WO2024128008A1 - Antibacterial agent and antiviral agent - Google Patents

Abstract

The present invention addresses the problem of providing: an antibacterial agent and an antiviral agent which are characterized by containing a pigment and a fatty acid metal salt; and an ink, a printed object, a paint, a coating, a plastic, a fiber, a film, and a cosmetic, etc., which are characterized by containing the antibacterial agent and the antiviral agent. An antibacterial agent and an antiviral agent according to the present invention contain a pigment and a fatty acid metal, and were discovered to have an antibacterial and antiviral action. A molded article containing the antibacterial agent and the antiviral agent were likewise discovered to have an antibacterial and antiviral action. The discovery successfully solved the above-mentioned problem.

Description

Antibacterial and antiviral agents

The present invention relates to antibacterial and antiviral agents.

In recent years, there has been a strong desire to maintain the cleanliness of living spaces, and many homes and public rooms have installed air purifiers and disinfectant sprays to maintain a clean environment. However, going beyond simple air purification by removing dirt and dust from the air, efforts are also being made to add high added value by providing antibacterial, antiviral, allergen removal, and deodorizing functions. Examples of applications that require such high added value include textile applications, plastic applications, and paint applications.

In textile applications, methods for imparting antibacterial or antiviral properties include kneading an antibacterial or antiviral agent into fibers and adhering a solution containing an antibacterial or antiviral agent to the fiber surface. The method of kneading an antibacterial or antiviral agent into fibers is generally considered to have high washing durability, but the high temperatures encountered during spinning raise concerns that organic antibacterial or antiviral agents may thermally decompose, and there has been a demand for improved heat resistance. On the other hand, the method of adhering to the fiber surface generally uses organic antibacterial or antiviral agents, such as quaternary ammonium salts, but there is an issue that the antibacterial or antiviral properties decrease after washing (Patent Document 1).

In paint applications, organic antibacterial or antiviral agents are used, just as in textile applications. However, acrylic/melamine-based paints and the like require a curing process using heat treatment, and organic antibacterial or antiviral agents, which are considered to have low heat resistance, can cause thermal deterioration of the treated surface and object (Patent Document 2). From this perspective, improved heat resistance is desired for applications involving high-temperature treatment.

Regarding the content of antibacterial or antiviral agents, it is necessary for them to be effective in relatively small amounts in any application, and an important technical issue is how to efficiently expose antibacterial or antiviral agents on the surfaces of fibers, plastics, coatings, etc. (Patent Documents 3 and 4)

JP 2013-76188 A JP 2017-014401 A JP 2006-28453 A JP 2022-93225 A

The problem that the present invention aims to solve is to provide an antibacterial agent, an antiviral agent, and inks, printed matter, paints, coatings, plastics, fibers, films, cosmetics, and the like that are characterized by containing said antibacterial agent or antiviral agent.

As a result of intensive research by the inventors to solve the above problems, they discovered that an antibacterial agent and an antiviral agent containing a pigment and a fatty acid metal salt have antibacterial and antiviral effects, and that molded articles containing said antibacterial and antiviral agents also have antibacterial and antiviral effects, thereby solving the above problems.

In other words, the present invention includes the following:

[1] An antibacterial agent or antiviral agent comprising an organic pigment or an inorganic pigment and a fatty acid metal salt.
[2] The antibacterial or antiviral agent according to [1], wherein a mass ratio of the organic pigment or inorganic pigment to the fatty acid metal salt is the organic pigment or inorganic pigment:fatty acid metal salt=99:1 to 50:50. [3] The antibacterial or antiviral agent according to 1 or 2, wherein the organic pigment is at least one selected from iron phthalocyanine, copper phthalocyanine, soluble azo, insoluble azo, quinacridone, perylene, or diketopyrrolopyrrole.
[4] The antibacterial and antiviral agent according to 1 or 2, wherein the inorganic pigment is at least one of iron (III) oxide and triiron tetroxide.
[5] The fatty acid metal salt is represented by the following general formula (1):

(In the general formula (1),
R is a hydrogen atom or a linear or branched alkyl group having 8 to 21 carbon atoms which may contain an alicyclic structure,
n is an integer ranging from 1 to 4, and when n is an integer of 2 or more, multiple R's may be the same or different.
M is lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or a rare earth.
[6] The antibacterial and antiviral agent according to 1 or 2, wherein the fatty acid metal salt is at least one selected from the group consisting of neodymium neodecanoate, lanthanum neodecanoate, and cobalt 2-ethylhexanoate.
[7] An ink, a printed matter, a paint, a coating, a plastic, a fiber, a film, or a cosmetic, comprising the antibacterial agent or antiviral agent according to any one of 1 to 6.

The antibacterial and antiviral agents of the present invention are water-insoluble, have antibacterial and antiviral properties, and have significantly higher heat and light resistance than dye-based antibacterial pigments. They also have antibacterial and antiviral properties in applications such as inks, printed matter, paints, coatings, plastics, fibers, films, and cosmetics, and can be used in a wide range of industrial fields.

Furthermore, the antibacterial and antiviral agents of the present invention exhibit pigment properties similar to those of conventional pigments, and can therefore be used in the same way as pigments, allowing for coloring and the addition of antibacterial and antiviral properties at the same time.

1 shows an SEM image of composition 1. This is the result of element mapping by SEM-EDS measurement performed at the same position and magnification as in FIG. 1, and the white parts indicate the distribution of neodymium.

The embodiments of the present invention described below only represent some of the embodiments of the present invention, and the present invention is not limited to the described contents as long as the gist of the invention is not significantly deviated from.

The antibacterial and antiviral agents of the present invention are described below.

[Organic pigments]
The organic pigment used in the antibacterial agent and antiviral agent of the present invention can be any known and commonly used pigment as long as it is a water-insoluble, fine-particle solid powder. For example, phthalocyanine-based, quinacridone-based, perylene-based, diketopyrrolopyrrole-based, soluble azo-based, insoluble azo-based, anthraquinone-based, perinone-based, thioindigo-based, dioxazine-based, isoindolinone-based, isoindoline-based, quinophthalone-based pigments and the like can be mentioned. In particular, phthalocyanine-based, quinacridone-based, perylene-based, diketopyrrolopyrrole-based, soluble azo-based, and insoluble azo-based pigments are preferred. These pigments can be used alone or in combination of two or more kinds. When the organic pigment has high antibacterial and antiviral properties, the antibacterial and antiviral agents of the present invention show particularly excellent antibacterial and antiviral effects, and are preferred.

[Phthalocyanine]
The phthalocyanine used in the present invention is not particularly limited, and any known and commonly used phthalocyanine can be used. The phthalocyanine used in the present invention is represented by the general formula (2).

(2)
(In the formula, M represents a metal selected from the group consisting of Cu, Fe, Zn, Co, Na, Mg, Al, Si, Ca, Ti, V, Mn, Ni, Cd, and Sn, or an oxymetal or metal halide thereof, or a metal-free substance. Each of R1 to R16 independently represents a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a carbonyl group, an alkoxy group, or a sulfonyl group.)

