed yarn, composite yarn, mixed weave, mixed knit, mixed cotton, etc. .

[Fibrous structure]
The fiber structure of the present invention may be in the form of yarn, in the form of fabric such as woven or knitted fabric, or in the form of textile products or the like obtained by processing them.

In the present invention, by adhering the silver chloride-supported titanium oxide and the quaternary ammonium salt to the fiber, and by including a polyurethane component in the fiber structure, high antiviral properties are exhibited. By using silver chloride-supported titanium oxide and a quaternary ammonium salt together, the quaternary ammonium salt destabilizes the virus, and the silver ion easily exhibits its performance against the virus, inactivating the virus in a short time. It is possible to Furthermore, as a polyurethane component, a polyurethane resin is used as a binder, silver chloride-supported titanium oxide and a quaternary ammonium salt are used in combination, or polyurethane fibers are present in the fiber structure, so that the performance is maintained even after repeated washing. It is possible to develop durability. It is believed that the high adhesion of the polyurethane resin to the fiber and/or the high exhaustion capacity of the polyurethane fiber contributed to the improvement in washing durability. Usually, when fibers or textile articles on which only silver chloride-supported titanium oxide and quaternary ammonium salts are present are washed with laundry detergents containing various surfactants, the antiviral properties are significantly improved after washing. However, the coexistence of a polyurethane component with silver chloride-supported titanium oxide and a quaternary ammonium salt can improve washing durability. obtain.

Furthermore, the silver chloride-supported titanium oxide contained in the fiber structure is 0.003 to 0.6% by mass, more preferably 0.01 to 0.1% by mass, and 0.02 to 0.05% by mass. % by weight is most preferred. If the amount of silver chloride-supported titanium oxide is too small, antiviral properties are not exhibited. On the other hand, too much may discolor the fiber structure.

Furthermore, the quaternary ammonium salt contained in the fiber structure is 0.0005 to 0.5% by mass, more preferably 0.005 to 0.1% by mass, and 0.01 to 0.05% by mass. % by weight is most preferred. If the amount of quaternary ammonium salt is too low, antiviral properties will not develop. On the other hand, if it is too large, the working liquid foams during working, making uniform working difficult.

When a polyurethane component is used as a binder in the present invention, it is important to control the amounts of the silver chloride-supported titanium oxide, the antiviral agent such as the quaternary ammonium salt, and the polyurethane resin. If the amount of binder used is increased compared to the antiviral agent in order to improve washing durability, the binder may inhibit the performance of the antiviral agent and the water absorption of the fabric.

When a polyurethane resin is used as the binder, the polyurethane resin contained in the fiber structure is 0.01 to 1.0% by mass, more preferably 0.05 to 0.7% by mass, and 0.1% by mass. ~0.5% by weight is most preferred. If the amount of polyurethane resin is small, the antiviral properties after washing are greatly reduced. On the other hand, when the weight percentage is between the upper limit and the lower limit, the fiber structure has higher washing durability without impairing the antibacterial/antiviral properties of the antibacterial/antiviral agent.

As described above, it is also possible to use polyurethane fibers as the fibers constituting the fiber structure instead of attaching the polyurethane resin as a binder to the fibers. The amount used is preferably 1 to 10% by mass based on the mass of the fibers constituting the fiber structure.

As a method of processing fibers with an antiviral agent consisting of silver chloride-supported titanium oxide and a quaternary ammonium salt, for example, a method of immersing fibers in a processing agent containing the antiviral agent and applying a processing agent to an article ( or coating) or spraying can be exemplified. The fibers to be immersed may be in the form of threads. It may be in the form of fabric such as woven or knitted fabric, or may be in the form of textile products or the like obtained by further processing them. Further, when a polyurethane resin is used as the binder, a processing agent containing the polyurethane resin together with the antiviral agent can be used. Hereinafter, as the processing method for attaching the silver chloride-supported titanium oxide and the quaternary ammonium salt to the fiber, pad, dry (Pad, Dry) processing and in-bath processing are preferable, and a polyurethane resin is used in combination as a binder resin. As a method, pad and dry processing are preferable. As the in-bath processing, it is preferable to immerse the fabric in the prepared processing liquid, then dry it at 100° C. or higher, and perform a curing treatment. As for the pad and dry processing, it is preferable to dip and nip the fabric in the processing liquid, then dry it at 130° C. or higher and cure it. However, there is no particular limitation as long as the desired antibacterial and antiviral article (or processed article) of the present invention can be obtained.

