JP7457672B2 - Antiviral processed textile products - Google Patents

Description

TECHNICAL FIELD The present invention relates to anti-virus treated textile products that have both antistatic properties and anti-viral properties and are excellent in washing durability.

It is expected that the use of antiviral processing on textile products will expand in the future, such as white coats in hospitals and nursing facilities, and work clothes in food factories. A method for evaluating the antiviral properties of textile products based on ISO 18184 has been established, and a mark certification system for antiviral processed textile products has been created by the Japan Textile Evaluation Technology Council, a general incorporated association.

However, for textile products, especially white coats and work clothes that require repeated washing, and linen products such as hospital sheets and curtains, improving their antiviral properties and their washing durability is an issue.

For example, Patent Documents 1 and 2 disclose resin molded articles and textile products in which an antiviral compound is fixed at least on the surface, in which the antiviral compound consists of a quaternary ammonium halogen compound. However, the quaternary ammonium salt disclosed herein contains only one chain of a straight-chain alkyl group having 10 or more carbon atoms, or contains two chains of straight-chain alkyl groups having at most 9 carbon atoms. The problem with these quaternary ammonium salts is that they have high water solubility and low washing durability. Furthermore, didecyldimethylammonium chloride, which is disclosed in Patent Documents 1 and 2, is designated as a deleterious substance, so its usage in textile products is limited, and even if safety is ensured, it cannot be washed properly. Currently, durability after washing only about 10 times has been achieved, and higher washing durability is required. In addition, white coats and work clothes are required to be free from static electricity, but because conventional quaternary ammonium salts are highly water-soluble, their antistatic properties currently have low washing durability. Ta.

WO2016-009928A1 Patent No. 5571577

The present invention was devised in consideration of the current state of the prior art described above, and its purpose is to provide a textile product that has excellent washing durability in both antiviral and antistatic properties while minimizing the amount of quaternary ammonium salt used. Furthermore, the present invention aims to provide an antiviral processed textile product suitable for use in clothing applications, etc., that has excellent durability against repeated washing and wearing in high-temperature industrial washing.

As a result of intensive studies to achieve the above object, the inventors of the present invention have combined a quaternary ammonium salt having one or more specific long-chain alkyl groups with a specific urethane polymer into a textile product made of synthetic fibers. It was discovered that a product with excellent antiviral and antistatic properties and excellent washing durability could be provided by containing the same, and the present invention was completed based on this finding.

上記式中、ｍ、ｎ、ｐ、ｑは０～２０の整数、Ｒ、Ｒ′は芳香族又は脂環族を含む環状アルキル基を示す。Ｒ及びＲ′は２、４、６位の炭素のいずれか１つ以上にメチレン基を有する芳香族環状アルキル基を含む。Ｘ^－はハロゲン化物イオンである。
（２）合成繊維がポリエチレンテレフタレート、ボリブチレンテレフタレート、及びポリトリメチレンテレフタレートからなる群の少なくとも一つの繊維からなり、式［Ｉ］～［ＩＩＩ］の群から選択される少なくとも一種の第四級アンモニウム塩が塩化ジデシルジメチルアンモニウムであることを特徴とする（１）に記載の抗ウイルス加工繊維製品。 That is, the present invention has been completed based on the above findings, and has the following configurations (1) to ( 2 ).
(1) An antiviral treated textile product comprising 60% by weight or more of synthetic fibers, characterized in that it contains 0.05 to 0.4% by weight of at least one quaternary ammonium salt selected from the group represented by the following formulas [I] to [III], and 0.5 to 20.0% by weight of a urethane polymer, and the urethane polymer is a cationic self-emulsifying polyester polyurethane and/or polycarbonate polyurethane .

In the above formula, m, n, p, and q are integers from 0 to 20, and R and R' are cyclic alkyl groups including aromatic and alicyclic groups. R and R' each include an aromatic cyclic alkyl group having a methylene group at any one or more of the carbons at the 2nd, 4th, and 6th positions. ^X- is a halide ion.
( 2 ) The antiviral processed textile product according to (1), characterized in that the synthetic fiber is at least one fiber selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, and the at least one quaternary ammonium salt selected from the group of formulas [ I ] to [III] is didecyldimethylammonium chloride.

