WO2023190895A1

WO2023190895A1 - Processing agent, processed article, and production method for processed article

Info

Publication number: WO2023190895A1
Application number: PCT/JP2023/013238
Authority: WO
Inventors: 雅彦山田
Original assignee: 大和紡績株式会社
Priority date: 2022-03-31
Filing date: 2023-03-30
Publication date: 2023-10-05

Abstract

Provided is a processing agent having excellent antiviral properties, antimicrobial properties, and odor elimination properties. The processing agent comprises: organic salts of first amino acids and second amino acids different from the first amino acids; a metal compound; and an aqueous solvent. The first amino acids are at least one of a fatty acid acyl amino acid having a basic functional group at a side chain thereof and a derivative thereof, the second amino acids are at least one of an α-amino acid and a derivative thereof, and the organic salts are formed of cations derived from the basic functional group of the first amino acids and anions derived from an anionic group of the second amino acids.

Description

Processing agents, processed articles, and methods for producing processed articles

The present invention relates to a processing agent, a processed article, and a method for producing a processed article.

With the recent rise in awareness regarding hygiene, various everyday items are being treated with antibacterial or antiviral treatments. Along with this, various antibacterial and antiviral processing agents have been proposed. For example, Patent Document 1 describes an antibacterial/antiviral composition for textiles containing a silver amino acid, a zinc amino acid, and a copper ion.

Japanese Patent Application Publication No. 2017-133137

However, the antibacterial/antiviral composition for textiles of Patent Document 1 needs to be used at a high concentration, resulting in high cost and poor productivity. Furthermore, since the antibacterial/antiviral composition for textiles of Patent Document 1 is physically bonded to textile products through aggregation, it is likely to fall off due to external loads on textile products (other processing, washing, etc.).

An object of the present invention is to provide a processing agent that has excellent antiviral, antibacterial, and deodorizing properties. Another object of the present invention is to provide a processed article to which the above-mentioned processing agent is attached, and a method for manufacturing the same.

The present invention
an organic salt of a first amino acid and a second amino acid different from the first amino acid;
metal compounds, and
an aqueous solvent,
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt relates to a processing agent formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.

The present invention also includes:
The product to be processed,
comprising an organic salt of a first amino acid and a second amino acid different from the first amino acid, which adheres to the article to be treated, and a metal compound;
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt relates to a processed article formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.

The present invention further includes:
Equipped with a process of bringing the processing agent into contact with the workpiece,
The processing agent is
an organic salt of a first amino acid and a second amino acid different from the first amino acid;
metal compounds, and
an aqueous solvent,
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt relates to a method for producing a processed article, in which the organic salt is formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.

According to the present invention, a processing agent having excellent antiviral, antibacterial, and deodorizing properties is provided. According to the present invention, there is further provided a processed article to which the above-mentioned processing agent is attached, and a method for manufacturing the same.

[Processing agent]
The processing agent according to the present disclosure includes an organic salt whose cation and anion are both amino acids, a metal compound having a metal ion as a cation, and an aqueous solvent.
Organic salts are formed by two types of amino acids. The first amino acids are at least one of fatty acylamino acids and derivatives thereof (hereinafter collectively referred to as "basic acylamino acids") having a basic functional group in the side chain. The second amino acids are at least one of α-amino acids and derivatives thereof (hereinafter collectively referred to as “α-amino acids”).

Compared to the case where a metal salt of an amino acid and another metal salt are used as in Patent Document 1, the processing agent according to the present disclosure uses an organic salt formed by two types of amino acids together with a metal compound. In particular, antiviral properties, antibacterial properties, and deodorizing properties are improved. According to the processing agent according to the present disclosure, further improvements in other functions can be expected. Other functions include, for example, antiallergic properties and pH control properties. Hereinafter, performance including at least antiviral properties, antibacterial properties, and deodorizing properties may be collectively referred to as "functionality".

Antiviral properties can be evaluated by antiviral activity values calculated based on JIS L 1922:2016 "Testing method for antiviral properties of textile products" or ISO 18184 (Textiles - Determination of antiviral activity of textile products). When the antiviral activity value is 2.0 or more, it can be said that the processing agent has antiviral properties, and when it is 3.0 or more, it can be said that it has excellent antiviral properties.

The processing agent according to the present disclosure is particularly useful as an "antiviral agent."

Antibacterial properties can be evaluated by an antibacterial test using Staphylococcus aureus NBRC 12732, a type of Gram-positive bacteria, and/or Klebsiella pneumoniae NBRC 13277, a type of Gram-negative bacteria. The antibacterial test using Staphylococcus aureus is carried out by the bacterial liquid absorption method according to JIS L 1902:2015 "Antibacterial test method and antibacterial effect of textile products".

The antibacterial property against Staphylococcus aureus is evaluated by the antibacterial activity value shown by the following formula. When the antibacterial activity value is 2.0 or more, it can be said that the processing agent has antibacterial properties against Staphylococcus aureus, and when it is 3.0 or more, it can be said that it has excellent antibacterial properties against Staphylococcus aureus. .

The antibacterial property against Klebsiella pneumoniae is also evaluated by the antibacterial activity value. When the antibacterial activity value is 2.0 or more, it can be said that the processing agent has antibacterial properties against Klebsiella pneumoniae, and when it is 3.0 or more, it can be said that it has excellent antibacterial properties against Klebsiella pneumoniae.

A processing agent can be said to have excellent antibacterial properties if it has excellent antibacterial properties against at least one of Staphylococcus aureus and Klebsiella pneumoniae. If antibacterial properties are observed against Staphylococcus aureus, it can be said that the processing agent also has antibacterial properties against Gram-positive bacteria. If antibacterial properties are observed against Klebsiella pneumoniae, it can be said that the processing agent further has antibacterial properties against other Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella enterica, Pseudomonas bacteria, and Moraxella bacteria.

Antibacterial activity value = (Mb-Ma)-(Mc-Mo)
Ma: The average value of the number of viable bacteria or the common logarithm of the ATP amount on the standard cloth immediately after inoculation with the test bacterial solution Mb: The average value of the number of viable bacteria or the common logarithm of the ATP amount after 18-hour incubation of the standard cloth Mo: Specimen The average value of the number of viable bacteria or the common logarithm of the amount of ATP immediately after inoculation of the test bacterial solution Mc: The average value of the number of viable bacteria or the common logarithm of the amount of ATP after culturing the specimen for 18 hours

The processing agent according to the present disclosure is particularly useful as an "antibacterial agent."

Deodorizing properties are measured using the "21. Deodorizing properties test (detection tube It can be evaluated using a method that complies with the ``Act, Gas Chromatography Method''.

The test conditions are as follows.
(Initial concentration of each odor component gas)
Ammonia 100ppm
Acetic acid 30ppm
Isovaleric acid 38ppm

The size of the sample used in the detector tube method is 100 cm ² (10 cm long x 10 cm wide). The size of the sample used in the gas chromatography method is 50 cm ² (5 cm long x 10 cm wide). After placing the sample in a sealed container, odor component gas adjusted to the initial concentration is sealed. After sealing the odor component gas and leaving it for 2 hours, the concentration of the odor component gas is measured.

The specific testing methods using the detector tube method and gas chromatography method are as follows.

(detector tube method)
A sealed 5 L Tedlar (registered trademark, hereinafter the same) bag is prepared, and 3 L of odor component gas is injected into the Tedlar bag using a syringe to reach a specified initial concentration. Two hours after injecting the odor component gas into the Tedlar bag, the concentration of the odor component gas present in the Tedlar bag is measured using a detection tube (blank test). This concentration is taken as the blank test concentration, and the average value is taken as Sb.