Further, when a water absorbing agent is used in combination, it may be used together in bath processing, pad processing, or dry processing. In-bath processing is preferably performed before antiviral processing. In the case of pad and dry processing, it may be performed simultaneously with antiviral processing, or two-step processing of antiviral processing and water-absorbing agent processing may be performed. Two-stage processing refers to performing one processing after the other processing. In order to obtain high antiviral washing durability, it is preferable to employ a two-step process in which the water-absorbing agent is processed after the antiviral process.

The thus-obtained fiber structure of the present invention can achieve an antiviral activity value of 2.0 or more after 10 washings at home according to the JISL1922:2016 plaque assay method.

The fiber structure of the present invention is preferably in the form of cloth, and is used for clothing such as casual wear and uniforms, bedding such as bed sheets and pillow covers, and small articles.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as it does not deviate from the gist thereof.

(Antiviral evaluation method)
The measurement was performed according to JIS L1922:2016 plaque measurement method. Details are shown below.
1. Place 0.4 g of the test piece in a vial, drop 0.2 mL of the test virus suspension, and then cover the vial.
2. Place the vial at 25° C. for 2 hours.
3. 20 mL of washing solution is added to wash out the test bacteria from the test piece, and the number of viable viruses in the washing solution is measured by the plaque assay method.
4. The antiviral activity value is calculated according to the following formula.
Antiviral activity value = {log (control sample, viable count after culture) - log (control sample, viable count immediately after inoculation)} - {log (test sample, viable count after culture) - log (test sample, viable count immediately after inoculation) number of bacteria)}
A standard cloth (cotton) was used for the control sample.

If the antiviral activity value≧3.0, it is passed. Influenza A virus (H3N2) ATCC VR-1679 was selected as the corresponding virus species. Viruses are broadly classified into those that have an outermost membrane called an envelope and those that do not. Influenza A viruses and novel coronaviruses are classified as viruses having an envelope.

(Antiviral evaluation after 10 washings at home)
Antiviral properties were evaluated according to the above JIS L1922:2016 plaque measurement method using test pieces that had been washed at home 10 times. The above home washing method used the JIS L0217:1995 103 method described later).

(How to wash at home)
JIS L0217:1995 103 method was used. Specifically, using a home electric washing machine (NA-F50B9 manufactured by Panasonic) with a centrifugal dehydrator specified in JIS C9606 001: 1993, 002: 2007, the liquid temperature is 40 to the water level line indicating the standard water amount. ℃ water, and 40 mL of JAFET standard combination detergent (containing polyoxyethylene alkyl ether and sodium alpha olefin sulfonate) is used. The sample and load cloth were added to the washing liquid so that the bath ratio was 1:30, and the operation was started.

After 25 minutes of washing treatment, the operation was stopped, the sample and load cloth were dehydrated in a dehydrator, and then the washing liquid was replaced with fresh water at a temperature of 30°C or less, and rinsing was performed for 2 minutes at the same bath ratio. After a 2 minute rinse, the run was stopped and the sample and load cloths were allowed to dry, rinsed again for 2 minutes, dried and line dried without direct sunlight.

(Evaluation of Texture) The texture of the resulting fiber structure was evaluated by sensory evaluation. ◯ (good), △ (slightly unsatisfactory) when slightly hard and restricting body movement, and × (poor) when too hard and giving a strong resistance to movement.

(Water absorption evaluation method)
JIS L1907:2010 dropping method was used. Attach the test piece to the test piece holding frame and adjust so that the height from the surface of the test piece to the tip of the burette is 10 mm. Next, drop a drop of water from the burette, and use a stopwatch to measure the time from when the drop reaches the surface of the test piece until the specular reflection disappears and only the wetness remains as the test piece absorbs the water drop. Measure to the nearest second.