According to the present invention, a textile product having antistatic and antiviral properties with excellent washing durability can be provided. In particular, the antiviral processed textile product of the present invention has the effect of reducing or inactivating viruses such as influenza virus and feline calicivirus, and also has antistatic properties with unprecedented washing durability. It is suitable for a wide range of applications that are frequently washed, including sports clothing, underwear, socks, bedding, clothing materials, and linen applications.

The antiviral processed fiber product of the present invention first contains synthetic fibers in an amount of 60% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more. If the content ratio is less than the above value, the initial antiviral performance is good, but the durability against repeated washing is insufficient, and it is not preferable for use in clothing that requires repeated washing. Examples of synthetic fibers include polyester fibers, polyamide fibers, acrylic fibers, polypropylene fibers, and polyurethane fibers, and it is preferable to use at least one of these synthetic fibers alone or in combination. As the synthetic fiber, polyester fiber is particularly preferred. As the polyester fiber, known ones such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, etc. can be used. Of course, in addition to fibers made of these homopolymers, it is also possible to use a combination of a plurality of such fibers, and it is also possible to use a composite spinning method to create a multilayer laminated structure or a core-sheath structure fiber. Furthermore, it may be a blended polymer in which copolymerized polyester or polyester is used as a matrix and other polymers are kneaded.

Examples of fibers that can be used in the textile products of the present invention in addition to the above-mentioned synthetic fibers include recycled fibers such as viscose rayon, copper ammonia rayon, and polynosic; semi-synthetic fibers such as cellulose acetate (triacetate, diacetate), and Promix. Known fibers can be used. In addition, known fibers such as cotton, hemp (flax, hemp, ramie, Manila hemp, sisal, etc.), wool, cashmere, mohair, alpaca, silk, kapok, kenaf, pineapple fiber, sugarcane fiber, hibiscus fiber, banana fiber, bamboo fiber, etc. Natural fibers can also be used. Further, the form of these fibers may be either short fibers or long fibers, and the cross-sectional shape may be a known cross-section such as a generally round cross-section, a rectangular cross-section, a multilobal cross-section, a hollow cross-section, etc. Furthermore, in addition to short fibers and long fibers, the yarn may be spun by a long/short composite spinning method.

In addition, the synthetic fibers mentioned above include textile products made of multifilament drawn yarn and/or false twisted yarn, nonwoven fabrics made of staple fibers, sheet-like materials such as spun yarn and paper, stuffed cotton, hard cotton, and spun yarn. It is preferable that the form is as follows. When the synthetic fiber is a multifilament drawn yarn and/or a false twisted yarn, the single yarn fineness is preferably 0.3 to 9.0 dtex. It is more preferably 0.5 to 8.0 dtex, and even more preferably 1.0 to 5.0 dtex. When the fiber is a staple fiber, the single yarn fineness is preferably 0.01 to 15.0 decitex. The above-mentioned single yarn fineness does not have to be a single fineness, and there is no restriction at all to use fibers of a plurality of finenesses in combination. Ultrafine fibers with a single filament fineness below the above range have a large fiber surface area and have good initial antiviral performance, but may tend to fall off due to repeated wearing or washing, resulting in decreased durability. In addition, with ultra-thick fibers whose single yarn fineness exceeds the above range, the fiber cross section is large, causing a strong prickly feeling at the sewing site, causing strong skin irritation, and making the textile product too hard. It becomes difficult to make it desirable for clothing or other uses.