For example, in the case of general pigments, if the phthalocyanine is metal-free, it is C.I. Pigment Blue 16; if the central metal of the phthalocyanine is copper, it is C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 76, C.I. Pigment Green 7, C.I. Pigment Green 36; if the central metal of the phthalocyanine is zinc, it is C.I. Examples of pigments include C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Blue 75 when the central metal of the phthalocyanine is cobalt, and C.I. Pigment Blue 79 when the central metal of the phthalocyanine is aluminum.

The central metal of the phthalocyanine is preferably copper, iron, zinc, cobalt, sodium, magnesium, aluminum, silicon, calcium, titanium, vanadium, manganese, nickel, cadmium, or tin, or metal-free phthalocyanine. These metals and the phthalocyanine ring may be unsubstituted or may have halogen substituents, and the number of substituents (n) is theoretically possible to be n = 0 to 16, but in order to express the function as a pigment, it is preferable to have substituents to the extent that the pigment is not dissolved in water or a solvent.

Among the above metal phthalocyanines, phthalocyanines with high antibacterial and antiviral properties are preferably used because they exhibit particularly high antibacterial and antiviral properties. Examples of central metals in phthalocyanines with high antibacterial and antiviral properties include iron, cobalt, sodium, magnesium, aluminum, silicon, manganese, nickel, cadmium, and tin.

Among these, phthalocyanines whose central metal is iron, sodium, magnesium, or cobalt are preferred because of their high antibacterial and antiviral effects, and phthalocyanines whose central metal is iron are particularly preferred in the present invention.

[Quinacridone]
The quinacridone used in the present invention is not particularly limited, and any known and commonly used quinacridone may be used. For example, the quinacridone represented by the general formula (3) is

(3)
(In the formula, R1 to R16 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a nitro group.)

For example, C.I. Pigment Violet 19, C.I. Pigment Red 122, Pigment Red 202, Pigment Red 207, Pigment Red 206, Pigment Red 209, etc. are listed. Among them, C.I. Pigment Violet 19 is preferable.

[Perylene]
The perylene used in the present invention is not particularly limited, and any known perylene may be used. For example, the perylene may be represented by the general formula (4).

(4)
(In the formula, R1 and R2 each independently represent a hydrogen atom, an alkyl group, or an aryl group.)

For example, C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 179, C.I. Pigment Red 178, C.I. Pigment Violet 29, C.I. Pigment Black 31, etc. are listed. Among them, C.I. Pigment Red 179 is preferable.

[Diketopyrrolopyrrole]
The diketopyrrolopyrrole used in the present invention is not particularly limited, and any known and commonly used diketopyrrolopyrrole may be used. For example, the diketopyrrolopyrrole may be represented by the following general formula (5):

(5)
(In the formula, R1 to R10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, or an amino group.)

For example, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Orange 71, C.I. Pigment Orange 73, etc. are listed. Among them, C.I. Pigment Red 254 is preferable.

[Soluble azo]
The soluble azo used in the present invention is not particularly limited, and any known and commonly used azo may be used. For example, the soluble azo may be represented by the general formulas (6) and (7).

(6)
(In the formula, R1 to R9 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, a nitro group, or the like. M represents barium, calcium, strontium, manganese, aluminum, or iron.)

(7)
(In the formula, R1 to R10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, a nitro group, or the like. M represents barium, calcium, strontium, manganese, aluminum, or iron.)

For example, C. I. Pigment Red 53:1, C.I. I. Pigment Red 53:2, C.I. I. Pigment Red 53:3, C.I. I. Pigment Red 49:1, C.I. I. Pigment Red 49: 2 C.I. I. Pigment Red 49:3, C.I. I. Pigment Red 50:1, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 48:4, C.I. I. C.I. Pigment Red 52:1, C.I. Pigment Red 63:1, C.I. Pigment Red 63:2, C.I. Pigment Red 64:1, C.I. Pigment Red 58:2, C.I. Pigment Red 58:4, C.I. Pigment Red 243, Examples include C.I. Pigment Red 61 and C.I. Pigment Red 60:1. Of these, C.I. Pigment Red 48:1 is preferred.

[Insoluble azo]
Insoluble azos can be classified into β-naphthol-based, naphthol AS-based, pyrazolone-based, acetoacetate arylide-based, benzimidazolone-based, etc., but the insoluble azos used in the present invention are not particularly limited, and known and commonly used ones can be used. Among them, acetoacetate arylide-based is preferred, and among them, disazo yellow-based is more preferred. For example, β-naphthol-based is represented by the general formula (8):

(8)
(In the formula, R1 to R10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, or a nitro group.)

Naphthol AS series has the general formula (9)

(9)
(In the formula, R1 to R15 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, or a nitro group.)

The pyrazolone system has the general formula (10)

(10)
(In the formula, R1 to R9 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, or a nitro group.)

　Acetoacetate arylide monoazo type is represented by the general formula (11)

(11)
(In the formula, R1 to R10 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, or a nitro group.)

Acetoacetate arylide disazo type has the general formula (12)

(12)
(In the formula, R1 to R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, a nitro group, or the like. A and B each independently represent an aryl group, or the like. C represents -CnHn+2 (n is 0 or more) or -O-CnHn+2-O- (n is 1 or more).)

The benzimidazolone series has the general formula (13)

(13)
(In the formula, R1 to R13 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a methoxy group, an aryl group, a cyano group, an amino group, or a nitro group.)
It is expressed as:

For example, C. I. Pigment Red 3, C.I. I. Pigment Orange 5, C.I. I. Pigment Red 5, C.I. I. Pigment Red 146, C.I. I. Pigment Violet 50, C.I. I. Pigment Blue 25, C.I. I. Pigment Orange 13, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 17, C.I. I. Examples of the pigments include C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 180, C.I. Pigment Yellow 154, and C.I. Pigment Red 185. Among these, C.I. Pigment Yellow 180 is preferred.

Phthalocyanine and condensed polycyclic pigments are often called crude pigments, and after production, they often have large particle sizes and uneven particle size, and depending on the application, they have poor dispersibility, so if necessary, a further process called pigmentization is required to achieve the desired particle size and crystal shape.

Many of the pigments used in the present invention, when made into pigments, exhibit crystalline properties rather than molecular properties. The crystalline properties create a band gap, and the transfer of electrons to advance the reaction occurs through the valence band or conduction band. When multiple pigments are present, the electrons necessary for the reaction can move between pigments, as in hopping conduction, even in the presence of the resin, making it possible for electrons to be accepted by specific functional groups in bacteria, etc.

On the other hand, in the case of dyes, the decomposition reaction occurs through an oxidation-reduction reaction, that is, when the molecule transitions from HOMO to LUMO, or when a specific atom comes into contact with a specific functional group of bacteria, etc.

In other words, because pigments have crystalline properties, their antibacterial and antiviral effects can extend beyond the area of contact with the pigment to an area slightly distant from the pigment. Specifically, in the case of dyes, the antibacterial properties disappear when the dye is covered with resin in a coating, etc., but in the case of pigments, the antibacterial and antiviral effects can be maintained even if the pigment is slightly covered with resin in a coating, etc.