Separately, take a ^100cm2 sample piece and place it in a 5L Tedlar bag. Next, 3 L of odor component gas is injected into the Tedlar bag using a syringe to reach a specified initial concentration. As in the blank test, the concentration of the odor component gas was measured using a detection tube 2 hours after the odor component gas was injected into the Tedlar bag, and the average value of the measured concentrations was taken as Sn.

(Gas chromatography method (GC method))
First, a raw odor solution for generating odor component gas is prepared. The ammonia raw odor solution is prepared by diluting 7.2 ml of ammonia water (ammonia concentration: 28%) with 100 ml of distilled water. The raw odor solution of acetic acid is prepared by diluting 0.5 ml of acetic acid reagent (acetic acid purity: 99.7%) with 100 ml of distilled water. The original odor solution of isovaleric acid is prepared by diluting 1 ml of isovaleric acid reagent (isovaleric acid purity: 98%) with 100 ml of distilled water, and further diluting 0.5 ml of the isovaleric acid diluted solution with 100 ml of distilled water. be done.

Next, conduct a blank test for each odor. A magnetic stirrer bar is placed in a 500 ml Erlenmeyer flask, 5 μl of the original odor solution of each odor is injected with a micropipette, and the flask is tightly stoppered. The magnetic stir bar in the Erlenmeyer flask is stirred with a magnetic stirrer, and after 2 hours, the residual gas in the Erlenmeyer flask is sampled with a syringe, and the concentration of the sampled residual gas is measured with a gas chromatograph analyzer. The average value of the peak areas of these measured values is defined as the numerical value Sb of the blank test.

Next, the procedure is carried out in the same manner as the blank test except that 50 cm ² of the sample is placed in a 500 ml Erlenmeyer flask, and after 2 hours, the remaining gas in the container is sampled in the same manner as in the blank test. The concentration of the sampled residual gas is measured using a gas chromatograph analyzer, and the average value of the peak areas of the measured values is taken as the numerical value Sn of the test using the sample.

(Odor reduction rate)
From the average value of gas concentration in a blank test (Sb) and the average value of gas concentration in the case of using a sample (Sn), measured by the detector tube method or gas chromatography method, the reduction rate of odor component gas is determined by the following formula. seek.
Odor reduction rate (%) = [(Sb-Sn)/Sb] x 100
Sb: Average value of gas concentration in blank test Sn: Average value of gas measurement values in test using sample

If the reduction rate of ammonia concentration is 70% or more, the reduction rate of acetic acid concentration is 70% or more, and the reduction rate of isovaleric acid concentration is 85% or more, the processing agent has excellent deodorizing properties. It can be said that it has.

The processing agent according to the present disclosure is particularly useful as a "deodorant".

In addition, according to the processing agent according to the present disclosure, these excellent functionalities are unlikely to deteriorate. The decrease in functionality occurs, for example, when processing agents (more specifically, metal ions) fall off from the processed product. Hereinafter, the ability to suppress a decline in functionality will be expressed as durability.

Durability can be evaluated by conducting each of the above tests using a sample that has been washed 10 times according to the JIS L 1930:2019 home washing test method for textile products (C4M method).

The reason why the processing agent according to the present disclosure improves functionality and furthermore durability is not clear, but it is thought to be as follows.
In the processing agent, the basic acylamino acids can form a complex with a metal ion derived from a metal compound through an amino group and a carboxy group. Furthermore, the basic functional group of the basic acylamino acids is positively charged in the processing agent and can chemically bond to the article to be processed, typified by fibers. For example, the above basic functional group and the hydroxyl group of the cellulose fiber can be covalently bonded.

α-Amino acids can also form complexes with metal ions derived from metal compounds through amino groups and carboxy groups.

The organic salt used in the present disclosure dissociates into a cation of basic acylamino acids and an anion of α-amino acids in the processing agent. On the other hand, it is thought that a reaction opposite to dissociation also occurs and an equilibrium state is reached. Thus, at least some organic salts may behave as ion pairs.

Therefore, the cation of the organic salt can chemically bond to the product to be treated while forming an ion pair with the anion. In addition, the two amino acids in the organic salt can each carry a different metal ion. Furthermore, since these metal ions form complexes with the above-mentioned amino acids, they are difficult to fall off. For these reasons, it is thought that functionality is improved and their durability is improved.

Furthermore, organic salts consisting of two types of amino acids can be expected to have high safety for the environment and the human body. Organic salts consisting of two types of amino acids are also less likely to cause yellowing of processed products due to heat.

The processing agent is in a mixed state and is more preferably in an aqueous solution. A miscible state means that each component is present in an aqueous solvent. At this time, each component may be hydrated in an aqueous solvent or may be dispersed in an aqueous solvent.

(organic salt)
The organic salt is a salt of α-amino acids and at least one of a fatty acylamino acid and its derivatives (basic acylamino acids) having a basic functional group in its side chain.

《α-Amino acids》
α-Amino acids are blended into processing agents as salts with basic acylamino acids. α-Amino acids can dissociate into anions in processing agents.

α-Amino acids have a structure in which an amino group is bonded to a carbon (α-carbon) to which a carboxy group is bonded, and generally RCH(NH ₂ )COOH (R is a group containing a hydrocarbon group) It is expressed as

α-Amino acids can be dissociated into anions derived from anionic groups. Examples of the anionic group include a carboxy group, a hydroxyl group, a phosphoric acid group, a sulfuric acid group, a sulfonic acid group, and a halogeno group. The group capable of dissociating into an anion in the processing agent may be a carboxy group bonded to the α-carbon. Due to the anionic group, α-amino acids can form salts with basic acylamino acids and can covalently bond with the article to be treated.

The α-amino acids may have a secondary amino group from the viewpoint of solubility in aqueous solvents. Such α-amino acids include, for example, tryptophan, histidine, proline and pyrrolidone carboxylic acid. Among these, the α-amino group may be a secondary amino group. Such α-amino acids include, for example, proline and pyrrolidone carboxylic acid.

The α-amino acids may have a nitrogen-containing heterocycle from the viewpoint of solubility in aqueous solvents. Such α-amino acids include, for example, the above-mentioned tryptophan, histidine, proline, and pyrrolidone carboxylic acid.

The α-amino acids may be pyrrolidone carboxylic acid. Pyrrolidone carboxylic acid has the following formula:

It is expressed as

The hydrogen atom bonded to the carbon atom of pyrrolidone carboxylic acid may be substituted. Examples of the substituent include an alkyl group, an acyl group, a hydroxyl group, an amino group, an alkylamino group, a nitro group, and a sulfonyl group.

《Basic acylamino acids》
Basic acylamino acids are blended into processing agents as salts with α-amino acids. Basic acylamino acids usually have a basic functional group in their side chain in addition to the amino group that amino acids have. Basic acylamino acids can dissociate into cations in processing agents. The basic functional groups of basic acylamino acids form cations.

Basic acylamino acids are formed by a basic amino acid and a fatty acid acyl group introduced into an amino group other than the basic functional group of the basic amino acid. A basic amino acid has a basic functional group in its side chain along with an amino group and a carboxy group. Hereinafter, acylated amino acids are referred to as "acyl amino acids."

Basic functional groups typically contain nitrogen. Examples of the basic functional group include a guanidino group (-NH-C(=NH)-NH ₂ ), an amino group (-NR ₂ , R is, for example, hydrogen or a hydrocarbon group having 1 to 4 carbon atoms), Examples include an imidazole group (-C ₃ H ₄ N ₂ ) and a cyano group (-C≡N). The basic functional group may be a guanidino group.

