JP7115521B2 - Fiber treatment agent - Google Patents

Description

The present invention relates to an antiviral agent composition containing an organosilicon compound and the organosilicon compound.

In recent years, there has been a growing interest in antiviral agents, and there is a demand for long-lasting antiviral agents. For example, a composition based on octadecyldimethyl(3-trialkoxysilylpropyl)ammonium chloride is known as an immobilizable antiviral agent (Patent Documents 1 and 2).

However, octadecyldimethyl(3-trialkoxysilylpropyl)ammonium chloride does not have sufficient durability, and in some cases the durability of its antiviral performance is reduced, so further improvements have been desired.

JP 2011-98976 A WO2015/141516

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an antiviral agent composition having excellent durability of antiviral performance.

As a result of intensive studies to achieve the above object, the present inventors have found that an antiviral agent composition containing a specific organosilicon compound has excellent durability and imparts long-lasting antiviral properties to articles such as fibers. The inventors have found that it is possible to achieve the present invention.

（式中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１～１０のアルキル基または炭素数６～１０のアリール基であり、Ｒ³は、炭素数１２～２４のアルキル基であり、Ｒ⁴およびＲ⁵は、それぞれ独立に、炭素数１～６のアルキル基であり、Ｘは、ハロゲン原子であり、ｍは、４～２０の整数であり、ｎは、１～３の整数である。）
２． ｍが８である１記載の抗ウイルス剤組成物、
３． １または２記載の抗ウイルス剤組成物で処理された物品、
４． 下記式（２）で表される有機ケイ素化合物

（式中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１～１０のアルキル基または炭素数６～１０のアリール基であり、Ｒ³は、炭素数１２～２４のアルキル基であり、Ｒ⁴およびＲ⁵は、それぞれ独立に、炭素数１～６のアルキル基であり、Ｘは、ハロゲン原子であり、ｎは、１～３の整数である。）
を提供する。 That is, the present invention
1. An antiviral agent composition containing an organosilicon compound represented by the following formula (1),

(wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ³ is an alkyl group having 12 to 24 carbon atoms, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, X is a halogen atom, m is an integer of 4 to 20, and n is an integer of 1 to 3. be.)
2. 1. The antiviral agent composition according to 1, wherein m is 8;
3. An article treated with the antiviral agent composition according to 1 or 2,
4. Organosilicon compound represented by the following formula (2)

(wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ³ is an alkyl group having 12 to 24 carbon atoms, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, X is a halogen atom, and n is an integer of 1 to 3.)
I will provide a.

The antiviral agent composition of the present invention is excellent in durability and can impart long-lasting antiviral properties to articles such as fibers.

The present invention will be specifically described below.
The antiviral agent composition of the present invention contains an organosilicon compound represented by the following formula (1).

The alkyl group of R ¹ having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, may be linear or branched, and specific examples thereof include methyl, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n- hexyl groups and the like.
Specific examples of the aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms include phenyl group and tolyl group.
Among these, R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

Examples of the alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms for R ² are the same as those for R ¹ , and among them, the methyl group is more preferable.

The alkyl group of R ³ having 12 to 24 carbon atoms, preferably 12 to 20 carbon atoms, more preferably 12 to 18 carbon atoms, may be linear or branched. dodecyl, 2-methylundecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n- Examples include tricosyl and n- tetracosyl groups . Among these, R ³ preferably has 14 to 18 carbon atoms, and more preferably an n-octadecyl group from the viewpoint of availability of raw materials and environmental load during use.

The alkyl group having 1 to 6 carbon atoms for R ⁴ and R ⁵ may be linear or branched, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Examples include s-butyl, t-butyl, n-pentyl and n- hexyl groups . Among these, both R ⁴ and R ⁵ are preferably alkyl groups having 1 to 3 carbon atoms, and more preferably methyl groups from the viewpoint of the availability of raw materials and environmental load during use.

m represents an integer of 4 to 20, preferably an integer of 6 to 12, particularly preferably 8. If it is less than 4, the durability is not sufficient, and if it exceeds 20, the content of the quaternary ammonium salt per unit mass decreases, resulting in decreased antiviral properties.
A chlorine atom, a bromine atom, etc. are mentioned as a halogen atom of X.

Organosilicon compounds suitable for the antiviral agent composition of the present invention include, in particular, those represented by the following formula (2).