(Discoloration evaluation)
Moreover, the discoloration property of the obtained fiber structure was evaluated by sensory evaluation. Compared to the unprocessed fabric, discoloration is sufficiently suppressed and there is almost no discoloration ◎ (excellent), discoloration is suppressed but slight discoloration is ◯ (good), discoloration is suppressed Slightly discolored was evaluated as Δ (slightly unsatisfactory), and markedly discolored was evaluated as x (defective).

<Example 1>
"HeiQ Viroblock NPJ03" manufactured by HeiQ Co. (silver chloride-supported titanium oxide: 0.3% by mass, quaternary ammonium salt component: 0.3% by mass) containing the following components A and B was prepared.
(A) Silver component: silver chloride-supported titanium oxide (B) Quaternary ammonium salt: hexadecyltrimethylammonium bromide The following polyurethane resin was prepared.
(C) Polyurethane resin: Polycarbonate-based urethane resin (superflex 460 solid content 38% by mass, anionic polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

(Test cloth)
As a test cloth, a white knitted fabric (cut to 40 cm long×30 cm wide) of 100 mass % polyester fiber was prepared (T100 in the table).

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing A and B was weighed to 125 g/L and C to 10 g/L, added to water and stirred to prepare a processing agent.

After the test cloth was sufficiently immersed in the processing agent, the test cloth was nipped (pickup rate: 80%) to remove excess processing agent. After that, it was dried and cured to obtain the polyester fiber structure of the present invention.

It was found that the obtained fiber structure had sufficient antiviral properties after about 10 washings, and the texture was almost unchanged compared to the unprocessed product.

<Example 2>
HeiQ's "HeiQ Viroblock NPJ03" (silver component: 0.3% by mass, quaternary ammonium salt component: 0.3% by mass) containing the following components A and B was prepared.
(A) Silver component: Same as Example 1 (B) Quaternary ammonium salt: Same as Example 1 (C) Polyurethane resin: Same as Example 1

(Test cloth)
As a test cloth, a white knitted fabric (cut to 40 cm long×30 cm wide) made of 100% by mass of cationic dyeable polyester fiber was prepared (CDP100).
Pickup rate 80%

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing A and B was weighed to 125 g/L and C to 10 g/L, added to water and stirred to prepare a processing agent.
The processing method was the same as in Example 1.

The obtained fiber structure had sufficient antiviral properties after about 10 washings, and the texture was almost unchanged compared with the unprocessed product.

<Example 3>
HeiQ's "HeiQ Viroblock NPJ03" (silver component: 0.3% by mass, quaternary ammonium salt component: 0.3% by mass) containing the following components A and B was prepared.
(A) Silver component: Same as in Example 1 (B) Quaternary ammonium salt: Same as in Example 1

(Test cloth)
As a test cloth, a white knitted fabric (cut into a length of 40 cm×width of 30 cm) containing 95% by mass of polyester fiber and 5% by mass of polyurethane fiber was prepared (T95/Pu5 in the table).
Pickup rate 80%

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing A and B was weighed to 125 g/L, added to water and stirred to prepare a processing agent.
The processing method was the same as in Example 1.

The obtained fiber structure had sufficient antiviral properties after about 10 washings, and the texture did not change as compared with the unprocessed product.

<Example 4>
HeiQ's "HeiQ Viroblock NPJ03" (silver component: 0.3% by mass, quaternary ammonium salt component: 0.3% by mass) containing the following components A and B was prepared.
(A) Silver component: Same as in Example 1 (B) Quaternary ammonium salt: Same as in Example 1

(Test cloth)
A white fabric (cut to 40 cm long×30 cm wide) of 90% by mass nylon fiber and 10% by mass polyurethane fiber was prepared (Ny90/Pu10 in the table).
Pickup rate 80%

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing A and B was weighed to 125 g/L, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The obtained fiber structure had sufficient antiviral properties after about 10 washings, and the texture did not change as compared with the unprocessed product.