The basic amino acid may have one selected from the group consisting of a heterocycle, an aromatic ring, a non-aromatic ring, and an aliphatic hydrocarbon group. The basic amino acid may have an aliphatic hydrocarbon group, and may have an aliphatic hydrocarbon group having 4 to 8 carbon atoms. In other words, the basic amino acid may be an aliphatic amino acid having 4 to 8 carbon atoms and having a basic functional group in its side chain. The basic amino acid may have the substituents listed in the description of pyrrolidone carboxylic acid.

Examples of basic amino acids include arginine, histidine, lysine, and ornithine. The basic amino acid may be arginine.

Fatty acid acyl groups are derived from fatty acids. The fatty acyl group is derived from, for example, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms. The above fatty acids may be linear or branched. Examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, undecylenic acid, petroselic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, and arachidonic acid. , coconut oil fatty acids, and palm kernel oil fatty acids. Among these, the fatty acid may be coconut oil fatty acid in terms of its influence on the environment and the human body.

The basic acylamino acid derivative may be an alkyl ester of the basic acylamino acid. In the alkyl ester of basic acylamino acid, the carboxy group of the acylamino acid is esterified with, for example, an alkyl group having 1 to 4 carbon atoms. From the viewpoint of stability of the processing agent, the derivative may be a C1 or C2 alkyl ester of a basic acylamino acid.

For example, the basic acylamino acid has the following formula:

(wherein A is a hydrocarbon group having a heterocycle, aromatic ring, non-aromatic ring or aliphatic hydrocarbon group, B is a basic functional group, R ¹ is a fatty acid residue, R ² is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms.)
It is expressed as

A is a hydrocarbon group having a heterocycle, an aromatic ring, a non-aromatic ring, or an aliphatic hydrocarbon group. A may be an aliphatic hydrocarbon group having a prime number of 4 to 8. A is a part of the above basic amino acid excluding the amino group, the carboxy group, the carbon atom to which these groups are bonded, and the basic functional group. B is the basic functional group described above. R ¹ is part of an acyl group and is a residue of the above fatty acid. R ² is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and may be a hydrocarbon group having 1 or 2 carbon atoms.

The organic salt may be N-coco fatty acid acyl-L-arginine ethyl DL-pyrrolidonecarboxylate from the viewpoint of solubility in aqueous solvents and effects on the environment and the human body. This organic salt has the following formula:

(In the formula, R ¹ is a residue of coconut oil fatty acid.)
It is expressed as

Coconut oil fatty acids contain multiple saturated fatty acids and unsaturated fatty acids. Coconut oil fatty acids include, for example, caprylic acid (saturated fatty acid with 8 carbon atoms), capric acid (saturated fatty acid with 10 carbon atoms), lauric acid (saturated fatty acid with 12 carbon atoms), and myristic acid (saturated fatty acid with 14 carbon atoms). , palmitic acid (saturated fatty acid with 16 carbon atoms), stearic acid (saturated fatty acid with 18 carbon atoms), oleic acid (unsaturated fatty acid with 18 carbon atoms), and linoleic acid (unsaturated fatty acid with 18 carbon atoms).

The combination of two types of amino acids constituting the organic salt is appropriately determined in consideration of handling properties (for example, solubility in aqueous solvents, stability, and processability).

The concentration of the organic salt is not particularly limited, and may be appropriately set in consideration of the viscosity of the processing agent, the method of adhesion of the processing agent to the processed product, the use of the processed product, etc. From the viewpoint of functionality, the concentration of organic salt in the processing agent may be 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0. It may be 15% by mass, and may be 0.2% by mass or more. The concentration of the organic salt may be 5% by mass or less, 1.5% by mass or less, and 1.0% by mass or less because the processing agent is easy to prepare and has excellent stability and handleability. The content may be 0.75% by mass or less, and may be 0.6% by mass or less. In one embodiment, the concentration of the organic salt is 0.01% by mass or more and 5% by mass or less.

It is desirable that the processing agent does not contain a salt of at least one of amino acids, acylamino acids, basic amino acids, and basic acylamino acids (hereinafter sometimes collectively referred to as "amino acids") and metal ions. Salts consisting of amino acids and metal ions change color when dissolved in an aqueous solvent, so they may stain the product to be treated.

Among these, it is desirable that the processing agent does not contain alkali metal salts of amino acids. This is because alkali metal salts of amino acids tend to aggregate, making quality control difficult. Examples of the alkali metal include Li (lithium), Na (sodium), K (potassium), and Cs (cesium). In particular, the processing agent desirably does not contain sodium salts and potassium salts of amino acids, and desirably does not contain sodium salts and potassium salts of acylamino acids. It is desirable that the processing agent does not contain, for example, an alkali metal salt of pyrrolidone carboxylic acid, an alkali metal salt of an acylamino acid, and an alkali metal salt of a basic acylamino acid. The expression that the processing agent does not contain a metal salt of an amino acid means that the amount of the amino acid metal salt added to the processing agent is less than 0.005% by mass.

(metal compound)
The metal compound is not particularly limited as long as it can generate (or release) metal ions in the processing agent. Examples of such metal compounds include metal salts and metal oxides.

The reason why the processing agent according to the present disclosure exhibits antibacterial and antiviral properties is not clear, but it is thought to be as follows. The metal compound contained in the processing agent according to the present disclosure generates metal ions in water, regardless of whether it is dissolved in water. In addition to exhibiting strong cationic properties, the generated metal ions have a small ionic radius, so they can strongly act on and destroy the membranes of bacteria and viruses. Antibacterial and antiviral properties are primarily caused by metal ions.

The reason why the processing agent according to the present disclosure exhibits a deodorizing effect on various odors is not clear, but it is thought to be as follows. Metal ions are present on the surface of the processing agent according to the present disclosure or an object treated using the processing agent. Oxygen in the air is activated by the catalytic action of these metal ions. The generated activated oxygen (superoxide: also called O ₂ ^- ) reacts with malodorous substances and exerts a deodorizing effect.

Examples of metal ions include Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Pt (platinum), Ag (silver), and Au (gold). Examples include ions of at least one selected metal. Among them, from the viewpoint of functionality, the metal may be at least one selected from the group consisting of Cu, Zn, Pt, Ag, and Au, and at least one selected from the group consisting of Cu, Zn, and Ag. It may be one type.

《Metal salt》
The metal salt is formed, for example, from the above metal ion and a counter anion. The metal salt dissociates into a metal ion and its counter anion in the processing agent.

As mentioned above, the counter anion is preferably derived from a source other than an amino acid. Examples of the counter anion include at least one selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, sulfate ion, hydroxide ion, nitrate ion, and acetate ion. Among them, from the viewpoint of production cost, etc., at least one selected from the group consisting of polyatomic ions such as sulfate ion, hydroxide ion, nitrate ion, and acetate ion may be used. The ion may be at least one selected from the group consisting of ions.

The metal salt is selected from the group consisting of, for example, Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Pt (platinum), Ag (silver) and Au (gold). at least one metal ion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, sulfate ion, hydroxide ion, nitrate ion, and acetate ion. It is formed from anion.

Specifically, the metal salt includes at least one selected from the group consisting of copper sulfate, copper chloride, copper acetate, zinc sulfate, zinc nitrate, zinc acetate, iron sulfate, and silver nitrate. Among them, from the viewpoint of functionality, it may be at least one selected from the group consisting of copper sulfate, copper acetate, zinc sulfate, zinc nitrate and silver nitrate, and at least one of copper sulfate, zinc sulfate and silver nitrate. It's fine.