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｘおよびｎは上記と同じである。）

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X and n are the same as above.)

Specific examples of organosilicon compounds that can be used in the antiviral agent composition of the present invention include octadecyldimethyl(4-trimethoxysilylbutyl)ammonium chloride, octadecyldimethyl(4-triethoxysilylbutyl)ammonium chloride, octadecyldimethyl ( 6-trimethoxysilylhexyl)ammonium chloride, octadecyldimethyl(6-triethoxysilylhexyl)ammonium chloride, octadecyldimethyl(8-trimethoxysilyloctyl)ammonium chloride, octadecyldimethyl(8-triethoxysilyloctyl)ammonium chloride, octadecyl Dimethyl(8-dimethoxymethylsilyloctyl)ammonium chloride, Octadecyldimethyl(8-diethoxymethylsilyloctyl)ammonium chloride, Octadecyldimethyl(10-trimethoxysilyldecyl)ammonium chloride, Octadecyldimethyl(10-triethoxysilyldecyl)ammonium chloride chloride, octadecyldimethyl(11-trimethoxysilylundecyl)ammonium chloride, octadecyldimethyl(11-triethoxysilylundecyl)ammonium chloride, octadecyldimethyl(12-trimethoxysilyldodecyl)ammonium chloride, octadecyldimethyl(12-triethoxy silyldodecyl)ammonium chloride, dodecyldimethyl(8-triethoxysilyloctyl)ammonium chloride, dodecyldimethyl(8-dimethoxymethylsilyloctyl)ammonium chloride, tetradecyldimethyl(8-triethoxysilyloctyl)ammonium chloride, tetradecyldimethyl( 8-dimethoxymethylsilyloctyl)ammonium chloride, octadecyldiethyl(8-triethoxysilyloctyl)ammonium chloride, octadecyldiethyl(8-dimethoxymethylsilyloctyl)ammonium chloride and the like.
Among these, octadecyldimethyl(4-trimethoxysilylbutyl)ammonium chloride, octadecyldimethyl(6-triethoxysilylhexyl)ammonium chloride, octadecyldimethyl(8-trimethoxysilyloctyl)ammonium chloride, octadecyldimethyl(8-triethoxysilyl) Octyl)ammonium chloride, octadecyldimethyl(8-dimethoxymethylsilyloctyl)ammonium chloride, octadecyldimethyl(8-diethoxymethylsilyloctyl)ammonium chloride, octadecyldimethyl(11-trimethoxysilylundecyl)ammonium chloride are preferred, and octadecyldimethyl (8-trimethoxysilyloctyl)ammonium chloride, octadecyldimethyl(8-triethoxysilyloctyl)ammonium chloride, octadecyldimethyl(8-dimethoxymethylsilyloctyl)ammonium chloride, octadecyldimethyl(8-diethoxymethylsilyloctyl)ammonium chloride is more preferred.

The organosilicon compound represented by the above formula (1) is obtained by combining an organosilicon compound represented by the following formula (A) and a tertiary amine represented by the following formula (B) in an air atmosphere or in a nitrogen atmosphere. It is obtained by reacting in an inert gas atmosphere.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｘ、ｍおよびｎは上記と同じである。）

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, m and n are the same as above.)

Examples of the organosilicon compound represented by the above formula (A) include 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 4-bromobutyltrimethoxysilane, 4-bromobutyltriethoxysilane, 6 -chlorohexyltrimethoxysilane, 6-chlorohexyltriethoxysilane, 6-bromohexyltrimethoxysilane, 6-bromohexyltriethoxysilane, 8-chlorooctyltrimethoxysilane, 8-chlorooctyltriethoxysilane, 8-chloro Octyldimethoxymethylsilane, 8-chlorooctyldiethoxymethylsilane, 8-bromooctyltrimethoxysilane, 8-bromooctyltriethoxysilane, 8-bromooctyldimethoxymethylsilane, 8-bromooctyldiethoxymethylsilane, 10-chloro Decyltrimethoxysilane, 10-chlorodecyltriethoxysilane, 10-bromodecyltrimethoxysilane, 10-bromodecyltriethoxysilane, 11-chloroundecyltrimethoxysilane, 11-chloroundecyltriethoxysilane, 11-bromo undecyltrimethoxysilane, 11-bromoundecyltriethoxysilane, 12-chlorododecyltrimethoxysilane, 12-chlorododecyltriethoxysilane, 12-bromododecyltrimethoxysilane, 12-bromododecyltriethoxysilane and the like. . These can be used individually by 1 type or in combination of 2 or more types.
Among these, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 6-chlorohexyltrimethoxysilane, 6-chlorohexyltriethoxysilane, 8-chlorooctyltrimethoxysilane, 8-chlorooctyltriethoxysilane Silane, 8-chlorooctyldimethoxymethylsilane, 8-chlorooctyldiethoxymethylsilane, 11-chloroundecyltrimethoxysilane, 11-chloroundecyltriethoxysilane are preferred, and 8-chlorooctyltrimethoxysilane, 8-chloro Octyltriethoxysilane, 8-chlorooctyldimethoxymethylsilane, and 8-chlorooctyldiethoxymethylsilane are more preferred.