<Example 5>
The following agents were prepared.
(A) Silver component: “HeiQ PureTAG” manufactured by HeiQ (containing 7.5% by mass of silver chloride supported on titanium oxide)
(B) Quaternary ammonium salt: hexadecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A, 0.38 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.
The processing method was the same as in Example 1.

As in Example 1, it was found that the obtained fiber structure had sufficient antiviral properties after about 10 washings, and the texture was almost unchanged compared to the unprocessed product.

<Example 6>
The following agents were prepared.
(A) Silver component: Same as in Example 5 (B) Quaternary ammonium salt: Tetrabutylammonium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A, 0.38 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

Although the obtained fiber structure was inferior to Examples 1 to 5, it was found to have sufficient antiviral properties after about 10 washings.

<Example 7>
The following agents were prepared.
(A) Silver component: Same as in Example 5 (B) Quaternary ammonium salt: Same as in Example 5
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
1.67 g/L of A, 0.38 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

Compared to Example 1, even if the amount of the silver component used was reduced, within the range defined by the present invention, although the performance was slightly inferior, it was found that high performance before and after washing could be obtained.

<Example 8>
The following agents were prepared.
(A) Silver component: Same as in Example 5 (B) Quaternary ammonium salt: Same as in Example 5
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
0.83 g/L of A, 0.38 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

It was found that even if the amount of the silver component used was further reduced from Example 7, high performance before and after washing could be obtained within the range defined by the present invention, although the performance was slightly inferior.

<Example 9>
The following agents were prepared.
(A) Silver component: Same as in Example 5 (B) Quaternary ammonium salt: Same as in Example 5
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A, 0.088 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

Compared to Example 1, even if the amount of the quaternary ammonium salt used was reduced, within the range specified in the present invention, although the performance was slightly inferior, it was found that high performance before and after washing was obtained.

<Example 10>
The following agents were prepared.
(A) Silver component: Same as in Example 5 (B) Quaternary ammonium salt: Same as in Example 5
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A, 0.038 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

From Example 7, it was found that even if the amount of the quaternary ammonium salt used was further reduced, high performance before and after washing could be obtained within the range defined by the present invention, although the performance was slightly inferior.

<Example 11>
"HeiQ Viroblock NPJ03" manufactured by HeiQ (silver chloride-supported titanium oxide: 0.3% by mass, quaternary ammonium salt component: 0.3% by mass) containing the following components A and B was prepared.
(A) Silver component: silver chloride-supported titanium oxide (B) Quaternary ammonium salt: cetrimonium chloride The following agents were prepared.
(C) Polyurethane resin: Polyether-based urethane resin (“Superflex” E-4800, solid content 40% by mass, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing A and B was weighed to 125 g/L and C to 10 g/L, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

<Example 12>
HeiQ's "HeiQ Viroblock NPJ03" (silver component: 0.3% by mass, quaternary ammonium salt component: 0.3% by mass) containing the following components A and B was prepared.
(A) Silver component: Same as in Example 1 (B) Quaternary ammonium salt: Same as in Example 1 (C) Polyurethane resin: Same as in Example 1 (D) Polyester resin: Polyester resin (Matsumoto Yushi Seiyaku Co., Ltd.) TM-SS21 solid content 10% by mass)

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing A and B is weighed to 125 g/L and C to 10 g/L, added to water and stirred to prepare working fluid A and D to 18.8 g/L. and added to water and stirred to prepare working fluid B.

After the test cloth was sufficiently immersed in the processing agent A, the test cloth was nipped (pickup rate: 80%) to remove excess processing agent. After that, the dried test cloth is sufficiently immersed in the processing liquid B, and then the test cloth is nipped (PickUp rate: 80%), excess processing liquid is removed, dried, and cured to obtain the polyester in the present invention. A system fiber structure was obtained.

The obtained fiber structure had sufficient antiviral properties after about 10 washings, and the texture was almost unchanged compared with the unprocessed product.