上記式中、ｍ、ｎ、ｐ、ｑは０～２０の整数、Ｒ、Ｒ′は芳香族又は脂環族を含む環状アルキル基を示す。Ｒ及びＲ′は２、４、６位の炭素のいずれか１つ以上にメチレン基を有する芳香族環状アルキル基を含む。Ｘ^－はハロゲン化物イオンである。 The antiviral processed textile product of the present invention comprises at least one quaternary ammonium salt or a derivative thereof (hereinafter also simply referred to as a quaternary ammonium salt) selected from the group of formulas [I] to [III] below. 05 to 0.4% by weight, preferably 0.10 to 0.35% by weight, and 0.5 to 20.0% by weight, preferably 1.0 to 15.0% by weight of the urethane polymer. It is characterized by

In the above formula, m, n, p, and q are integers of 0 to 20, and R and R' are aromatic or alicyclic-containing cyclic alkyl groups. R and R' contain an aromatic cyclic alkyl group having a methylene group at one or more of the 2nd, 4th, and 6th carbon positions. X ⁻ is a halide ion.

The quaternary ammonium salts or derivatives thereof represented by the above formulas [I] to [III] preferably contain a long-chain alkyl group. For example, benzalkonium chloride, mono(trimethylammonium chloride methylene)alkyltoluene, didecyldimethylammonium chloride, didecyldimethylammonium bromide, normal hexadecyltrimethylammonium bromide, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, cetrine Examples include dophanium chloride, tetraethylammonium bromide, domiphene bromide, benzyldimethyltetradecylammonium chloride, and benzyldimethylhexadecylammonium chloride. Particularly preferred is didecyldimethylammonium chloride and its derivatives. Additionally, polymers such as poly-oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride, poly[oxyethylene (dimethyl iminio) trimethylene (dimethyl iminio) ethylene dichloride], and polydiallyl dimethyl ammonium chloride can also be used. . These may be used alone or in combination of two or more.

Quaternary ammonium salts or their derivatives are generally used widely in various industries as germicides, disinfectants, emulsifiers, rust inhibitors, antistatic agents, etc., but excessive use can cause mild skin irritation and irritation to mucous membranes, including the eyes. In particular, in the case of textile products, excessive use is likely to cause skin irritation through percutaneous absorption, so it is preferable to use them at the lowest possible concentration. According to the present invention, the durability to washing is very excellent, so that durability can be maintained with a minimum amount of attachment without using an excessive amount of quaternary ammonium salt or its derivative. That is, the amount of quaternary ammonium salt used in the present invention relative to the fiber weight is preferably about 0.05 to about 0.4% owf, more preferably about 0.1 to about 0.37% owf, and even more preferably about 0.14 to about 0.36% owf, so that the content of quaternary ammonium salt is as specified in the present invention. If the amount used is less than the above range, it becomes difficult to exhibit sufficient antiviral properties, and if the amount used exceeds the above range, there is a risk of increased irritation to the human body during wear.

The antiviral processed fiber product of the present invention is characterized by containing a urethane polymer in addition to the above-mentioned quaternary ammonium salt. This urethane-based polymer is preferably attached to textile products in the same manner as the quaternary ammonium salt, and preferably forms a film on at least the surface of the textile products. The urethane-based polymer can be either solvent-based or water-based, but it is convenient to use a water-based urethane polymer to adhere to the fibers at the same time as the quaternary ammonium salt and the like. By containing the urethane polymer, the durability of the various functionalities of the quaternary ammonium salt and the like against washing with anionic detergents can be increased. In the present invention, the amount of the urethane polymer to be used based on the fiber weight is preferably about 0.1 to about 10.0% owf, more preferably about 0.2 to about 6.0% owf, more preferably about 0.25 to about 4.0% owf. If the amount used is less than the above range, the antistatic property after washing will not be maintained sufficiently, and if it exceeds the above range, it may become difficult to use for various purposes.

Water-based urethane polymers include water dispersions in which self-emulsifying urethane polymers with water-soluble functional groups are dispersed in the molecule, or emulsification under strong mechanical shearing force in combination with surfactants. An aqueous dispersion of a forced emulsification type urethane polymer can be used. The urethane polymer in the aqueous dispersion is obtained by reacting a polyol with an organic polyisocyanate.