Examples of the tertiary amine represented by the above formula (B) include dodecyldimethylamine, dodecyldiethylamine, tridecyldimethylamine, tridecyldiethylamine, tetradecyldimethylamine, tetradecyldiethylamine, pentadecyldimethylamine, pentadecyldiethylamine, hexa Decyldimethylamine, hexadecyldiethylamine, heptadecyldimethylamine, heptadecyldiethylamine, octadecyldimethylamine, octadecyldiethylamine, nonadecyldimethylamine, nonadecyldiethylamine, eicosyldimethylamine, eicosyldiethylamine, heneicosyldimethylamine, heneico sildiethylamine, docosyldimethylamine, docosyldiethylamine, tricosyldimethylamine, tricosyldiethylamine, tetracosyldimethylamine, tetracosyldiethylamine and the like. These can be used individually by 1 type or in combination of 2 or more types.
Among these, octadecyldimethylamine and octadecyldiethylamine are preferred, and octadecyldimethylamine is more preferred.

Although the above reaction can be carried out without a solvent, it can be carried out in an alcoholic solvent such as methanol or ethanol, if necessary, as long as the reaction is not inhibited.
The reaction temperature is preferably 80 to 150°C, more preferably 100 to 130°C. The reaction time is preferably 1 to 30 hours, more preferably 5 to 25 hours.
The use ratio of the organosilicon compound represented by the above formula (A) and the tertiary amine represented by the above formula (B) during the reaction is 1 mol of the tertiary amine (B) to the organosilicon compound. (A) is preferably 0.7 to 1.3 mol.

The content of the organosilicon compound represented by the above formula (1) contained in the antiviral agent composition of the present invention is not particularly limited, but from the viewpoint of antiviral properties, it is 0.0001 relative to the entire composition. ~40% by mass is preferable, and 0.001 to 10% by mass is more preferable.

The antiviral agent composition of the present invention may further contain water, alcohols such as methanol and ethanol, other additives, and the like, as long as the objects of the present invention are not impaired. Other additives include organic acids such as citric acid, surfactants, and the like, and by adding these, a highly stable composition can be obtained.

By applying the antiviral agent composition of the present invention to various materials, articles, etc., it is possible to impart antiviral properties to these materials. Specific examples of the above materials and articles include natural fibers such as cotton, silk and wool, regenerated fibers such as rayon, semi-synthetic fibers such as acetate, vinylon, polyester, nylon, polyethylene, polypropylene, polyurethane, and polyaramid fibers. synthetic fibers, composite fibers of these fibers (polyester/cotton, etc.); various metals such as iron, stainless steel, aluminum, nickel, zinc, and copper; acrylic resins, phenolic resins, epoxy resins, polycarbonate resins, polybutylene terephthalate resins and inorganic materials such as glass, titanium, ceramics, cement, and mortar.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Comparative Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Synthesis of Organosilicon Compound>
[Synthesis Example 1-1]
42.4 g of 4-chlorobutyltrimethoxysilane, 59.6 g of octadecyldimethylamine (Lipomin DM18D, manufactured by Lion Corporation, hereinafter the same), and 102 g of methanol were placed in a 300 mL pressurized reaction vessel purged with nitrogen, and the mixture was heated at 120°C. The reaction was allowed to proceed for 20 hours. After the reaction, filtration was performed to obtain 200 g of a methanol solution of octadecyldimethyl(4-trimethoxysilylbutyl)ammonium chloride (solid concentration: 50% by mass).