<Example 13>
HeiQ's "HeiQ Viroblock NPJ03" (silver component: 0.3% by mass, quaternary ammonium salt component: 0.3% by mass) containing the following components A and B was prepared.
(A) Silver component: Same as in Example 1 (B) Quaternary ammonium salt: Same as in Example 1 (C) Polyurethane resin: Same as in Example 1 (D) Compatibility improver: Anionic surfactant ( Labelin FC-45M manufactured by K&D Fine Chemicals)

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing A and B was weighed to 125 g/L and C and D to 10 g/L, added to water and stirred to prepare a processing agent.
The processing method was the same as in Example 1.

The obtained fiber structure had sufficient antiviral properties after about 10 washings, and the texture was almost unchanged compared with the unprocessed product.

(Confirmation of presence or absence of aggregates)
The working liquid prepared above was checked for the presence or absence of aggregates by the following method. As a result, no aggregates were confirmed.

[Presence or absence of aggregates]
300 ml of the working fluid prepared above was stirred at 3000 rpm for 5 minutes, and then left for 1 hour to check the state. If the working fluid separates into two layers or semi-solid aggregates are generated, there is an occurrence of aggregates, and there is no change in the state of the working fluid immediately after preparation. If no aggregates were found, it was determined that no aggregates were generated.

For comparison, the same working fluid as the working fluid used in Example 1 was prepared, and the occurrence of aggregates was confirmed by the above method. Agglomeration was observed which was not present immediately after preparation of the working fluid.

<Comparative Example 1>
The following agents were prepared.
(A) Silver component: Same as in Example 5 (B) Quaternary ammonium salt: No addition (C) Polyurethane resin: Same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The resulting fibrous structure had poor performance from unwashed. It can be seen that the combined use of the silver component and the quaternary ammonium salt is important.

<Comparative Example 2>
The following agents were prepared.
(A) Silver component: Silver chloride-supported aluminosilicate (B) Quaternary ammonium salt: Same as in Example 5 (C) Polyurethane resin: Same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
0.38 g/L of A, 0.38 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The resulting fibrous structure had poor performance from unwashed. It can be said that the silver component must be silver chloride-supported titanium oxide.

<Comparative Example 3>
The following agents were prepared.
(A) Silver component: Same as in Example 1 (B) Quaternary ammonium salt: Same as in Example 1 (C) Polyurethane resin: No addition

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing components A and B was weighed to 125 g/L, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The obtained fiber structure had high antiviral properties similar to those of Example 1 when it was not washed, but after 10 washings, the performance was greatly reduced. It was found that the combined use of a polyurethane component as a resin or fiber is necessary.

<Comparative Example 4>
The following agents were prepared.
(A) Silver component: Same as Example 5 (B) Quaternary ammonium salt: Same as Example 5 (C) Polyurethane resin: Same as Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
0.33 g/L of A, 0.38 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The resulting fibrous structure did not exhibit sufficient antiviral properties. It is thought that the amount of silver component used was small and insufficient for virus inactivation.

<Comparative Example 5>
The following agents were prepared.
(A) Silver component: Same as Example 5 (B) Quaternary ammonium salt: Same as Example 5 (C) Polyurethane resin: Same as Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A, 0.0050 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The resulting fibrous structure did not exhibit sufficient antiviral properties. It is thought that the amount of quaternary ammonium salt used was small and insufficient for virus inactivation.

<Comparative Example 6>
The following agents were prepared.
(A) Silver component: Same as Example 5 (B) Quaternary ammonium salt: Same as Example 5 (C) Polyurethane resin: Same as Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A, 0.38 g/L of B, and 0.13 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The obtained fiber structure had excellent antiviral properties as in Example 1 only when it was not washed, but the amount of polyurethane resin as a binder attached to the fiber was small, so after 10 washings resulted in a large decrease in performance.

<Comparative Example 7>
The following agents were prepared.
(A) Silver component: Same as Example 5 (B) Quaternary ammonium salt: Same as Example 5 (C) Polyurethane resin: Same as Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
150 g/L of A, 0.38 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The obtained fiber structure had high antiviral properties after being washed about 10 times, but the discoloration of the fabric was large because the ratio of the mass of silver chloride-supported titanium oxide to the amount of fiber structure material was large. It has a great effect on the color of things.