As the polyol used in the above reaction, any of polyester polyols, polyether polyols, polycarbonate polyols, and polyolefin polyols can be used, but polyester polyols, polycarbonate polyols, and polyether polyols are preferably used from the viewpoint of washing durability. . Particularly preferred are polyester polyols and polycarbonate polyols. That is, the urethane-based polymer is preferably made of polyester-based polyurethane and/or polycarbonate-based polyurethane.

Polycarbonate polyols can be obtained by reacting a carbonic acid derivative such as diphenyl carbonate, dimethyl carbonate, or phosgene with a diol. Examples of such diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propylene glycol, neopentyl glycol, 1,3- and 1,4-butanediol, 3-methylpentanediol, hexamethylene glycol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, and cyclohexanedimethanol. Among these, polycarbonate polyols using 1,6-hexanediol are preferred in terms of increasing the durability of the antiviral effect in high-temperature washing.

Examples of polyester polyols include condensation products of low molecular weight polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propylene glycol, neopentyl glycol, 1,3- and 1,4-butanediol, 3-methylpentanediol, hexamethylene glycol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, and cyclohexanedimethanol with polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuran acid, endomethinetetrahydrofuran acid, and hexahydrophthalic acid.

Examples of the polyether polyol include various polyether polyols such as polyethylene glycol, polypropylene glycol, polyethylene polytetramethylene glycol, polypropylene polytettremethylene glycol, and polytetramethylene glycol.

Further, examples of the organic polyisocyanate used in the above reaction include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. Examples of organic polyisocyanates are shown below, and aliphatic and alicyclic polyisocyanates are preferably selected from the viewpoint of weather resistance.

Examples of aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate, but hexamethylene diisocyanate (HDI) is preferred in terms of the washing durability of the antiviral effect.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, etc. Among them, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,3-bis(isocyanate methyl)cyclohexane are preferred from the viewpoint of antiviral effect and washing durability.

Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and 4,4'-diisocyanate. Examples include benzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

Examples of aromatic aliphatic polyisocyanates include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α,α-tetramethylxylylene diisocyanate, etc.

The molecular weight of the urethane-based polymer is preferably made as large as possible by introducing a branched structure or an internal crosslinked structure, and preferably has a number average molecular weight of 50,000 to 10,000,000. When this molecular weight is increased, it becomes easier to obtain a coating film with excellent weather resistance and water resistance.

For the purpose of imparting water dispersibility to the urethane polymer, it is preferable to add a water-soluble functional group material to introduce a cationic functional group or anionic functional group. Such water-soluble functional group materials include (a) mono- or dialkanol carboxylic acids or mono- or disulfonic acids neutralized with tertiary amines or alkali metals, (b) polyethylene oxide or methoxypolyethylene oxide, (c) Examples include organic or inorganic acid neutralized products of mono- or dialkanolamines, or quaternary ammonium salts thereof obtained by reaction with alkyl halides, dialkyl sulfates, and the like. Among these, from the viewpoint of ease of emulsification, (a) neutralized products of mono- or dialkanol carboxylic acids or sulfonic acids, and (c) neutralized products of organic or inorganic acids or quaternary mono- or dialkanolamines. Ammonium salts are preferred. In the present invention, (c) an organic or inorganic acid neutralized product or a quaternary ammonium salt of a mono- or dialkanolamine is used because making the urethane polymer cationic leads to further improvement in washing durability. Particularly preferred.

In order to introduce a cationic functional group, an alkanolamine such as dimethylaminoethanol or methyldiethanolamine is first introduced. Next, when introducing a neutralizing base, an organic carboxylic acid such as formic acid or acetic acid, or an inorganic acid such as hydrochloric acid or sulfuric acid is added, and when introducing a quaternary ammonium salt, methyl chloride is added as a quaternizing reagent. , alkyl halides such as methyl bromide, and dialkyl sulfates such as dimethyl sulfate. Among the above, from the viewpoint of ease of emulsification, a combination of methyldiethanolamine and an organic carboxylic acid or a combination of methyldiethanolamine and dimethyl sulfuric acid is preferred.