[Synthesis Example 1-2]
48.0 g of 6-chlorohexyltrimethoxysilane, 59.6 g of octadecyldimethylamine, and 108 g of methanol were placed in a 300 mL pressurized reaction vessel purged with nitrogen, and reacted at 120° C. for 20 hours. After the reaction, filtration was performed to obtain 206 g of a methanol solution of octadecyldimethyl(6-trimethoxysilylhexyl)ammonium chloride (solid concentration: 50% by mass).

[Example 1-1]
53.8 g of 8-chlorooctyltrimethoxysilane, 59.6 g of octadecyldimethylamine, and 113 g of methanol were placed in a 300 mL pressurized reaction vessel purged with nitrogen, and reacted at 120° C. for 20 hours. After the reaction, filtration was performed to obtain 220 g of a methanol solution of octadecyldimethyl(8-trimethoxysilyloctyl)ammonium chloride (solid concentration: 50% by mass).

[Synthesis Example 1-3]
62.2 g of 11-chloroundecyltrimethoxysilane, 59.6 g of octadecyldimethylamine, and 122 g of methanol were placed in a 300 mL pressurized reaction vessel purged with nitrogen, and reacted at 120° C. for 20 hours. After the reaction, filtration was performed to obtain 235 g of a methanol solution of octadecyldimethyl(11-trimethoxysilylundecyl)ammonium chloride (solid concentration: 50% by mass).

[Example 1-2]
62.2 g of 8-chlorooctyltriethoxysilane, 59.6 g of octadecyldimethylamine, and 122 g of ethanol were placed in a 300 mL pressurized reaction vessel purged with nitrogen, and reacted at 120° C. for 20 hours. After the reaction, filtration was performed to obtain 235 g of an ethanol solution of octadecyldimethyl(8-triethoxysilyloctyl)ammonium chloride (solid concentration: 50% by mass).

[Comparative Synthesis Example 1-1]
39.7 g of 3-chloropropyltrimethoxysilane, 59.6 g of octadecyldimethylamine, and 99.3 g of methanol were placed in a 300 mL pressurized reaction vessel purged with nitrogen, and reacted at 120° C. for 20 hours. After the reaction, filtration was performed to obtain 190 g of a methanol solution of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (solid concentration: 50% by mass).

[Comparative Synthesis Example 1-2]
48.2 g of 3-chloropropyltriethoxysilane, 59.6 g of octadecyldimethylamine, and 107.8 g of ethanol were placed in a 300 mL pressurized reaction vessel purged with nitrogen, and reacted at 120° C. for 20 hours. After the reaction, filtration was performed to obtain 210 g of an ethanol solution of octadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride (solid concentration: 50% by mass).

<Production of antiviral agent composition>
[Example 2-1]
1 g of the methanol solution of octadecyldimethyl(4-trimethoxysilylbutyl)ammonium chloride obtained in Synthesis Example 1-1, 99 g of ion-exchanged water, and 0.1 g of citric acid were placed in a 200 mL mixing vessel purged with nitrogen and stirred at 25°C for 1 hour. After stirring for hours, a colorless and transparent liquid was obtained.

[Example 2-2]
1 g of the methanol solution of octadecyldimethyl(6-trimethoxysilylhexyl)ammonium chloride obtained in Synthesis Example 1-2, 99 g of ion-exchanged water, and 0.1 g of citric acid were placed in a 200 mL mixing vessel purged with nitrogen, and stirred at 25°C for 1 hour. After stirring for hours, a colorless and transparent liquid was obtained.

[Example 2-3]
1 g of the methanol solution of octadecyldimethyl(8-trimethoxysilyloctyl)ammonium chloride obtained in Example 1-1, 99 g of ion-exchanged water, and 0.1 g of citric acid were placed in a 200 mL mixing vessel purged with nitrogen, and stirred at 25°C for 1 hour. After stirring for hours, a colorless and transparent liquid was obtained.

[Example 2-4]
1 g of the methanol solution of octadecyldimethyl(11-trimethoxysilylundecyl)ammonium chloride obtained in Synthesis Example 1-3, 99 g of ion-exchanged water, and 0.1 g of citric acid were placed in a 200 mL mixing vessel purged with nitrogen, and stirred at 25°C. After stirring for 1 hour, a colorless and transparent liquid was obtained.