For example, among phthalocyanine metal species, metal species that are more likely to undergo oxidation-reduction of metal ions in electrochemical reactions are expected to have higher antibacterial and antiviral properties than metal species that are more likely to undergo oxidation-reduction of the phthalocyanine ring.

The pigment may be in a particulate or needle shape, and there is no particular limit to the shape. There are no particular limits to the particle size or aspect ratio, but in general, the average particle size of finely divided or refined pigment is preferably 20 to 300 nm, and the aspect ratio is preferably about 1 to 10, and more preferably 20 to 200 nm, and the aspect ratio is about 1 to 5.

[Inorganic pigments]
Inorganic pigments used in the antibacterial and antiviral agents of the present invention include metal compounds such as titanium, zinc, lead, chromium, iron, cobalt, cadmium, and copper, high-carbon substances such as carbon black, metal powders such as aluminum and copper, and nanoparticles of gold and silver, but are not particularly limited and publicly known and commonly used pigments can be used. In addition, they are classified according to their usage characteristics into extender pigments, white pigments, colored pigments, and pearl pigments, but can be used without particular limitations. Examples of extender pigments include clay minerals and silica, examples of white pigments include titanium dioxide, and examples of colored pigments include pigments such as iron oxide, ultramarine, Prussian blue, and carbon black. Among the inorganic pigments, iron oxide is particularly preferred. These pigments can be used alone or in combination of two or more.

The iron oxide used in the present invention is not particularly limited, and any known and commonly used iron oxide can be used. Black iron oxide refers to _triiron tetroxide and is expressed as _Fe3O4 (or _FeOFe2O3 ), red iron oxide refers to iron( _III ) oxide and is expressed as _Fe2O3 , and yellow iron oxide refers to _{ferric hydroxide} and is expressed as _Fe2O3.H2O (or _FeOOH ). Among the above iron oxides, black iron oxide and red iron oxide are particularly preferred.

For example, C.I. Pigment Black 11, C.I. Pigment Red 101, C.I. Pigment Red 102, C.I. Pigment Brown 6, C.I. Pigment Yellow 42, C.I. Pigment Yellow 43, etc. are listed. Among them, C.I. Pigment Black 11 and C.I. Pigment Red 101 are preferable.

The pigments of the present invention can be organic or inorganic pigments used alone or in combination.

[Fatty acid metal salt]
The fatty acid metal salt used in the antibacterial and antiviral agents of the present invention contains, as a metal species, lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth. Among these, neodymium, lanthanum, and cobalt have high antibacterial and antiviral effects and are therefore preferred in the present invention.

The fatty acid metal salt used in the antibacterial and antiviral agents of the present invention is, for example, a compound represented by the following general formula (14).

(In the general formula (14),
R is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms;
n is an integer ranging from 1 to 4;
M is lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or a rare earth.

In the general formula (14), when n is an integer of 2 or more, the multiple R's may be the same or different.

The alkyl group having 1 to 21 carbon atoms represented by R may be a straight-chain alkyl group, a branched alkyl group, or may contain an alicyclic structure.

The alkyl group of R having 1 to 21 carbon atoms corresponds to a carboxylic acid residue obtained by removing the carboxyl group (COOH) from a carboxylic acid having 2 to 22 carbon atoms, represented by RCOOH, used in the production of fatty acid metal salts. Examples of the carboxylic acid residue include acetic acid residue, propionic acid residue, butanoic acid residue, pentanoic acid residue, acrylic acid residue, methacrylic acid residue, octylic acid residue (2-ethylhexanoic acid residue), neodecanoic acid residue, naphthenic acid residue, isononanoic acid residue, tung oil acid residue, tall oil fatty acid residue, coconut oil fatty acid residue, soybean oil fatty acid residue, linseed oil fatty acid residue, safflower oil fatty acid residue, dehydrated castor oil fatty acid residue, tung oil fatty acid residue, lauric acid residue, myristic acid residue, palmitic acid residue, stearic acid residue, isostearic acid residue, and oleic acid residue.

The alkyl group having 1 to 21 carbon atoms for R is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 11 carbon atoms, and even more preferably an acetic acid residue, a propionic acid residue, a butanoic acid residue, a pentanoic acid residue, a 2-ethylhexanoic acid residue, an isononanoic acid residue, a neodecanoic acid residue, or a naphthenic acid residue, from the viewpoint of adhesion to substrates described below.

M is lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum or rare earth, preferably bismuth, neodymium, magnesium, cobalt, copper, silver or zinc, more preferably bismuth, neodymium or magnesium.

If the metal in the fatty acid metal salt is bismuth, neodymium or magnesium, discoloration caused by the addition of antibacterial or antiviral agents can be prevented.

In the present invention, rare earth means one or more selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

n is a number determined by the ionic valence of the metal atom of M. For example, if M is boron, n is 3, and if M is cobalt, n is 2.

The fatty acid metal salts that are antibacterial and antiviral agents of the present invention also include fatty acid metal borate salts. The fatty acid metal borate salts are, for example, compounds represented by the following general formula (15).

(In the general formula (15),
R is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms;
M is boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or a rare earth.

In the general formula (15), the alkyl group of R having 1 to 21 carbon atoms is the same as the alkyl group of R having 1 to 21 carbon atoms in the general formula (14). Similarly, in the general formula (15), the metal of M is the same as the metal of M in the general formula (14).

The fatty acid metal salts used in the antibacterial and antiviral agents of the present invention can be used alone or in combination of two or more types.

Fatty acid metal salts can be produced by known methods, and commercially available products may also be used.

The fatty acid metal salts used in the antibacterial and antiviral agents of the present invention are neodymium neodecanoate, lanthanum neodecanoate, and cobalt 2-ethylhexanoate, which have high antibacterial and antiviral effects and are preferred in the present invention.

[Antibacterial and antiviral agents]
The antibacterial agent and antiviral agent of the present invention are compositions containing a pigment and a fatty acid metal salt, and may be present in either a form in which each is attached to the other, or a form in which one is coated on the other. In particular, a form in which the surface of the pigment is coated with the fatty acid metal salt is preferred.

The ratio of pigment to fatty acid metal salt in the antibacterial and antiviral agents of the present invention is, by mass, pigment: fatty acid metal salt = 99:1 to 50:50, preferably 98:2 to 60:40, and particularly preferably 95:5 to 70:30. If the ratio of fatty acid metal salt is 1% or more of the antibacterial and antiviral agents, this is preferred from the standpoint of antibacterial and antiviral properties, and if the ratio of fatty acid metal salt is 50% or less of the antibacterial and antiviral agents, this is preferred from the standpoint of ease of handling, so it is preferable that the ratio of pigment to fatty acid metal salt satisfies the above range.