The concentration of the metal salt is not particularly limited, and may be appropriately set in consideration of the viscosity of the processing agent, the method of adhesion of the processing agent to the processed product, the use of the processed product, etc.

From the viewpoint of functionality, the concentration of the metal salt in the processing agent may be 0.0001% by mass or more, 0.001% by mass or more, 0.005% by mass or more, 0.0001% by mass or more, 0.001% by mass or more, 0.005% by mass or more, The amount may be 0.01% by mass or more, and may be 0.02% by mass or more. From the viewpoint of suppressing discoloration due to oxidation of metal ions, the concentration of the metal salt may be 10% by mass or less, 5% by mass or less, 2% by mass or less, and 1.5% by mass or less. may be 1% by mass or less, may be 0.5% by mass or less, and may be 0.1% by mass or less. In one embodiment, the concentration of the metal salt is 0.0001% by mass or more and 10% by mass or less. Even when the concentration of the metal salt is as low as this, the processing agent according to the present disclosure exhibits excellent functionality.

When the metal is Ag, the concentration of the metal salt (i.e., silver salt) in the processing agent may be 0.0001% by weight or more, may be 0.0005% by weight or more, and may be 0.001% by weight or more. It may be 0.005% by mass or more. The concentration of silver salt in the processing agent may be 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, and 0.1% by mass or less. It may be less than 0.01% by mass, and may be less than 0.01% by mass. In one embodiment, the concentration of the silver salt is 0.0001% by mass or more and 5% by mass or less. When the metal is Cu, the concentration of the metal salt (i.e., copper salt) in the processing agent may be 0.001% by mass or more, may be 0.005% by mass or more, and 0.01% by mass or more. It may be. The concentration of the copper salt in the processing agent may be 10% by weight or less, 5% by weight or less, 2% by weight or less, and 0.5% by weight or less. In one embodiment, the concentration of the copper salt is 0.001% by mass or more and 10% by mass or less.

From the viewpoint of functionality, the ratio of the mass of organic salt W _O to the mass of metal salt W _M in the processing agent (W _O /W _M ) may be from 500/1 to 1/2, and from 300/1 to It may be 1/1, it may be 200/1 to 5/1, it may be 150/1 to 10/1.

The ratio of the mass W _O of the organic salt and the mass W _Ag of the silver salt in the processing agent (W _O /W _Ag ) may be from 500/1 to 1/1, and from 300/1 to 10/1. Often, it may be between 200/1 and 20/1, and between 150/1 and 20/1. The ratio of the mass W _O of the organic salt and the mass W _Cu of the copper salt in the processing agent (W _O /W _Cu ) may be 200/1 to 1/1, and may be 100/1 to 5/1. It may well be between 50/1 and 10/1.

《Metal oxide》
The metal oxide may be at least one selected from the group consisting of silver oxide (Ag ₂ O), zinc oxide (ZnO), and copper (II) oxide (CuO).

The metal oxide may be blended into the processing agent while being contained in at least one of the phosphate glass and the inorganic phosphate compound (hereinafter sometimes referred to as "matrix material"). Metal oxides incorporated into the structure of the matrix material dissociate in the presence of moisture and are gradually eluted as metal ions. That is, part or all of the metal oxide can be dissociated into metal ions in the processing agent.

A matrix material containing a metal oxide (hereinafter sometimes referred to as a "metal-containing matrix") can be produced by, for example, heating the material of the matrix material and a metal salt that serves as a metal source for the desired metal oxide. This can be obtained by: Through heat treatment or the like, the metal salt becomes a metal oxide and is supported in the matrix material.

Phosphate glass contains, for example, phosphorus (P), boron (B), and Group 2 elements (alkaline earth metal elements including magnesium) as essential components.

Examples of inorganic phosphate compounds include hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ), silicate apatite (part of the PO ₄ ^3- ions of hydroxyapatite is replaced with SiO ₄ ^4-) , ), titanium hydrogen phosphate hydrate, zirconia hydrogen phosphate hydrate, and zirconium phosphate.

The matrix material may be a phosphate glass. Phosphate glass, for example, contains 35 to 65 mol% of diphosphorus pentoxide (P ₂ O ₅ ), 5 to 25 mol % of diboron trioxide (B ₂ O ₃ ), and Group 2 elements ( 5 to 55 mol% of oxides of alkaline earth metals (including magnesium), and sodium oxide (Na ₂ O), potassium oxide (K ₂ O), silicon oxide (SiO ₂ ) and aluminum oxide (Al ₂ O). ₃ ) 0 to 20 mol% of at least one selected from the group consisting of: As a result, metal ions can be rapidly eluted from the metal oxide supported within the structure of the phosphate glass in the presence of moisture, making it easier to exhibit excellent functionality.

The P ₂ O ₅ contained in the phosphate glass may be 35 to 60 mol%, and may be 40 to 60 mol%. B ₂ O ₃ may be from 7 to 25 mol%, and from 10 to 20 mol%. The Group 2 element oxide may be 10 to 50 mol%, and may be 10 to 40 mol%. At least one selected from Na ₂ O, K ₂ O, SiO ₂ and Al ₂ O ₃ may be present in an amount of 0 to 20 mol %.

The metal oxide is contained, for example, in an amount of 0.2% by mass or more and 10% by mass or less with respect to 100% by mass of the metal-containing matrix (total of matrix material and metal oxide). The content of metal oxide may be 0.4% by mass or more. The content of metal oxides may be 5% by mass or less, and may be 3.5% by mass or less.

In particular, the metal-containing matrix contains 40-60 mol% of P ₂ O ₅ , 10-20 mol% of B ₂ O ₃ , 10-40 mol% of Group 2 element oxides, Na ₂ O, A phosphate-based glass containing 0 to 20 mol% of at least one selected from the group consisting of K ₂ O, SiO ₂ and Al ₂ O ₃ , and a metal oxide contained therein. The content of the material may be 0.2% by mass or more and 5% by mass or less based on 100% by mass of the metal-containing matrix. Processing agents containing this metal-containing matrix can exhibit particularly excellent functionality.

From a functionality point of view, the concentration of the metal-containing matrix in the processing agent may be 0.01% by weight or more, 0.05% by weight or more, 0.10% by weight or more, 0. It may be .30% by mass or more, and it may be .50% by mass or more. From the viewpoint of suppressing discoloration due to oxidation of metal ions, the concentration of the metal-containing matrix may be 20% by mass or less, may be 10% by mass or less, may be 5% by mass or less, and may be 3.0% by mass. The amount may be less than or equal to 1.5% by mass. In one embodiment, the concentration of the metal-containing matrix is greater than or equal to 0.01% by weight and less than or equal to 20% by weight. Even when the concentration of the metal-containing matrix is as low as this, the processing agent according to the present disclosure exhibits excellent functionality.

From the functionality point of view, the ratio of the mass W _O of the organic salt in the processing agent to the mass W _P of the metal-containing matrix (W _O /W _P ) may be from 1/10 to 15/7, and may be 3/14. ˜1/1, and may be 3/10 to 3/4.

(Quaternary ammonium salt)
Processing agents of the present disclosure may include quaternary ammonium salts. A quaternary ammonium salt is a salt of a quaternary ammonium ion and its counter anion.