[Example 2-5]
1 g of the ethanol solution of octadecyldimethyl(8-triethoxysilyloctyl)ammonium chloride obtained in Example 1-2, 99 g of ion-exchanged water, and 0.1 g of citric acid were placed in a 200 mL mixing vessel purged with nitrogen, and the mixture was stirred at 25°C for 1 hour. After stirring for hours, a colorless and transparent liquid was obtained.

[Comparative Example 2-1]
1 g of the methanol solution of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride obtained in Comparative Synthesis Example 1-1, 99 g of ion-exchanged water, and 0.1 g of citric acid were placed in a 200 mL mixing vessel purged with nitrogen, and the mixture was stirred at 25°C. After stirring for 1 hour, a colorless and transparent liquid was obtained.

[Comparative Example 2-2]
1 g of the ethanol solution of octadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride obtained in Comparative Synthesis Example 1-2, 99 g of ion-exchanged water, and 0.1 g of citric acid were placed in a 200 mL mixing vessel purged with nitrogen, and stirred at 25°C. After stirring for 1 hour, a colorless and transparent liquid was obtained.

<Manufacturing of processed goods>
[Examples 3-1 to 3-5, Comparative Examples 3-1 and 3-2]
5 g of T/C fiber (polyester/cotton composite fiber) was immersed in each of the antiviral compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2 for 30 seconds, T/C fibers treated with the antiviral composition were made by removing the fibers and drying them at 80° C. for 10 minutes.

<Evaluation of antiviral properties>
Antiviral properties of the obtained fibers were evaluated by the following method. Evaluation was performed by the virus reduction rate calculated by the following method. Table 1 shows the results.
[Fiber]: T/C fiber treated with an antiviral agent composition, washed in a household washing machine (model number NA-VX86002, manufactured by Panasonic Corporation, standard course, detergent: JAFET standard detergent) 5 times and 10 times Textile after washing [Virus used]: Influenza virus H1N1 IOWA strain [Cultured cells]: MDCK cells [Method for preparing virus solution]: MDCK cells were inoculated with influenza virus. After adsorption at 37°C for 1 hour, the inoculum virus solution was removed and washed twice with sterilized PBS. MEM medium was added and cultured for 5 days at 37° C. in the presence of 5% CO ₂ . The culture supernatant was collected, centrifuged at 3,000 rpm for 30 minutes, the centrifugation supernatant was dispensed and stored at -70°C or lower to obtain a virus solution.
[Measurement of virus titer]: 0.4 mL of virus solution was added to the fiber, placed in a sterilized vial, and sealed. The sample was allowed to stand at room temperature (25° C.) for 1 hour as the sensitization time. After the sensitization time had elapsed, 20 mL of cell maintenance medium was added to the vial and mixed well to wash out the virus. The washed-out solution was further subjected to 10-fold serial dilution with a cell maintenance medium, each diluted solution was inoculated into cultured cells in a microplate, and cultured at 37° C. for 5 days. After culturing, each culture solution was collected, the presence or absence of virus growth was confirmed by hemagglutination reaction, and the virus titer (TCID50) was measured.
[Virus reduction rate (%)]: 100 × [(virus titer in untreated fiber - virus titer in the above fiber) / (viral titer in untreated fiber)]

As shown in Table 1, the fibers treated with the antiviral agent compositions of Examples 3-1 to 3-5 exhibited excellent long-lasting antiviral properties, and the antiviral properties of Examples 2-3 and 2-5 (Examples 3-3 and 3-5), particularly excellent durability was obtained.
On the other hand, in Comparative Examples 3-1 and 3-2, repeated washing resulted in loss of antiviral properties and poor durability.

Claims (4)

A fiber treatment agent comprising an antiviral agent composition containing an organosilicon compound represented by the following formula (1).

(wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ³ is an alkyl group having 12 to 24 carbon atoms, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, X is a halogen atom, m is 8 , and n is an integer of 1 to 3.) The fiber treatment agent according to claim 1 , wherein the content of the organosilicon compound represented by formula (1) in the antiviral agent composition is 0.0001 to 40% by mass based on the total composition . A fiber treated with the fiber treatment agent according to claim 1 or 2. 4. The fiber according to claim 3, selected from natural fibers, regenerated fibers, semi-synthetic fibers, synthetic fibers and composite fibers of these fibers.