When the surface of the pigment is coated with a fatty acid metal salt, the mass ratio of pigment:fatty acid metal salt is preferably 99:1 to 50:50, more preferably 98:2 to 60:40, and particularly preferably 95:5 to 70:30. The coating thickness of the fatty acid metal salt is preferably 1 to 10 nm. If the above range is satisfied, it is preferable from the viewpoint of ease of handling.

In the present invention, "antibacterial" means the effect of reducing the number of bacteria, the effect of inactivating bacteria, the effect of reducing the infectivity of bacteria, etc. Similarly, in the present invention, "antiviral" means the effect of reducing the number of viruses, the effect of inactivating viruses, the effect of reducing the infectivity of viruses, etc.

In the present invention, the bacteria to be treated with antibacterial agents are not particularly limited, and may be either bacteria or fungi. Examples of bacteria include gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, and Legionella; and gram-positive bacteria such as Staphylococcus aureus and Clostridium bacteria. Examples of fungi include yeasts such as Candida, Rhodotorula, and baker's yeast; and molds such as red mold and black mold.

In the present invention, there are no particular limitations on the viruses that are the target of antiviral treatment, and any of the known enveloped viruses (viruses that have an envelope) and non-enveloped viruses (viruses that do not have an envelope) may be used.

Examples of the enveloped viruses include coronavirus, influenza virus, rubella virus, Ebola virus, measles virus, chickenpox/shingles virus, herpes virus, mumps virus, arbovirus, respiratory syncytial virus, SARS virus, hepatitis virus (e.g., hepatitis A virus, hepatitis B virus, hepatitis C virus, hepatitis D virus, hepatitis E virus, etc.), yellow fever virus, AIDS virus, rabies virus, hantavirus, dengue virus, Nipah virus, lyssavirus, etc.

Examples of the non-enveloped viruses include adenovirus, norovirus, rotavirus, human papillomavirus, poliovirus, enterovirus, coxsackievirus, human parvovirus, encephalomyocarditis virus, polyomavirus, BK virus, rhinovirus, and feline calicivirus.

(Antibacterial effect)
Examples of indicators of antibacterial activity include a bacterial growth test using a culture kit or an antibacterial test specified in the JIS standard.

The main purpose of using culture kits is to understand the phenomenon in which common bacteria and fungi present in nature, such as food, air, and water, grow in the culture medium of the culture kit by observing the occurrence of colonies. However, by contacting the culture medium with a substance that has antibacterial properties, a certain amount of bacteria and fungi are killed or their growth is inhibited, so that colonies do not grow or the occurrence of colonies is delayed. Bacterial growth tests using culture kits can be evaluated by regular observation of the above phenomenon.

Examples of the common bacteria and fungi include, but are not limited to, Escherichia coli, Staphylococcus aureus, Bacillus cereus, Salmonella enterica, Pseudomonas aeruginosa, fungi, etc., or common live bacteria containing the bacteria and fungi.

Any commonly used culture kit can be used, such as the Sanai Biochecker, a simple microorganism measuring device (manufactured by Sanai Oil Co., Ltd.), or Compact Dry, a medium for measuring bacterial counts (manufactured by Nissui Pharmaceutical Co., Ltd.).

　The antibacterial tests specified in the JIS standard mainly target typical gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, and Moraxella, as well as gram-positive bacteria such as Staphylococcus aureus, MRSA, and Streptococcus pyogenes. In general, a test bacterial liquid is inoculated into a sample, and the bacterial liquid is placed in close contact with a film or glass and exposed to light for a certain period of time or left to stand in the dark, after which the collected bacterial liquid is diluted and cultured on an agar medium. After culture, the number of colonies that emerge is compared to determine the antibacterial activity value. Specifically, these include JIS R1702 Antibacterial test method and antibacterial effect for photocatalyst antibacterial processed products, JIS R1752 Antibacterial test method and antibacterial effect for visible light responsive photocatalyst processed products, JIS L1902 Antibacterial test method and antibacterial effect for textile products, JIS Z2801 Antibacterial processed products - Antibacterial test method and antibacterial effect, and the bacterial liquid absorption method, transfer method, bacterial transfer method, halo method, etc., as specified in JIS L1902 Antibacterial test method and antibacterial effect for textile products.

(Antiviral effect)
As an index of the antiviral action, antiviral tests defined in JIS standards and ISO standards can be mentioned.
Antiviral tests specified in the JIS and ISO standards are mainly targeted at typical enveloped influenza viruses, non-enveloped feline caliciviruses, or bacteriophages. In general, a virus liquid or bacteriophage liquid is inoculated into a sample, and the liquid is irradiated with light for a certain period of time while in contact with a film or glass or left to stand in a dark place, and the collected liquid is diluted and cultured on an agar medium. After culturing, the number of plaques is compared to determine the antiviral activity value. Alternatively, a virus liquid is inoculated into a sample, and the sample is irradiated with light for a certain period of time while in contact with a film or glass via the virus liquid or left to stand in a dark place, and the virus liquid on the sample is washed off and collected, and the virus infectivity is compared to determine the antiviral activity value. Specifically, examples of such antiviral tests include JIS R1706 Antiviral Test Method for Photocatalytic Materials--Method Using Bacteriophage Qβ, JIS R1756 Antiviral Test Method for Visible Light Response Photocatalytic Materials--Method Using Bacteriophage Qβ, ISO21702 Measurement of antiviral activity on plastics and other non-porous surfaces, and JIS L1922 Antiviral Test Method for Textile Products.

<Antibacterial property evaluation of coating film>
Antibacterial tests were carried out against Staphylococcus aureus (NBRC 12732) and Escherichia coli (NBRC 3972) using the following method.
A 5 cm x 5 cm coating film that had been cleaned by ultraviolet irradiation was inoculated with 0.1 ml of test bacteria liquid, and the bacteria liquid was placed in contact with a film or glass and left to stand in a dark place for 8 or 24 hours. The collected bacteria liquid was then diluted and cultured on an agar medium. After the culture, the antibacterial activity value was determined by comparing the number of colonies that had developed. The calculation formula is R = (U _t -U ₀ ) - (A _t -U ₀ ) = U _t -A _t (R: antibacterial activity value, U ₀ : average value of logarithm of viable bacteria count immediately after inoculation of unprocessed products, U _t : average value of logarithm of viable bacteria count after 8 or 24 hours of unprocessed products, A _t : average value of logarithm of viable bacteria count after 8 or 24 hours of processed products). The processed product is a coating film formed from a dispersion containing the test object, and the unprocessed product is a coating film formed from a PET film or a solution consisting of a synthetic resin, a polyurethane resin, and a solvent. As a guideline for antibacterial activity value, for example, JIS Z 2801:2021 Antibacterial processed products - Antibacterial test method, antibacterial effect specifies that the criterion for antibacterial effect is 2.0 or more. Also, an antibacterial activity value of 2.0 means that the processed product inhibited the growth of bacteria after the test by 99% compared to the unprocessed product. However, it does not necessarily mean that bacteria do not grow.