Examples of the quaternary ammonium ion include tetramethylammonium ion, monoalkyltrimethylammonium ion, dialkyldimethylammonium ion, trialkylmonomethylammonium ion, tetraalkylammonium ion, alkyldimethylethylammonium ion, alkyldimethylbenzylammonium ion, and alkyldimethylammonium ion. Examples include pyridinium ions. These may be used alone or in combination of two or more. In particular, the quaternary ammonium ion may be a dialkyldimethylammonium ion. The alkyl group contained in the quaternary ammonium ion is a hydrocarbon group having 3 or more carbon atoms, and may be a hydrocarbon group having 8 to 18 carbon atoms. The alkyl group may contain two or more types of alkyl groups having 8 to 18 carbon atoms.

Examples of the counter anion include chloride ion, bromide ion, fluoride ion, iodide ion, hydroxide ion, phosphate ion, nitrate ion, and sulfate ion, and other molecular ions (polyatomic ions). These may be used alone or in combination of two or more. Counter anions may be chloride and phosphate ions.

The concentration of the quaternary ammonium salt is not particularly limited, and may be appropriately set in consideration of the viscosity of the processing agent, the method of adhesion of the processing agent to the processed article, the use of the processed article, etc. The concentration of the quaternary ammonium salt in the processing agent may be 0.05% by mass or more, 0.075% by mass or more, and 0.1% by mass or more. In terms of influence on the environment and the human body, the concentration may be 2% by mass or less, 1% by mass or less, and 0.5% by mass or less. In one embodiment, the concentration of the quaternary ammonium salt is 0.05% by mass or more and 2% by mass or less.

The source of the quaternary ammonium salt is not particularly limited. The source of quaternary ammonium salts may be included, for example, in processing agents or processing agents that are commercially available for other uses (eg, dye fixation).

Quaternary ammonium salts have conventionally been used as antiviral agents, but may cause yellowing of processed articles due to heat. Further, when the article to be treated is a fiber, the article can be washed with a detergent containing an anionic surfactant. Then, the quaternary ammonium salt may be masked by the surfactant of the detergent, and the desired antiviral properties may not be exhibited.

In the present disclosure, quaternary ammonium salts may not be used, or the amount used may be reduced. Therefore, yellowing of the processed article due to heat is further suppressed, and functionality can be exhibited. However, as noted above, this disclosure does not exclude the use of quaternary ammonium salts.

(Aqueous solvent)
Examples of the aqueous solvent include pure water, distilled water, ion exchange water, industrial water, and tap water. The processing agent may contain an organic solvent, if necessary.

(binder resin)
The processing agent according to the present disclosure may further include a binder resin. Durability can be further improved by fixing the organic salt and the metal compound to the treated article via the binder resin. "Adhesion" refers to being more firmly attached than "adhesion."

The binder resin is not particularly limited, and examples include acrylic resin, polyvinyl alcohol, ethylene/vinyl acetate resin, polyurethane resin, polyamide resin, polyester resin, silicone resin, and fluorine resin. Binder resins may be used singly or in combination of two or more.

The blending amount of the binder resin is also not particularly limited, and may be, for example, 0.1% by mass or more, or 1.0% by mass or more of the processing agent. The blending amount of the binder resin may be 50% by mass or less of the processing agent, and may be 15% by mass or less. In one embodiment, the blending amount of the binder resin is 0.1% by mass or more and 50% by mass or less of the processing agent. The binder resin may be included in any form. For example, a commercially available agent containing a binder resin may be blended into a mixture containing an organic salt, a metal compound, an aqueous solvent, and the like.

(Crosslinking agent)
The processing agent according to the present disclosure may further include a crosslinking agent. The durability can be further improved by attaching the organic salt and the metal compound to the article to be treated in a crosslinked state or by crosslinking the organic salt and the article to be treated by the crosslinking agent.

The crosslinking agent is not particularly limited, and examples thereof include amino resins, acid anhydrides, polyepoxy compounds, silane compounds, melamine resins, glyoxal resins, and isocyanate compounds having at least one of an isocyanate group and a blocked isocyanate group. The crosslinking agents may be used alone or in combination of two or more. Among these, it may be an isocyanate compound.

The blending amount of the crosslinking agent is also not particularly limited, and may be, for example, 0.1% by mass or more, or 1.0% by mass or more of the processing agent. The blending amount of the crosslinking agent may be 50% by mass or less of the processing agent, and may be 15% by mass or less. In one embodiment, the amount of the crosslinking agent is 0.1% by mass or more and 50% by mass or less of the processing agent. The crosslinking agent may be included in any form. For example, a commercially available agent containing a crosslinking agent may be incorporated into a mixture containing an organic salt, a metal compound, an aqueous solvent, and the like.

In the present disclosure, an organic salt coordinated to a metal ion can be bonded to a processed article through a chemical bond. Therefore, even if the binder resin and/or crosslinking agent is not used or the amount used is reduced, the processing agent is difficult to fall off. However, as noted above, this disclosure does not exclude the use of binder resins and/or crosslinking agents.

The processing agent further contains other components as necessary. Other components include, for example, a softener that improves the texture of the article to be treated, a dye fixing agent, an antistatic agent, and a water repellent. The other components are preferably those that do not easily destabilize the metal ions derived from the metal compound or those that do not easily form complexes with the metal ions, and more preferably those that do not form complexes with the metal ions.

[Processed goods]
The processed article according to the present disclosure includes an article to be treated, and an organic salt and a metal compound attached to the article to be treated. Organic salts and metal compounds are derived from the processing agents mentioned above. This processed article exhibits high functionality. Furthermore, this processed article is less likely to lose its functionality. The processed article can be durable, in other words wash-resistant, even when washed repeatedly.

The amount of organic salt and metal compound deposited is not particularly limited, and may be appropriately set depending on the form of the metal compound, the usage form of the processed article, etc.

・When using metal salts In order to facilitate the performance, the total adhesion amount (mass) of the organic salt and metal salt may be 0.01% or more of the mass of the product to be treated, and 0.025 % or more, and may be 0.04% or more. From the viewpoint of cost and the like, the total amount of organic salt and metal salt deposited may be 8% or less, 5% or less, or 2% or less of the mass of the article to be treated. A preferable total amount of the organic salt and metal salt deposited is 0.01% or more and 8% or less of the mass of the article to be treated.

- When using a metal-containing matrix In order to facilitate the performance, the total amount (mass) of the organic salt and the metal-containing matrix may be 3.0% or more of the mass of the product to be treated, and 1. It may be .5% or more, and it may be .65% or more. From the viewpoint of cost etc., the total amount of the organic salt and the metal-containing matrix deposited may be 2.0% or less, 1.5% or less, 1.2% or less of the mass of the product to be treated. It may be. A preferable total amount of the organic salt and metal-containing matrix deposited is 1.0% or more and 2.0% or less of the mass of the article to be treated.

The organic salt and the metal compound may be attached (fixed) to the article to be treated via a binder resin.

(Product to be processed)
The article to be treated may contain at least one selected from the group consisting of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers. The processing agent according to the present disclosure particularly tends to form chemical bonds with fibers. The processing agent according to the present disclosure is suitable for antiviral processing of fibers.

Natural fibers are broadly classified into vegetable fibers and animal fibers. Examples of plant fibers include cotton, linen, and pulp. Examples of animal fibers include feathers, silk, and animal hair (wool, angora, cashmere, mohair, and camel). Examples of regenerated fibers include regenerated cellulose fibers such as rayon, polynosic, cupro, and solvent-spun cellulose fibers. Examples of semi-synthetic fibers include acetate and triacetate. Examples of synthetic fibers include polyester, polyolefin, polyamide, polyurethane, and acrylic.