In addition, although a quaternary ammonium salt, which is an antiviral agent, is used in the present invention, when this quaternary ammonium salt is washed with a detergent containing an anionic surfactant, even if sufficient rinsing is performed, the quaternary ammonium salt It was found that the antiviral and antistatic properties of ammonium salts deteriorate more quickly. In the present invention, especially when a cationic urethane polymer is used, it is possible to suppress the deterioration of the performance of the quaternary ammonium salt of the antiviral agent, and it is possible to further extend the washing durability of the antiviral agent. Ta. The reason for this is thought to be that the presence of a cationic functional group around the antiviral agent prevents the anionic surfactant from masking the quaternary ammonium salt of the antiviral agent.

When preparing an aqueous dispersion of a urethane-based polymer, a single-chain low-molecular-weight diol such as ethylene glycol or 1,4-butanediol may be added to localize the urethane bond within the molecule. Also, a single-chain polyol such as trimethylolpropane or glycerin may be added to introduce a branched structure into the molecule. The addition of these single-chain polyols localizes the urethane bond or introduces a branched structure, which has the effect of improving the water resistance of the resulting aqueous dispersion of the urethane-based polymer.

When preparing an aqueous dispersion of a urethane polymer, a chain extender may be added in order to increase the molecular weight of the urethane polymer and improve water resistance and weather resistance. As the chain extender, diamines and polyamines which also serve the function of introducing internal crosslinking structures are used. Examples of diamines include ethylenediamine, trimethylenediamine, piperazine, and isophoronediamine, and examples of polyamines include diethylenetriamine, dipropylenetriamine, and triethylenetetramine.

When preparing an aqueous dispersion of a urethane polymer, a surfactant may be used to more stably disperse the urethane polymer. As the surfactant, cationic surfactants and nonionic surfactants are preferably used.

The method for preparing the aqueous dispersion of the urethane polymer is not particularly limited, but generally, a stoichiometric excess of polyisocyanate is reacted with the total of the functional groups reactive with the isocyanate groups contained in the polyol, the water-soluble functional group introduction material, the single-chain polyol, and the chain extender to synthesize an isocyanate-terminated urethane prepolymer, and then the water-soluble functional groups are neutralized and dispersed and emulsified in water. Then, an equivalent amount of chain extender less than the remaining isocyanate groups is added to cause an interfacial polymerization reaction between the isocyanate groups in the emulsion micelles and the polyamine of the chain extender to generate urea bonds. This improves the crosslink density in the emulsion micelles, and a three-dimensional crosslinked structure is formed. In this way, the formation of a three-dimensional crosslinked structure results in a coating film that exhibits excellent water resistance and weather resistance. Then, the solvent used is removed as necessary to obtain an aqueous dispersion of the urethane polymer.

Commercial products of the urethane polymer used in the present invention include, for example, cationic self-emulsifying polyurethane such as HDI polyurethane "Superflex 620" (ester type) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and "Super "Flex 650" (carbonate type), "Permarin UC-20" (ether type) manufactured by Sanyo Chemical Industries, Ltd., "Parasurf UP-22" (ether type) manufactured by Ohara Palladium Chemical Co., Ltd., etc. Examples of the nonionic polyurethane resin include Superflex 500M (ester type) and Superflex E2000 (ester type), but as mentioned above, it is more preferable to use a cationic self-emulsifying polyurethane.

The antiviral processed textile product of the present invention can be easily obtained by post-processing a primary textile product such as a woven fabric, knitted fabric, or nonwoven fabric with an antiviral processing agent consisting of at least one quaternary ammonium salt and/or its derivative selected from the group of formulas [I] to [III] and a urethane polymer. As a post-processing method, known methods such as exhaustion method, padding method, spray method, coating method, and printing method can be adopted. For example, in the case of exhaustion method, it is possible to perform a dyeing in the same bath treatment, or a separate bath treatment at any step after dyeing. In the case of padding method, after dyeing, a predetermined amount of chemical solution is picked up by a mangle padder or the like and then heat treated. Heat treatment method can be performed by known methods such as pad dry method, pad dry cure method, pad steam cure method, and pad dry bake method. In addition, the above methods can be used in combination as necessary.