<Antiviral property evaluation of coating film>
Antiviral tests were carried out using bacteriophage Qβ (NBRC 20012, host E. coli (NBRC 106373)) and bacteriophage Φ6 (NBRC105899, host Pseudomonas syringae (NBRC14084)) in the following manner.
A test phage liquid was inoculated onto a 5 cm x 5 cm coating film, and the phage liquid was allowed to stand in the dark for 4 hours while being attached to a film or glass. The collected phage liquid was then diluted and cultured on an agar medium. After the culture, the antiviral activity value was determined by comparing the number of colonies that emerged. The calculation formula is V _D : Antiviral activity value (dark): [V _D = Log (B _D ) - Log (C _D )] (D: dark, B _D : infectivity value of unprocessed product after standing in the dark for 4 hours, C _D : infectivity value of processed product after standing in the dark for 4 hours). The processed product is a coating film formed from a dispersion containing the test object, and the unprocessed product is a coating film formed from a PET film or a solution consisting of a synthetic resin, a polyurethane resin, and a solvent.
Here, for example, an antiviral activity value of 2.0 means that the treated product inhibited phage proliferation after the test by 99% compared to the untreated product, but does not necessarily mean that phage proliferation did not occur.

By utilizing the antibacterial and antiviral agents of the present invention, it is possible to provide inks, printed matter, paints, coatings, plastics, fibers, films, cosmetics, and the like. The applications detailed below are examples, and the antibacterial and antiviral agents of the present invention can be used for any application having antibacterial, sterilizing, and antiviral properties.

(Ink applications)
The antibacterial agent and antiviral agent of the present invention can provide a printing ink having antibacterial and antiviral effects. The printing ink can be prepared by mixing the antibacterial agent and antiviral agent of the present invention with various known and commonly used binder resins, various solvents, various additives, etc., according to a conventional preparation method. Specifically, the liquid ink can be prepared by preparing a liquid ink base ink having a high pigment concentration and using various binders, various solvents, various additives, etc.

The antibacterial and antiviral agents of the present invention make it possible to manufacture PU inks and NC inks with antibacterial and antiviral properties, and are suitable as organic compositions for gravure printing inks and flexographic printing inks. PU inks consist of PU resins, pigments, solvents, and various additives, while NC inks consist of NC resins, pigments, solvents, and various additives. The PU resin is not particularly limited as long as it has a urethane structure in its skeleton, and includes polyurethane, polyurethane polyurea, etc. Examples of the solvent include aromatic organic solvents such as toluene and xylene, ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone, ester-based solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate, alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono-n-propanol. Examples of the solvent include (poly)alkylene glycol monoalkyl ether solvents such as ethyl ether, ethylene glycol mono-i-propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol mono-i-propyl ether, (poly)alkylene glycol monoalkyl ether acetate solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, and other ether solvents such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether. The solvents may be used alone or in combination of two or more. Examples of additives that can be used include anionic, nonionic, cationic, and amphoteric surfactants, rosins such as gum rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleic rosin, hardened rosin, and phthalic acid alkyd resin, pigment derivatives, dispersants, wetting agents, adhesive aids, leveling agents, defoamers, antistatic agents, trapping agents, antiblocking agents, and wax components.

When the antibacterial agent or antiviral agent of the present invention is used as a printing ink, the printing ink using the antibacterial agent or antiviral agent of the present invention prepared as described above can be used by diluting it with ethyl acetate, polyurethane varnish, or polyamide varnish. The printing ink can be prepared by using a known, conventional method.

(Paint applications)
When the antibacterial agent and antiviral agent of the present invention are used as a paint having antibacterial and antiviral activity, various resins can be used as the paint, such as acrylic resin, melamine resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, and phenol resin.

Solvents used in paints include aromatic solvents such as toluene, xylene, and methoxybenzene; acetate ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxyethyl propionate; alcohol solvents such as methanol, ethanol, propanol, n-butanol, and isobutanol; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, and pyridine; lactone solvents such as γ-butyrolactone; carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate; and water. Suitable solvents include polar solvents such as propionates, alcohols, ethers, ketones, nitrogen compounds, lactones, and water that are soluble in water.

Also, when pigment additives and/or antibacterial and antiviral agents are dispersed or mixed in liquid resin to form a resin composition for paint, conventional additives such as dispersants, fillers, paint adjuvants, drying agents, plasticizers and/or auxiliary pigments can be used. This is achieved by dispersing or mixing each component alone or several together, by collecting all the components together, or by adding them all at once.   

　Dispersing machines for dispersing mixtures containing antibacterial and antiviral agents prepared for specific applications as described above include known dispersing machines such as dispersers, homomixers, paint conditioners, scandex, bead mills, attritors, ball mills, two-roll mills, three-roll mills, and pressure kneaders, but are not limited to these. Antibacterial and antiviral agents are dispersed by adding resins and solvents so that the viscosity is such that dispersion is possible using these dispersing machines. The high-concentration paint base after dispersion has a solids content of 5-20%, and resins and solvents are further mixed into this for use as a paint.

(for plastics)
The antibacterial agent and antiviral agent of the present invention can also be used for plastic applications having antibacterial and antiviral effects. When obtaining plastic molded products, for example, thermoplastic resins (plastics) for thermoforming such as injection molding and press molding, such as polyolefins such as polyethylene and polypropylene, and polyvinyl chloride resins, are used, and the antibacterial agent and antiviral agent of the present invention can be used by kneading them into these resins by a conventionally known method.

(Cosmetic applications)
The antibacterial and antiviral agents of the present invention can be used as cosmetics. There are no particular limitations on the cosmetics used, and the antibacterial and antiviral agents of the present invention can be used in various types of cosmetics.

The cosmetic product may be of any type so long as it can effectively exert its function. The cosmetic product may be a lotion, cream gel, spray, etc. Examples of the cosmetic product include skin care cosmetics such as face wash, makeup remover, toner, beauty essence, pack, protective emulsion, protective cream, whitening cosmetics, and UV protection cosmetics; makeup cosmetics such as foundation, face powder, makeup base, lipstick, eye makeup, blusher, and nail enamel; hair care cosmetics such as shampoo, hair rinse, hair treatment, hair styling agent, permanent wave agent, hair dye, and hair growth agent; and body care cosmetics such as body cleansing cosmetics, deodorant cosmetics, and bath additives.

The antibacterial and antiviral agents of the present invention used in the cosmetic can be appropriately set according to the type of cosmetic. The content in the cosmetic is usually in the range of 0.1 to 99% by mass, and generally, it is preferable that the amount is in the range of 0.1 to 10% by mass. On the other hand, in makeup cosmetics, the amount may be in the range of 5 to 80% by mass, 10 to 70% by mass, or 20 to 60% by mass. When the amount of the composition of the present invention contained in the cosmetic is in the above range, the functions such as coloring can be effectively expressed, and the functions required of the cosmetic can be maintained.