The article to be treated may include fibers having hydroxyl groups on the surface. Examples of the fibers having hydroxyl groups on the surface include cellulose fibers such as the above-mentioned vegetable fibers and regenerated cellulose fibers. Since the hydroxyl groups on the fiber surface and the basic functional groups of the basic acylamino acids can be covalently bonded, durability is further improved.

The article to be treated may be the above-mentioned fibers themselves, may be threads obtained by twisting at least one of the above-mentioned fibers, or may be a fibrous structure formed from the above-mentioned fibers or threads. The article to be treated may be pretreated in various ways.

The yarn may be a monofilament yarn, a multifilament yarn, or a spun yarn. The fineness and length of the fibers or threads are not particularly limited, and are appropriately set depending on the purpose and the like.

Examples of fiber structures include woven fabrics, knitted fabrics, non-woven fabrics, granular cotton (also referred to as beaded cotton or granular cotton, etc.) in which fibers are aggregated in granular form, and lumps formed by entangled fibers (also referred to as batting). Can be mentioned. Fiber structures can be used, for example, in bedding products such as duvet covers, bed sheets, and pillowcases; general clothing such as nightwear (pajamas), underwear, and cut shirts; stuffing for down, coats, futons, cushions, etc.; curtains and tablecloths. Bathroom supplies such as hand towels, bath towels and foot mats; Industrial materials such as industrial filters and tents; Sanitary materials such as infection prevention masks, mask filters, gauze and bandages.

The processing agent according to the present disclosure is difficult to fall off from the processed product and has excellent durability. Therefore, the article to be treated may be used repeatedly or washed repeatedly.

[Method for manufacturing processed articles]
The processed article according to the present disclosure is manufactured, for example, by a method including a step of bringing the above-mentioned processing agent into contact with the above-mentioned object to be processed.

When the article to be treated is a fiber or thread, the fiber or thread may be used to form a fibrous structure after the contact step. The article to be processed may be a fibrous structure before being cut, or may be a fibrous structure after being cut and sewn.

(Contact process)
The method of bringing the processing agent and the article to be processed into contact is not particularly limited. Examples of the contact method include a dipping method and a spraying method (eg, a spray method and an inkjet method). The dipping method is preferably used for fibers, threads, and fiber structures (which may be before or after sewing). The mode of dipping may be continuous or batch processing. After soaking, the processing agent may penetrate into the interior of the fiber or thread by heating. The spraying method is particularly preferably used for textile structures after sewing.

The contact method also includes a coating method. The coating method is particularly preferably used for the fibrous structure before sewing (and even before cutting). The coating method is not particularly limited, and includes, for example, a die coating method, a knife coating method, a roll coating method (for example, a gravure coating method, a flexo coating method), a rotary printing method, and a flat printing method. In the coating method, a processing agent containing a binder resin may be used.

The processing agent is brought into contact with the article to be processed so that the total amount of organic salt and metal compound deposited falls within the above range. The conditions of the contact step (temperature, humidity, presence or absence of load, processing speed of the workpiece, etc.) are not particularly limited, and are appropriately set according to the shape and type of the workpiece, the viscosity of the processing agent, etc.

The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are based on mass unless otherwise specified.

[Example 1]
(1) Preparation of processing agent As shown in Table 1, a processing agent was prepared by dissolving an organic salt and a metal compound in an aqueous solvent.

(2) Preparation of processed article A jersey knitted fabric made of 100% by mass cotton yarn (number 30) was prepared as a processed article.
After passing the jersey knitted fabric through a processing agent at room temperature, it was squeezed with a mangle (pickup rate 100%). Then, it was dried at 150° C. for 2 minutes to obtain a processed article.

[Example 2-8, Comparative Example 1-3]
Each component was mixed as shown in Table 1 to prepare each processing agent. Processed articles were produced in the same manner as in Example 1 using each processing agent. Impregnation conditions were adjusted so that the pickup rate was 100%.

In Examples 1-4 and Comparative Example 2, the product name CAE manufactured by Ajinomoto Co., Inc. was used as the N-coconut oil fatty acyl-L-arginine ethyl DL-pyrrolidone carboxylate.
In Example 5 and Comparative Example 3, Super Amide, a product name manufactured by Service Tech Japan Co., Ltd., which is a mixture of N-coconut oil fatty acid acyl-L-arginine ethyl DL-pyrrolidone carboxylate and dialkyldimethylammonium salt, was used. Art F was used. The alkyl group of the dialkyldimethylammonium salt contains multiple types of alkyl groups having 8 to 18 carbon atoms. The counteranion of the dialkyldimethylammonium salt is the chloride ion.
In Example 6, zinc sulfate was used as the metal salt.

In Example 7, a commercially available silver-based phosphate glass was used as the metal-containing matrix 1. The metal-containing matrix 1 has a composition containing 55 mol% of _P2O5 , 15 mol% of _B2O3 , 20 mol% of _MgO , and 10 mol% of _aluminum oxide ( _Al2O3 ₎ . Silver oxide (Ag ₂ O) is contained in an amount of 2.0% by mass based on 100% by mass of the metal-containing matrix 1 .
In Example 8, as the metal-containing matrix 2, commercially available silver-based phosphate glass (Ag ₂ O.3(P ₂ O _5.CaO )m.9(B ₂ O ₃ )n, m=10~ 15, n=1-2) was used. Silver oxide (Ag ₂ O) is contained in an amount of 2.9% by mass based on 100% by mass of the metal-containing matrix 2 .

[evaluation]
(1) Antiviral property and its durability Based on ISO18184 (Textiles - Determination of antiviral activity of textile products), an antiviral test was conducted under the following conditions and procedures. As specimens, processed articles (L0) obtained in Examples and Comparative Examples before washing, and processed articles (L0) obtained in Examples after washing 10 times according to the JIS L 1930 C4M method. Article (L10) was used.

(Test condition)
・Test virus: Human influenza virus (H3N2)
・Host cell: MDCK cell (canine kidney-derived cell)
・Washing solution: SCDLP medium ・Action conditions: 25°C, 2 hours ・Infectious titer measurement method: Plaque measurement method

(Procedure of test)
First, host cells were infected with the test virus and cultured at 37°C for a predetermined period of time. Thereafter, centrifugation was performed at 4° C. and 1000×g for 15 minutes to obtain a supernatant (virus suspension). The obtained virus suspension was diluted 10 times with sterile distilled water to prepare a concentration of 1×10 ⁷ to 5×10 ⁷ PFU/mL to obtain test virus suspension C.
Next, 0.2 mL of test virus suspension C was inoculated to 0.4 g of the specimen. After acting at 25° C. for 2 hours, 20 mL of washout solution was added and stirred with a vortex mixer to wash out the virus from the sample. The washed out solution was serially diluted and the virus infectivity titer was measured by plaque assay. Finally, the antiviral activity value was calculated using the following formula.
Mv=lg(Va)-lg(Vb)
Mv: Antiviral activity value lg (Va): Common logarithm of the virus infectivity of the standard cloth (PFU/standard cloth) immediately after inoculation lg (Vb): Virus infectivity of the specimen after standing for 2 hours (PFU/sample) common logarithm of

The antiviral activity value was evaluated as follows.
Antiviral activity value≧3.0: Sufficient effect 3.0>Antiviral activity value≧2.0: Effective

(2-1) Antibacterial properties against Staphylococcus aureus An antibacterial test was carried out by the bacterial liquid absorption method according to JIS L 1902:2015 "Antibacterial test method and antibacterial effect of textile products". Using Staphylococcus aureus NBRC 12732, the antibacterial activity value expressed by the following formula was calculated to evaluate antibacterial properties. The above processed article (L0) was used as a specimen.