The temperature conditions for the post-processing treatment vary depending on the type of fiber used, but for example in the case of an exhaustion method, they can be appropriately set in the range of 70 to 135°C, more preferably 90 to 130°C. Further, in the case of the padding method, the dry temperature range of 100 to 130°C and the curing temperature range of 140 to 190°C can be exemplified in the pad (dry) curing method. A more preferable curing temperature is 160° C. to 180° C. for 30 seconds to 2 minutes. The higher the curing temperature, the higher the residual rate of quaternary ammonium salts after washing. However, quaternary ammonium salts are easily decomposed at high temperatures, and cannot be cured at temperatures above 200°C or for long periods of 5 minutes or more. They tend to gradually decompose on the fibers, reducing the amount of active ingredients. In addition, excessive heat treatment causes adverse effects on the physical properties of the fabric such as various fastnesses, and is also a cause of yellowing, so it is desirable to avoid it.

Quaternary ammonium salts tend to cause yellowing, especially phenol yellowing, and if necessary, it is preferable to keep the pH of the fabric after processing in the acidic range of 3 to 6 to suppress yellowing. For the dough pH, a nonvolatile organic acid such as malic acid or oxalic acid can be appropriately used.

Among the quaternary ammonium salts used in the present invention, those with relatively large molecular weights have reduced water solubility, but in order to process such quaternary ammonium salts uniformly and stably into fibers, they can be used in combination with nonionic surfactants. Nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene (hydrogenated) castor oils, polyoxyalkylene alkylphenols, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan alkyl esters, polyoxyalkylene sorbitan fatty acid ... Examples include fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides, polyoxyalkylene fatty acid bisphenyl ethers, polypropylene glycol, polyether-modified silicones, i.e., polyoxyalkylene-modified diorganopolysiloxanes, polyglyceryl-modified silicones, glyceryl-modified silicones, sugar-modified silicones, perfluoropolyether surfactants, polyoxyethylene-polyoxypropylene block copolymers, and alkyl polyoxyethylene-polyoxypropylene block copolymer ethers. Among these, polyoxyethylene-added nonionic surfactants such as polyoxyalkylene alkyl ethers and polyoxyalkylene fatty acid esters are preferably used.

The nonionic surfactant preferably has an HLB of 7 to 18. More preferably HLB 8-16, still more preferably HLB 10-14. Specifically, polyoxyethylene sorbitan fatty acid ester (HLB12.5), polyoxyethylene sorbitan fatty acid ester (HLB11), polyoxyethylene glycerin fatty acid ester, etc. are preferably used.

There are no particular restrictions on the organic solvent as long as it is miscible with water, but examples include alcohols such as methanol, ethanol, and isopropyl alcohol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, and diethyl ether. Examples include ethers and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. Note that the ratio of water and organic solvent is not particularly limited.

The antiviral processed textile product of the present invention can have an antiviral activity value Mv against influenza viruses of 3.0 or more after 20 washes, and an antiviral activity value Mv of 3.0 or more even after 30 washes. The quaternary ammonium salt used in the present invention has a high affinity for hydrophobic fibers, particularly polyester fibers and polyurethane fibers, and therefore can improve washing durability.

Viruses are broadly classified into enveloped viruses and non-enveloped viruses. The envelope is a membrane-like structure found in some virus particles (virions) such as herpes simplex virus and influenza virus. It constitutes the outermost shell. The envelope is mostly composed of lipids and can be easily destroyed by treatment with alcohol or organic solvents, so viruses without envelopes are generally more difficult to inactivate than viruses with envelopes. .