The cosmetics may contain, depending on the type of cosmetic, the antibacterial and antiviral agents of the present invention as well as acceptable cosmetic ingredients such as carriers, pigments, oils, sterols, amino acids, moisturizers, powders, colorants, pH adjusters, fragrances, essential oils, cosmetic active ingredients, vitamins, essential fatty acids, sphingolipids, self-tanning agents, excipients, fillers, emulsifiers, antioxidants, surfactants, chelating agents, gelling agents, thickeners, emollients, humectants, moisturizers, minerals, viscosity adjusters, flow adjusters, keratolytic agents, retinoids, hormonal compounds, alpha hydrochloride, and the like. These may include keto acids, alpha keto acids, antimycobacterial agents, antifungal agents, antibacterial agents, antiviral agents, analgesics, antiallergy agents, antihistamines, anti-inflammatory agents, anti-irritants, antitumor agents, immune system boosters, immune system suppressants, antiacne agents, anesthetics, disinfectants, insect repellents, skin cooling compounds, skin protectants, skin penetration enhancers, exfoliants, lubricants, fragrances, dyes, bleaching agents, hypopigmenting agents, preservatives, stabilizers, pharmaceuticals, light stabilizers, and spherical powders.

The cosmetic product can be produced by mixing the antibacterial agent, antiviral agent and other cosmetic ingredients of the present invention.
Furthermore, cosmetics containing the antibacterial and antiviral agents of the present invention can be used in the same manner as ordinary cosmetics, depending on the type of the cosmetic, etc.

When the antibacterial agent or antiviral agent of the present invention is used in paints or plastics, it is preferable that the antibacterial agent or antiviral agent of the present invention is present on the paint surface or in the vicinity of the plastic surface. The above adjustment can be made by adjusting the type of alkyl group R in the fatty acid metal salt represented by the above formula (14) or by controlling the dispersion conditions according to the type of resin used in the paint or plastic.

It has been found that the antibacterial and antiviral properties are particularly excellent when the antibacterial and antiviral agents of the present invention contain a composition in which the surface of a pigment is coated with a fatty acid metal salt. The reason for this is unclear, but it is speculated that when the composition in which the surface of a pigment is coated with a fatty acid metal salt, the uncoated pigment, or the uncoated fatty acid metal salt migrates to the vicinity of the surface of a paint film or plastic, the remaining components also tend to migrate to the vicinity of the surface.

The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples means "% by mass."

The pigments used in Examples 1 to 15 and Comparative Examples 1 to 13 are listed below.

(iron phthalocyanine)
The iron phthalocyanine used was P-26 (manufactured by Sanyo Pigment Co., Ltd.).

(Copper Phthalocyanine)
As copper phthalocyanine, C.I. Pigment Blue 15:3, product name: FASTOGEN BLUE PA5380 (manufactured by DIC Corporation) was used.

(Brominated chlorinated zinc phthalocyanine)
As the brominated chlorinated zinc phthalocyanine, C.I. Pigment Green 58, product name: FASTOGEN GREEN A110 (manufactured by DIC Corporation) was used.

(Quinacridone)
As the quinacridone, C.I. Pigment Violet 19, product name: FASTOGEN SUPER RED 7061BCONC (manufactured by DIC Corporation) was used.

(Perylene)
As perylene, C.I. Pigment Red 179, product name: PERRINDO MAROON 179 229-6438 (manufactured by DIC Corporation) was used.

(Diketopyrrolopyrrole)
As the diketopyrrolopyrrole, C.I. Pigment Red 254, product name: FASTOGEN SUPER RED 254 226-0200 (manufactured by DIC Corporation) was used.

(azobarium salts)
The azobarium salt used was C.I. Pigment Red 48:1, product name: SYMULER RED 3109 (manufactured by DIC Corporation).

(Diazolidinium)
The disazo used was C.I. Pigment Yellow 180, product name: SYMULER Fast Yellow BY2000GT (manufactured by DIC Corporation).

(black iron oxide)
The black iron oxide used was C.I. Pigment Black 11, product name: C33-134 SunCROMA Black Iron Oxide (manufactured by Sun Chemical Co.).

(red iron oxide)
The red iron oxide used was C.I. Pigment Red 101, product name: C33-128 SunCROMA Red Iron Oxide (manufactured by Sun Chemical Co.).

The methods for preparing the fatty acid metal salts used in Examples 1 to 15 and Comparative Examples 1 to 13 are described below.

(Preparation of neodymium neodecanoate)
A 1.0 L separable flask was charged with 224.8 g of neodecanoic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 60.0 g of neodymium oxide (manufactured by Kanto Chemical Co., Ltd.), and reacted at 130° C. After that, the mixture was dehydrated under reduced pressure at 0.08 bar using an aspirator at 130° C. for 2 hours to obtain neodymium neodecanoate. The obtained neodymium neodecanoate was a light purple, highly viscous, sticky solid.

(Preparation of lanthanum neodecanoate solution)
83.1 g of neodecanoic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 21.5 g of lanthanum oxide (manufactured by Kanto Chemical Co., Ltd.) were reacted at 130° C., and the mixture was dehydrated under reduced pressure at 130° C., after which 107.6 g of cyclohexane was added to obtain 208.5 g of a lanthanum neodecanoate solution. The lanthanum content in the obtained lanthanum neodecanoate solution was 8.8% by mass.

(Preparation of Cobalt 2-Ethylhexanoate Solution)
319.0 g of 2-ethylhexanoic acid (Kanto Chemical Co., Ltd.) and 100.0 g of cobalt hydroxide (FUJIFILM Wako Pure Chemical Industries, Ltd.) were reacted at 130° C., and the mixture was dehydrated under reduced pressure at 130° C., and 134.2 g of a petroleum hydrocarbon was added to obtain 502.3 g of a cobalt 2-ethylhexanoate solution. The cobalt content in the obtained cobalt 2-ethylhexanoate solution was 12 mass %.

The products obtained by distilling off the solvent from the neodymium neodecanoate and lanthanum neodecanoate solutions and the products obtained by distilling off the solvent from the cobalt 2-ethylhexanoate solution prepared above were soluble in isobutanol, methyl ethyl ketone, and toluene, but insoluble in acetone and propylene glycol monomethyl ether acetate. The solubility was evaluated by adding 0.1 g of the products obtained by distilling off the solvent from the neodymium neodecanoate or lanthanum neodecanoate solutions or the products obtained by distilling off the solvent from the cobalt 2-ethylhexanoate solution and 2.0 g of solvent to a screw bottle (13.5 mL), mixing, and leaving the mixture for a while. If no solids remained and the solution was transparent, the product was rated as "dissolved." If solids remained or the solution was cloudy, the product was rated as "insoluble."

The methods for preparing the compositions used in Examples 1 to 15 are described below. The amounts of pigment and fatty acid metal salt used in preparing the compositions are shown in Table 1.

(Preparation of Composition 1)
In a 0.5 L separable flask, 5.0 g of neodymium neodecanoate and 60.0 g of isobutanol (Kanto Chemical Co., Ltd.) were mixed and stirred, and then 20.0 g of iron phthalocyanine and 120.0 g of water were added and refluxed for 1 hour with stirring. Then, 120.0 g of water was added and the solvent was distilled off, followed by filtration, washing, drying and pulverization to obtain Composition 1.