(2-2) Antibacterial properties against Klebsiella pneumoniae An antibacterial test was carried out by the bacterial liquid absorption method according to JIS L 1902:2015 "Antibacterial test method and antibacterial effect of textile products". Antibacterial activity was evaluated using Klebsiella pneumoniae NBRC 13277 by calculating the antibacterial activity value shown by the above formula. The above processed article (L0) was used as a specimen.

(3) Deodorizing property and its durability "21. Deodorizing" described in the SEK Mark Textile Product Certification Standards (established by: Textile Evaluation Technology Council, Product Certification Department, revised date: April 1, 2022) Evaluation was made using a method compliant with the "Sensitivity Test (Detector Tube Method, Gas Chromatography Method)". The above processed articles (L0) and (L10) were used as samples.

(Initial concentration of odor component gas)
The initial concentration of the odor component gas used in evaluating the deodorizing properties was adjusted to the following concentration.
Ammonia 100ppm
Acetic acid 30ppm
Isovaleric acid 38ppm
(sample)
Samples of the following sizes were cut out from the processed articles (L0) and (L10).
Sample used in the detector tube method: 100cm ² (10cm long x 10cm wide)
Sample used in gas chromatography: 50cm ² (5cm long x 10cm wide)

Test methods using the detector tube method and gas chromatography method are as follows.
(detector tube method)
3 L of odor component gas was injected into a 5 L Tedlar bag using a syringe to reach a specified initial concentration, and the bag was sealed. Two hours after the odor gas was injected into the Tedlar bag, the concentration of the odor gas present in the Tedlar bag was measured using a detection tube (blank test). This concentration was taken as the blank test concentration, and the average value was taken as Sb.

Next, the above sample was placed in a 5L Tedlar bag. Subsequently, 3 L of odor component gas was injected into the above Tedlar bag using a syringe to reach a specified initial concentration, and the bag was sealed. As in the blank test, the concentration of the odor gas was measured using a detection tube 2 hours after the odor gas was injected into the Tedlar bag, and the average value of the measured concentrations was taken as Sn.

(Gas chromatography method (GC method))
First, a raw odor solution for generating odor component gas was prepared. An ammonia raw odor solution was prepared by diluting 7.2 ml of ammonia water (ammonia concentration: 28%) with 100 ml of distilled water. The raw odor solution of acetic acid was prepared by diluting 0.5 ml of acetic acid reagent (acetic acid purity: 99.7%) with 100 ml of distilled water. The original odor solution of isovaleric acid is prepared by diluting 1 ml of isovaleric acid reagent (isovaleric acid purity: 98%) with 100 ml of distilled water, and further diluting 0.5 ml of the isovaleric acid diluted solution with 100 ml of distilled water. did.

Next, a blank test was conducted for each odor. A magnetic stirrer bar was placed in a 500 ml Erlenmeyer flask, 5 μl of the original odor solution of each odor was injected with a micropipette, and the flask was tightly stoppered. The magnetic stir bar in the Erlenmeyer flask was stirred with a magnetic stirrer, and after 2 hours, the residual gas in the Erlenmeyer flask was sampled with a syringe, and the concentration of the sampled residual gas was measured with a gas chromatograph analyzer. The average value of the peak areas of these measured values was taken as the numerical value Sb of the blank test.

Next, the operation was carried out in the same manner as the blank test except that the above sample was placed in a 500 ml Erlenmeyer flask, and after 2 hours, the residual gas in the container was sampled in the same manner as in the blank test. The concentration of the sampled residual gas was measured using a gas chromatograph analyzer, and the average value of the peak areas of the measured values was taken as the numerical value Sn of the test using the sample.

(Odor reduction rate)
From the average value of gas concentration in a blank test (Sb) and the average value of gas concentration in the case of using a sample (Sn), measured by the detector tube method or gas chromatography method, the reduction rate of odor component gas is determined by the following formula. I asked for
Odor reduction rate (%) = [(Sb-Sn)/Sb] x 100
Sb: Average value of gas concentration in blank test Sn: Average value of gas measurement values in test using sample

The processed articles (L0) using the processing agents of Examples 1-8 all had antiviral activity values of 2.0 or more and had antiviral properties. The processed articles (L10) using the processing agents of Examples 1-4 and 6-8 also had antiviral activity values of 2.0 or more, and had antiviral durability. From this result, it is expected that the processed article (L10) using the processing agent of Example 5 also has high antiviral durability.

The processed articles (L0) using the processing agents of Examples 1-2 and 6 both have antibacterial properties against Staphylococcus aureus of 3.0 or higher, and antibacterial properties against Klebsiella pneumoniae of 3.0 or higher, making them excellent. It had antibacterial properties. Considering the mechanism by which the above functionality is exhibited, it is expected that the processed articles (L0) using the processing agents of Examples 3-5 and 7-8 also have high antibacterial properties. Furthermore, as mentioned above, considering that the processed article (L10) has high antiviral durability, it is expected that the processed article (L10) also has high antibacterial durability. be done.

The processed articles (L0) using the processing agents of Examples 1-2 and 6 had excellent deodorizing properties against ammonia, acetic acid, and isovaleric acid. Furthermore, the processed articles (L10) using the processing agents of Examples 1-2 and 6 had excellent deodorizing durability against ammonia and acetic acid. Considering the mechanism for exhibiting the functionality described above, it is expected that the processed articles (L10) using the processing agents of Examples 1-2 and 6 will also have excellent durability in deodorizing properties against isovaleric acid. Ru. Similarly, processed articles (L0) and processed articles (L10) using the processing agents of Examples 3-5 and 7-8 also have high deodorizing properties and durability against any gas. It is expected that

On the other hand, the processed article of Comparative Example 1 (L0) using the amino acid metal salt did not exhibit antiviral properties. This is considered to be because the metal salt of pyrrolidone carboxylic acid could not covalently bond to the fiber and was not fixed on the fiber. The processed article of Comparative Example 1 (L0) is also not expected to exhibit antibacterial and deodorizing properties.

The processed articles of Comparative Examples 2 and 3 (L0) in which no metal compound was used also did not exhibit antiviral activity. This is thought to be due to the fact that although the organic salt was covalently bonded to the fiber, it did not contain metal ions and was unable to sufficiently inactivate the virus. The processed articles (L0) of Comparative Examples 2 and 3 are also not expected to exhibit antibacterial and deodorizing properties.

(4) Metal adhesion amount The metal (Ag) content present in the processed article (LO) and processed article (L10) obtained in Example 2 was measured using inductively coupled plasma mass spectrometry (ICP-MS). did.

As a result, the Ag content per 1 g of processed article (LO) was 6.8 μg/g, and the Ag content per 1 g of processed article (L10) was 3.7 μg/g. From this, it was confirmed that the processed article according to the present disclosure retained a sufficient amount of Ag even after washing. Note that no Ag ions were detected in the unprocessed product.