Examples of enveloped viruses include influenza virus, measles virus, rubella virus, AIDS virus, and herpes virus. Further, typical examples of viruses without an envelope include norovirus, rotavirus, poliovirus, adenovirus, and enterovirus. The quaternary ammonium salt used in the present invention tends to be less effective against non-enveloped viruses, but the quaternary ammonium salt of the present invention has two identical linear alkyl groups having 18 or more carbon atoms. has excellent antiviral effects against non-enveloped viruses.

The virus-processed textile product of the present invention can maintain a frictional charging voltage of 1500 V or less after 5 washes, and a frictional charging voltage of 2000 V or less after 10 washings. If it is desired to further enhance the antistatic property, steartrimonium chloride or behentrimonium chloride may be used in combination with the quaternary ammonium salt.

The virus-treated textile product of the present invention exhibits antistatic and antiviral properties with excellent washing durability, and furthermore, there is little change in texture, discoloration, or fabric properties, making it suitable for use in hospital gowns and other items. It can also be used in a wide range of fields, including rental uniforms such as food gowns, sheets, curtains, innerwear, shirts, school uniforms, and gym clothes.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In addition, the physical property measurement method in Examples is based on the following.

(Washing method)
The washing process was carried out under the following conditions in accordance with the "Washing method for SEK mark textile products" (revised October 30, 2020, document number JEC326) published by the Product Certification Department of the Textile Evaluation Technology Council.
- Washing was carried out using a standard washing method (method described in 1995 edition JIS L0217:1995 103 method), drying was performed by hanging, and evaluation samples were prepared after washing 10 and 20 times. Further, in accordance with the high temperature accelerated washing method of JEC326, the product was washed at 80°C in a washer washing machine, rinsed in a home washing machine, and the washing method specified for 10 washings was repeated 3 times to obtain 30 high temperature washings.

(Antiviral test)
Evaluation was performed according to the method described in the 2014 edition of ISO18184. The following two types of viruses were tested.
・Influenza A virus (H3N2) (ATCC VR-1679)
・Feline calicivirus (F-9) (ATCC VR-782)

(Antistatic property)
Measured using JIS-L1094:2004 7.2 B method (frictional charging voltage measurement method).

(Example 1)
(100% polyester fabric)
Full dull false twisted polyethylene terephthalate yarn 167 dtex 48 filament (trade name: Toyobo Ester) was used for the warp and weft, and was woven with a plain weave structure at a warp density of 90 threads/inch and a weft density of 70 threads/inch (polyester blend ratio 100%).

The grey fabric was subjected to continuous scouring, liquid flow relaxation, and dry heat presetting in the usual manner, and then dyed with disperse dyes using a Hisaka Seisakusho high-pressure liquid flow dyeing machine in the presence of 2% owf of a polyester-based water-absorbing SR agent (trade name: SR-1000,) manufactured by Takamatsu Oil & Fat Co., Ltd., under moist heat conditions of 130°C. After dyeing, the fabric was subjected to the usual reduction washing process using sodium hydrosulfite and soda ash, followed by washing in hot water and water, and after dehydration, dried in an open-weave state using a short loop dryer.

Next, the fabric obtained by the above method was treated by a pad dry cure method using a solution of Formulation 1 below. Incidentally, the resin padding of the fabric was carried out using a dry-on-wet method (a method in which dried fabric is dipped in a chemical solution and then squeezed to apply a predetermined amount of the chemical to the fabric).

The mangle pressure was applied to the W. of the 100% polyester fabric. P. The U% (wet pickup rate, liquid adhesion rate per fiber weight) was adjusted to 50%. An aqueous solution of Formulation 1 was applied with a padder and squeezed with a mangle. Heat treatment was performed at a drying temperature of 120°C and a curing temperature of 170°C for 1 minute, also serving as a final setting. The fabric weight of the obtained fabric was 130 g/m ² .

Formulation 1:
Didecyldimethylammonium chloride 0.7% solution
Superflex 650 (solid content 26% by weight) 10.0% solution
(Cationic polycarbonate polyurethane)
Malic acid 1.0% solution

The amount of didecyldimethylammonium chloride deposited on the fabric was 0.35% owf, the amount of Superflex 650 deposited was 5.0% owf (on the weight of fiber: fiber weight ratio), and the active ingredient was 1.3% owf. %owf. Table 1 shows the evaluation results of the obtained processed cloth.