(Preparation of Compositions 2, 5 to 15)
In a 0.5 L separable flask, fatty acid metal salt and 30.0 g of isobutanol (Kanto Chemical Co., Ltd.) were mixed and stirred, and then pigment and 60.0 g of water were added and refluxed for 1 hour with stirring. Then, 60.0 g of water was added and the solvent was distilled off, followed by filtration, washing, drying and pulverization to obtain a composition.

(Compositions 3 and 4)
The fatty acid metal salt was distilled off using a 50 mL eggplant flask, and 30.0 g of isobutanol (Kanto Chemical Co., Ltd.) was added and transferred to a 0.5 L separable flask. Then, the pigment and 60.0 g of water were added, and the mixture was refluxed for 1 hour while stirring. Then, 60.0 g of water was added, and the solvent was distilled off, followed by filtration, washing, drying, and pulverization to obtain a composition.

Elemental mapping was carried out by SEM-EDS measurement on the obtained compositions 1 to 15. As a result, for compositions 1 to 15, elements corresponding to the metal species of the fatty acid metal salt were detected in the same location as the particle image, and it is inferred that the fatty acid metal salt adheres to or covers the pigment surface. For SEM-EDS, the obtained compositions were platinum-deposited and measured using a scanning electron microscope (SEM, product name: JSM-IT200 (LA) (manufactured by JEOL Ltd.)) equipped with an energy dispersive X-ray analyzer (EDS). The measurement conditions were a working distance (WD) of 10 mm, an accelerating voltage of 15.0 or 20.0 kv, and a visual field of 1000x to 5000x.

For example, the SEM-EDS results for composition 1 are shown in Figures 1 and 2. Figure 1 shows an SEM image of composition 1, and Figure 2 shows the results of element mapping by SEM-EDS measurement at the same position and magnification as Figure 1, with the white areas indicating the distribution of neodymium. As the particle image and neodymium are detected in the same place, it can be inferred that a fatty acid metal salt is attached to or coated on the iron phthalocyanine surface.

　Below is a description of how to prepare the coating film used in the antibacterial and antiviral tests.

The following resins were used in preparing the coating film:
Resin 1: Synthetic resin (product name: V343-306SA (manufactured by DIC Graphics Corporation, solid content concentration: 25%, weight ratio of solvent: methyl ethyl ketone/ethyl acetate/toluene = 35/20/20)
Resin 2: Synthetic resin (product name: V343-306SA (manufactured by DIC Graphics Corporation, solid content concentration: 25%, weight ratio of solvents: methyl ethyl ketone/ethyl acetate/toluene = 35/20/20)) from which the solvent components have been distilled off. Resin 3: Polyurethane resin (product name: Sanprene IB-D12 (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration: 30%, weight ratio of solvents: methyl ethyl ketone/isopropanol = 47/23)
Resin 4: Polyurethane resin (product name: Sanprene IB-D12 (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration: 30%, weight ratio of solvent: methyl ethyl ketone/isopropanol = 47/23)) obtained by distilling off the solvent component

The solvents used in preparing the coating were acetone (Kanto Chemical Co., Ltd.) and propylene glycol monomethyl ether acetate (PGMEA, Kanto Chemical Co., Ltd.), or methyl ethyl ketone (MEK, Kanto Chemical Co., Ltd.) and toluene (Kanto Chemical Co., Ltd.).

The formulations used to prepare the coating films of Examples 1 to 15 and Comparative Examples 1 to 13 are shown in Tables 2 and 3. In Examples 1 to 15, coating films were prepared using the compositions obtained in the composition preparation step according to the formulation in Table 2, while in Comparative Examples 1 to 13, coating films were prepared by mixing pigments or fatty acid metal salts according to the formulations in Table 3. The amount added refers to the weight ratio of the composition, pigment, or fatty acid metal salt contained relative to the resin solid content in the coating film.

(Examples 1 to 15)
Using the formulations in Table 2, each coating film was obtained in the following manner.

The antibacterial agent, antiviral agent, resin, solvent, and 80 g of 1/8 inch steel beads were placed in a plastic bottle and shaken for 30 minutes in a paint conditioner to obtain a dispersion.

The resulting dispersion was applied to a 188 μm PET film using a No. 6 bar coater, dried with a dryer, and further dried at 150°C for 15 minutes to obtain the coatings of Examples 1 to 15.

(Comparative Examples 1 to 13)
Using the formulations in Table 3, each coating film was obtained in the following manner.

Pigment or fatty acid metal salt, resin, solvent, and 80 g of 1/8 inch steel beads were placed in a plastic bottle and shaken for 30 minutes with a paint conditioner to obtain a dispersion.

The resulting dispersion was applied to a 188 μm PET film using a No. 6 bar coater, dried with a dryer, and further dried at 150°C for 15 minutes to obtain the coatings of Comparative Examples 1 to 13.

<Antibacterial test 1>
With reference to JIS R 1752:2020, an antibacterial test was conducted on Escherichia coli (NBRC3972) using the following method.

　A 5 cm x 5 cm coating that had been cleaned by UV irradiation was inoculated with 0.1 ml of test bacteria liquid, and the liquid was left in a dark place for 24 hours while attached to a film or glass. The collected bacteria liquid was then diluted and cultured on an agar medium. After culture, the antibacterial activity value was calculated by comparing the number of colonies that emerged. The calculation formula is R = (Ut - U0) - (At - U0) = Ut - At (R: antibacterial activity value, U0: average logarithm of the number of live bacteria immediately after inoculation in the unprocessed product, Ut: average logarithm of the number of live bacteria after 24 hours in the unprocessed product, At: average logarithm of the number of live bacteria after 24 hours in the processed product). The processed product is a coating film formed from a dispersion containing the test object, and the unprocessed product is a PET film.

<Antibacterial test 2>
An antibacterial test was carried out in the same manner as in <Antibacterial Test 1>, except that Staphylococcus aureus (NBRC12732) was used instead of Escherichia coli (NBRC3972).

<Antibacterial test 3>
With reference to JIS R 1752:2020, an antibacterial test was conducted on Escherichia coli (NBRC3972) using the following method.

　A 5cm x 5cm coating that had been cleaned by UV irradiation was inoculated with 0.1ml of test bacteria liquid, and the bacteria liquid was left in contact with a film or glass in a dark place for 8 hours. The collected bacteria liquid was then diluted and cultured on an agar medium. After culture, the antibacterial activity value was calculated by comparing the number of colonies that emerged. The calculation formula is R = (Ut - U0) - (At - U0) = Ut - At (R: antibacterial activity value, U0: average logarithm of the number of live bacteria immediately after inoculation on unprocessed products, Ut: average logarithm of the number of live bacteria 8 hours after inoculation on unprocessed products, At: average logarithm of the number of live bacteria 8 hours after processing). The processed product is a coating film formed from a dispersion containing the test object, and the unprocessed product is a coating film formed from a solution consisting of synthetic resin, polyurethane resin, and solvent.