The present disclosure includes the following aspects.
(Aspect 1)
an organic salt of a first amino acid and a second amino acid different from the first amino acid;
metal compounds, and
an aqueous solvent,
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt is a processing agent formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.
(Aspect 2)
The processing agent according to aspect 1, wherein the amino acid forming the first amino acids has an aliphatic hydrocarbon group having 4 to 8 carbon atoms.
(Aspect 3)
The processing agent according to aspect 1 or 2, wherein the amino acid forming the first amino acids is arginine.
(Aspect 4)
The processing agent according to any one of aspects 1 to 3, wherein the fatty acid acyl group contained in the first amino acids is derived from a saturated or unsaturated fatty acid having 8 to 22 carbon atoms.
(Aspect 5)
The processing agent according to any one of aspects 1 to 4, wherein the first amino acid contains an alkyl ester of a fatty acylamino acid having 1 to 4 carbon atoms and having a basic functional group in its side chain.
(Aspect 6)
The processing agent according to any one of aspects 1 to 5, wherein the anionic group of the second amino acid is a carboxy group bonded to the α-carbon.
(Aspect 7)
The processing agent according to any one of aspects 1 to 6, wherein the α-amino group of the second amino acid is a secondary amino group.
(Aspect 8)
The processing agent according to any one of aspects 1 to 7, wherein the second amino acid has a nitrogen-containing heterocycle.
(Aspect 9)
The processing agent according to any one of aspects 1 to 8, wherein the second amino acid is pyrrolidone carboxylic acid.
(Aspect 10)
The metal compound is
ions of at least one metal selected from the group consisting of iron, cobalt, nickel, copper, zinc, platinum, silver and gold;
A metal salt formed from at least one anion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, sulfate ion, hydroxide ion, nitrate ion, and acetate ion. , the processing agent according to any one of aspects 1 to 9.
(Aspect 11)
The processing agent according to aspect 10, wherein the metal salt includes at least one of copper sulfate, zinc sulfate, copper acetate, and silver nitrate.
(Aspect 12)
The processing agent according to aspect 10 or 11, wherein the ratio of the mass W _O of the organic salt to the mass W _M of the metal salt (W _O /W _M ) is 500/1 to 1/2.
(Aspect 13)
The metal compound is at least one metal oxide selected from the group consisting of silver oxide, zinc oxide, and copper oxide,
The processing agent according to any one of aspects 1 to 9, wherein the metal oxide is contained in at least one of a phosphate glass and an inorganic phosphate compound.
(Aspect 14)
The metal oxide is contained in an amount of 0.2% by mass or more and 10% by mass or less with respect to a total of 100% by mass of the metal oxide and at least one of the phosphate glass and the inorganic phosphate compound. , the processing agent of aspect 13.
(Aspect 15)
The phosphate glass is
35 to 65 mol% of diphosphorus pentoxide,
5 to 25 mol% diboron trioxide,
5 to 55 mol% of an oxide of a Group 2 element, and
The processing agent according to aspect 13 or 14, which contains 0 to 20 mol% of at least one selected from the group consisting of sodium oxide, potassium oxide, silicon oxide, and aluminum oxide.
(Aspect 16)
The ratio of the mass W _O of the organic salt to the mass W _P of at least one of the phosphate glass containing the metal oxide and the inorganic phosphate compound (W _O /W _P ) is 1/10. The processing agent according to any one of aspects 13 to 15, which is 15/7.
(Aspect 17)
The product to be processed,
comprising an organic salt of a first amino acid and a second amino acid different from the first amino acid, which adheres to the article to be treated, and a metal compound;
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt is a processed article formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.
(Aspect 18)
The processed article according to aspect 17, wherein the article to be treated includes at least one selected from the group consisting of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers.
(Aspect 19)
Equipped with a process of bringing the processing agent into contact with the workpiece,
The processing agent is
an organic salt of a first amino acid and a second amino acid different from the first amino acid;
metal compounds, and
an aqueous solvent,
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt is formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.

The processing agent of the present invention has excellent antiviral, antibacterial, and deodorizing properties, and is therefore suitable for various uses.

This application claims priority based on Japanese Patent Application No. 2022-060418 filed in Japan on March 31, 2022, and the entire content thereof is incorporated herein by reference.

Claims

an organic salt of a first amino acid and a second amino acid different from the first amino acid;
metal compounds, and
an aqueous solvent,
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt is a processing agent formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.
The processing agent according to claim 1, wherein the amino acid forming the first amino acids has an aliphatic hydrocarbon group having 4 to 8 carbon atoms.
The processing agent according to claim 1 or 2, wherein the amino acid forming the first amino acids is arginine.
The processing agent according to any one of claims 1 to 3, wherein the fatty acid acyl group contained in the first amino acids is derived from a saturated or unsaturated fatty acid having 8 to 22 carbon atoms.
The processing agent according to any one of claims 1 to 4, wherein the first amino acids include an alkyl ester having 1 to 4 carbon atoms of a fatty acylamino acid having a basic functional group in its side chain.
The processing agent according to any one of claims 1 to 5, wherein the anionic group of the second amino acid is a carboxy group bonded to the α-carbon.
The processing agent according to any one of claims 1 to 6, wherein the α-amino group of the second amino acid is a secondary amino group.
The processing agent according to any one of claims 1 to 7, wherein the second amino acid has a nitrogen-containing heterocycle.
The processing agent according to any one of claims 1 to 8, wherein the second amino acid is pyrrolidone carboxylic acid.
The metal compound is
ions of at least one metal selected from the group consisting of iron, cobalt, nickel, copper, zinc, platinum, silver and gold;
A metal salt formed from at least one anion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, sulfate ion, hydroxide ion, nitrate ion, and acetate ion. , the processing agent according to any one of claims 1 to 9.
The processing agent according to claim 10, wherein the metal salt includes at least one of copper sulfate, zinc sulfate, copper acetate, and silver nitrate.
The processing agent according to claim 10 or 11, wherein a ratio (W O /W M ) between the mass W O of the organic salt and the mass W M of the metal salt is 500/1 to 1/2.
The metal compound is at least one metal oxide selected from the group consisting of silver oxide, zinc oxide, and copper oxide,
The processing agent according to any one of claims 1 to 9, wherein the metal oxide is contained in at least one of a phosphate glass and an inorganic phosphate compound.
The metal oxide is contained in an amount of 0.2% by mass or more and 10% by mass or less with respect to a total of 100% by mass of the metal oxide and at least one of the phosphate glass and the inorganic phosphate compound. , the processing agent according to claim 13.
The phosphate glass is
35 to 65 mol% of diphosphorus pentoxide,
5 to 25 mol% diboron trioxide,
5 to 55 mol% of an oxide of a Group 2 element, and
The processing agent according to claim 13 or 14, which contains 0 to 20 mol% of at least one selected from the group consisting of sodium oxide, potassium oxide, silicon oxide, and aluminum oxide.
The ratio of the mass W O of the organic salt to the mass W P of at least one of the phosphate glass containing the metal oxide and the inorganic phosphate compound (W O /W P ) is 1/10. The processing agent according to any one of claims 13 to 15, which is ˜15/7.
The product to be processed,
comprising an organic salt of a first amino acid and a second amino acid different from the first amino acid, which adheres to the article to be treated, and a metal compound;
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt is a processed article formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.
The processed article according to claim 17, wherein the article to be treated includes at least one selected from the group consisting of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers.
Equipped with a process of bringing the processing agent into contact with the workpiece,
The processing agent is
an organic salt of a first amino acid and a second amino acid different from the first amino acid;
metal compounds, and
an aqueous solvent,
The first amino acids are at least one of a fatty acylamino acid and a derivative thereof having a basic functional group in its side chain,
The second amino acids are at least one of α-amino acids and derivatives thereof,
The organic salt is formed by a cation derived from the basic functional group of the first amino acid and an anion derived from the anionic group of the second amino acid.