(Example 2)
Except that Superflex 650 in Example 1 was changed to Superflex 620 (cationic polyester polyurethane) (solid content 30% by weight) 10% solution (adhesion amount 5% OWF, active ingredient 1.5% OWF) , the same processing as in Example 1 was performed. Table 1 shows the evaluation results of the obtained processed cloth.

Example 3
The same processing as in Example 1 was carried out, except that the concentration of Superflex 650 in Example 1 was changed from 10.0% solution to 2.0% solution (adhesion amount 1.0% owf, 0.26% owf as active ingredient). The evaluation results of the obtained processed fabric are shown in Table 1.

(Example 4)
The same processing as in Example 1 was performed except that the concentration of didecyldimethylammonium chloride in Example 1 was changed from 0.7% solution to 0.3% solution (adhesion amount was 0.15% owf). Table 1 shows the evaluation results of the obtained processed cloth.

(Example 5)
Except that Superflex 650 in Example 1 was changed to Superflex 500M (nonionic polyester polyurethane) (solid content 45% by weight) 6% solution (adhesion amount 3% OWF, active ingredient 1.35% OWF). The same processing as in Example 1 was performed. Table 1 shows the evaluation results of the obtained processed cloth.

(Comparative example 1)
Superflex 650 in Example 1 was changed to acrylic binder NK Binder A-12HN (solid content 45% by weight) 6% solution (adhesion amount 3% OWF, active ingredient 1.35% OWF) manufactured by Shin Nakamura Chemical Co., Ltd. Except for this, the same processing as in Example 1 was performed. Table 1 shows the evaluation results of the obtained processed cloth.

(Comparative Example 2)
Processing was carried out in the same manner as in Example 1, except that Superflex 650 was omitted from Formulation 1 of Example 1. The evaluation results of the obtained processed fabric are shown in Table 1.

As is clear from Table 1, all of Examples 1 to 5, which satisfy the requirements of the present invention, were excellent in antiviral and antistatic properties before and after repeated washing, whereas Comparative Example 1, which was a formulation that did not use a urethane polymer, was inferior in antiviral and antistatic properties after repeated washing, and Comparative Example 2, which was a formulation that did not use either a urethane polymer or a quaternary ammonium salt, was inferior in antiviral properties before and after repeated washing, and in antistatic properties after repeated washing.

The antiviral processed fiber product of the present invention has excellent washing durability in both antistatic and antiviral properties, and can be widely used for various clothing, bedding, household materials, etc. Especially for white coats, preventive clothing, curtains, and various work clothes worn in various medical institutions such as hospitals and nursing care/nursing facilities, as well as workplaces where food is handled such as food factories and kitchens, pharmaceutical factories, and beverage factories, which place particular emphasis on hygiene. It can be applied to work clothes, work clothes, etc. worn at work sites.

Claims (2)

A textile product containing 60% by weight or more of synthetic fibers, and at least one quaternary ammonium salt selected from the group of formulas [I] to [III] below. 05 to 0.4% by weight, and 0.5 to 20.0% by weight of a urethane polymer, and the urethane polymer consists of a cationic self-emulsifying polyester polyurethane and/or a polycarbonate polyurethane. An antiviral processed textile product characterized by :

In the above formula, m, n, p, and q are integers of 0 to 20, and R and R' are aromatic or alicyclic-containing cyclic alkyl groups. R and R' contain an aromatic cyclic alkyl group having a methylene group at one or more of the 2nd, 4th, and 6th carbon positions. X ⁻ is a halide ion. The synthetic fiber is made of at least one fiber from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, and at least one quaternary ammonium salt selected from the group of formulas [I] to [III] is chlorinated. The antiviral processed textile product according to claim 1, characterized in that it is didecyldimethylammonium.