<Antibacterial test 4>
An antibacterial test was carried out in the same manner as in <Antibacterial Test 3>, except that Staphylococcus aureus (NBRC12732) was used instead of Escherichia coli (NBRC3972).

<Antiviral test 1>
With reference to JIS R 1756:2020, an antiviral test was performed using bacteriophage Qβ (NBRC20012, host Escherichia coli (NBRC106373)) by the following method.

　A 5 cm x 5 cm coating was inoculated with a test phage liquid, and the phage liquid was left to stand in a dark place for 4 hours while it was attached to a film or glass. The collected phage liquid was then diluted and cultured on an agar medium. After culture, the antiviral activity value was calculated by comparing the number of colonies that emerged. The calculation formula is VD: Antiviral activity value (dark): [VD = Log (BD) - Log (CD)] (D: dark, BD: infectivity value of unprocessed product after standing in a dark place for 4 hours, CD: infectivity value of processed product after standing in a dark place for 4 hours). The processed product is a coating film made from a dispersion containing the test object, and the unprocessed product is a PET film.

<Antiviral test 2>
With reference to JIS R 1756:2020, an antiviral test was performed using bacteriophage Qβ (NBRC20012, host Escherichia coli (NBRC106373)) by the following method.

　A 5cm x 5cm coating was inoculated with a test phage liquid, and the phage liquid was left to stand in a dark place for 4 hours while attached to a film or glass. The collected phage liquid was then diluted and cultured on an agar medium. After culture, the antiviral activity value was calculated by comparing the number of colonies that emerged. The calculation formula is VD: Antiviral activity value (dark): [VD = Log (BD) - Log (CD)] (D: dark, BD: infectivity value of unprocessed product after standing in a dark place for 4 hours, CD: infectivity value of processed product after standing in a dark place for 4 hours). The processed product is a coating film formed from a dispersion containing the test object, and the unprocessed product is a coating film formed from a solution consisting of synthetic resin, polyurethane resin, and solvent.

<Antiviral test 3>
An antiviral test was carried out in the same manner as in <Antiviral Test 2>, except that bacteriophage Φ6 (NBRC105899, host Pseudomonas syringae (NBRC14084)) was used instead of bacteriophage Qβ (NBRC20012, host Escherichia coli (NBRC106373)).

Antibacterial test 1 was carried out on the coatings of Example 1 and Comparative Examples 1 and 2. The results are shown in Table 4.

Antibacterial test 2 was carried out on the coatings of Example 1 and Comparative Examples 1 and 2. The results are shown in Table 5.

Antibacterial Test 3 was conducted on Examples 3, 5 to 10, 12, and 13, and Comparative Examples 5 to 10, 12, and 13. The results are shown in Table 6.

Antibacterial test 4 was carried out on Examples 2, 4 to 15, and Comparative Examples 3 to 13. The results are shown in Table 7.

Antiviral test 1 was carried out on the coatings of Example 1 and Comparative Examples 1 and 2. The results are shown in Table 8.

Antiviral test 2 was carried out on Examples 2, 3, 5-10, 12-13 and Comparative Examples 3-10, 12, and 13. The results are shown in Table 9.

Antiviral Test 3 was carried out on Examples 2 to 11, 14 to 15, and Comparative Examples 3 to 11. The results are shown in Table 10.

The results in Tables 4, 5, and 8 show that the coating film of Example 1 exhibits superior antibacterial and antiviral properties compared to the coating films of Comparative Examples 1 and 2.

The results in Tables 7, 9, and 10 show that the coating film of Example 2 exhibits superior antibacterial and antiviral properties compared to the coating films of Comparative Examples 3 and 4. Comparing Example 2 and Comparative Example 4, it was found that higher antibacterial and antiviral properties were expressed when the coating film was produced using the composition obtained in the composition preparation, rather than simply mixing the pigment and fatty acid metal salt when producing the coating film.

The results of Examples 1 to 4 and Comparative Examples 1 to 4 in Tables 4 and 5 to 10 show that compositions using various fatty acid metal salts exhibit excellent antibacterial and antiviral properties. Therefore, it can be said that various fatty acid metal salts can be used as the fatty acid metal salts that constitute the antibacterial and antiviral agents of the present invention.

The results of Examples 5 to 11 and Comparative Examples 5 to 11 in Tables 6, 7, 9, and 10 show that by preparing a composition, it is possible to improve the antibacterial and antiviral activity of organic pigments that do not have antibacterial or antiviral properties. Therefore, it can be said that various organic pigments can be used as the pigments that make up the antibacterial and antiviral agents of the present invention.

The results of Examples 12 and 13 and Comparative Examples 12 and 13 in Tables 6, 7 and 9 show that the antibacterial and antiviral activities of inorganic pigments that do not have antibacterial or antiviral properties are improved by preparing the composition. Therefore, it can be said that various inorganic pigments can be used as the pigments that make up the antibacterial and antiviral agents of the present invention.

The results for Examples 2, 14, and 15 in Tables 7 and 10 show that all of them have high antibacterial and antiviral properties, but as the ratio of neodymium neodecanoate to iron phthalocyanine increases, the antibacterial and antiviral properties decrease slightly. This is because neodymium neodecanoate is a sticky solid, and as the ratio of neodymium neodecanoate to iron phthalocyanine increases, the composition aggregates more and does not disperse uniformly in the coating film, which is thought to be why the antibacterial and antiviral properties decrease.

Claims (7)

1. An antibacterial and antiviral agent characterized by containing an organic or inorganic pigment and a fatty acid metal salt.
2. The antibacterial and antiviral agent according to claim 1, wherein the mass ratio of the organic or inorganic pigment to the fatty acid metal salt is 99:1 to 50:50 (organic or inorganic pigment: fatty acid metal salt).
3. The antibacterial and antiviral agent according to claim 1 or 2, wherein the organic pigment is at least one selected from iron phthalocyanine, copper phthalocyanine, soluble azo, insoluble azo, quinacridone, perylene, and diketopyrrolopyrrole.
4. The antibacterial and antiviral agent according to claim 1 or 2, wherein the inorganic pigment is at least one of iron oxide (III) and triiron tetroxide.
5. The fatty acid metal salt is represented by the following general formula (1):
   (In the general formula (1),
   R is a hydrogen atom or a linear or branched alkyl group having 8 to 21 carbon atoms which may contain an alicyclic structure,
   n is an integer ranging from 1 to 4, and when n is an integer of 2 or more, multiple R's may be the same or different.
   M is lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or a rare earth.
   The antibacterial agent or antiviral agent according to claim 1 or 2, characterized in that it is represented by the formula:
6. The antibacterial and antiviral agent according to claim 5, wherein the fatty acid metal salt is at least one selected from neodymium neodecanoate, lanthanum neodecanoate, and cobalt 2-ethylhexanoate.
7. Inks, printed matter, paints, coatings, plastics, fibers, films, and cosmetics that contain the antibacterial and antiviral agents described in claim 1 or 2.

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