<Comparative Example 8>
The following agents were prepared.
(A) Silver component: Same as Example 5 (B) Quaternary ammonium salt: Same as Example 5 (C) Polyurethane resin: Same as Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
5.0 g/L of A, 13 g/L of B, and 10 g/L of C were weighed, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The resulting fiber structure had a large variation in antiviral properties and a large variation in the activity value. Since the amount of the quaternary ammonium salt used was excessive compared to other examples and comparative examples, the working fluid bubbled vigorously during processing, which is considered to be the cause of uneven processing.

<Comparative Example 9>
The following agents were prepared.
(A) Silver component: Same as Example 1 (B) Quaternary ammonium salt: Same as Example 1 (C) Polyurethane resin: Same as Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
"HeiQ Viroblock NPJ03" containing components A and B was weighed to 125 g/L and C to 50 g/L, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The obtained fiber structure was poor in performance since it had not been washed, and had a hard texture and was unsatisfactory. Since the amount of polyurethane resin used was excessive, it is thought that the silver component and the quaternary ammonium salt were coated, impairing the performance.

<Comparative Example 10>
The following agents were prepared.
(A) Silver component: Silver chloride (B) Quaternary ammonium salt: Hexadecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
They were weighed so that A was 0.38 g/L, B was 0.38 g/L, and C was 10 g/L, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The obtained fiber structure was excellent in antiviral properties as in Example 1 when it was not washed, but after 10 washings, the performance was greatly reduced. It is considered that the silver chloride was easily removed during washing and the performance after washing was degraded compared to the case where silver chloride was supported on titanium oxide.

<Comparative Example 11>
The following agents were prepared.
(A) Silver component: no addition (B) Quaternary ammonium salt: hexadecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)
(C) polyurethane resin: same as in Example 1

(Test cloth)
The test fabric was the same as in Example 1.

(Preparation of working fluid and method for working therewith)
They were weighed so that B was 0.38 g/L and C was 10 g/L, added to water and stirred to prepare a processing agent.

The processing method was the same as in Example 1.

The resulting fibrous structure did not exhibit sufficient antiviral properties. It was found necessary to use a combination of silver component and quaternary ammonium salt.

Claims (5)

A fibrous structure in which silver chloride-supported titanium oxide and a quaternary ammonium salt are attached to fibers, and a fibrous structure containing a polyurethane component, wherein the silver chloride-supported Titanium oxide is 0.003 to 0.6% by mass, the quaternary ammonium salt is 0.0005 to 0.5% by mass, satisfies the following (1) and / or (2), and JISL1922: 2016 plaque A fiber structure having an antiviral activity value of 2.0 or more after 10 washings at home by a measurement method.
(1) The polyurethane component is a polyurethane resin adhered as a binder to the fibers constituting the fiber structure, and the adhered amount thereof is 0.01 to 1.0% by mass with respect to the mass of the fiber structure. .
(2) Polyurethane fibers in which the polyurethane component is included as fibers constituting the fiber structure. 2. The fiber structure according to claim 1, wherein said polyurethane resin is a polycarbonate-based urethane resin. The fiber structure according to claim 1 or 2, further satisfying the following (3) or (4).
(3) The ionicity of the polyurethane resin is cationic or nonionic.
(4) The ionicity of the polyurethane resin is anionic, and the polyurethane resin is attached to the fibers together with the compatibility improver. 3. The fiber structure according to claim 1 or 2, which has an antiviral activity value of 3.0 or more after about 10 washings at home according to the JISL1922:2016 plaque assay method. Fibers are immersed in an aqueous solution of the titanium oxide supporting silver chloride and the quaternary ammonium salt, or an aqueous solution of the titanium oxide supporting silver chloride, the quaternary ammonium salt, and the polyurethane resin, and then at a temperature of 130° C. or higher. 3. The method for producing a fiber structure according to claim 1 or 2, wherein drying and curing are performed with.