CN118216520A - Antibacterial/antiviral composition, antibacterial/antiviral fabric, and antibacterial/antiviral film - Google Patents

Antibacterial/antiviral composition, antibacterial/antiviral fabric, and antibacterial/antiviral film Download PDF

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CN118216520A
CN118216520A CN202311753089.4A CN202311753089A CN118216520A CN 118216520 A CN118216520 A CN 118216520A CN 202311753089 A CN202311753089 A CN 202311753089A CN 118216520 A CN118216520 A CN 118216520A
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antibacterial
antiviral
mass
acid
metal
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河中俊介
藤田幸介
中村厚
中野宏明
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DIC Corp
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DIC Corp
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Abstract

The purpose of the present disclosure is to provide an antibacterial/antiviral composition, which suppresses the decrease in transparency of an article to be coated, exhibits excellent emulsion stability, excellent compatibility, and high antibacterial and antiviral properties, and an antibacterial/antiviral fabric and an antibacterial/antiviral film. The present disclosure is an antibacterial/antiviral composition comprising a core-shell structure having a core portion containing a metal compound (B) which is poorly soluble in an aqueous solvent (A) having a hydrogen bond term dH of 18.0 or more relative to a Hansen solubility parameter, an organic solvent (C) which is soluble in the metal compound (B), and a shell portion containing a surfactant (D) having an HLB value in the range of 11 to 18, and satisfying the following formula (1). dHC-dHA/. Gtoreq.30.0 (1).

Description

Antibacterial/antiviral composition, antibacterial/antiviral fabric, and antibacterial/antiviral film
Technical Field
The present disclosure relates to an antibacterial and antiviral composition, an antibacterial and antiviral fabric, and an antibacterial and antiviral film.
Background
Efforts have been made to impart antibacterial or antiviral properties to products (fiber/film/coated plates) that come into contact with the human hand in living spaces, and the interest in antiviral activity has been further raised due to the generation of novel coronaviruses. Thus, there is an increasing need in the world for "antibacterial and antiviral" products that reduce the likelihood of infection with pathogenic bacteria or viruses by human hands.
For example, patent document 1 describes an antibacterial composition containing an organic silver-based antibacterial agent such as silver behenate and an anti-coloring agent such as a polyhalogenated compound, and a molded article containing the composition. Further, by the technique of patent document 1, not only excellent antibacterial properties are provided, but also chemical changes of these resin components at the time of application or molding are suppressed, discoloration of the resin composition or resin molded product is prevented or reduced, and deterioration of antibacterial effect can also be prevented.
Patent document 2 describes a technique for forming metal ultrafine particles from a fatty acid metal salt containing a metal having an atomic weight of 50 to 200, and heating the resin at a temperature higher than the pyrolysis temperature of the fatty acid metal salt and lower than the thermal degradation temperature of the resin. Further, by the technique of patent document 2, the excellent adsorptivity, antibacterial property, and effect of inactivating minute proteins, etc. possessed by the metal ultrafine particles can be more effectively exhibited.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-248125
Patent document 2: japanese patent application laid-open No. 2010-121145
Disclosure of Invention
Problems to be solved by the invention
In the antibacterial composition containing the organic silver-based antibacterial agent described in patent document 1 and the technique using the silver compound such as silver fatty acid described in patent document 2, antibacterial properties are ensured by adding the antibacterial composition or the silver compound to a desired resin or the like or applying the antibacterial composition or the silver compound to a substrate. However, in the technique of patent document 1, the dispersibility of the organic silver-based antibacterial agent varies depending on the chemical structure of the organic silver-based antibacterial agent to be used and the compatibility with the resin to be blended, and therefore, there is a problem that so-called phase separation occurs in which the organic silver-based antibacterial agent aggregates depending on the kind of the resin. In addition, since a silver compound of the prior art typified by patent document 2 is often made of a particulate material, there is a problem that transparency of an article to be coated is impaired. Even in the case of an aqueous composition containing a metal compound having antibacterial or antiviral properties, which does not form a particulate metal material, the miscibility of the resin with the aqueous composition is poor depending on the hydrophilicity/hydrophobicity of the material itself such as the resin that is the object of compounding the aqueous composition, and as a result, phase separation occurs or the antibacterial or antiviral properties are reduced.
Accordingly, an object of the present disclosure is to provide an antibacterial/antiviral composition, an antibacterial/antiviral fabric, and an antibacterial/antiviral film, each of which suppresses a decrease in transparency of an article to be coated, exhibits excellent emulsion stability, and has excellent compatibility, high antibacterial/antiviral properties.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the present invention as shown in any one of the following [1] to [10] is achieved by using a specific composition to suppress a decrease in transparency of an article to be coated, and exhibiting excellent emulsion stability, excellent compatibility, high antibacterial and antiviral properties.
[1] An antibacterial and antiviral composition comprising:
An aqueous solvent (A) having a Hansen solubility parameter (HSP value) with a hydrogen bond term dH of 18.0 or more,
A metal compound (B) which is hardly soluble in the aqueous solvent (A),
An organic solvent (C) which is soluble in the metal compound (B),
A surfactant (D) having an HLB value within the range of 11 to 18,
The antibacterial and antiviral composition satisfies the following formula (1).
/dHC-dHA/≥3O.O (1)
(In the above formula (1), dHC represents a hydrogen bond term dH of the Hansen solubility parameter (HSP value) of the above organic solvent (C), dHA represents a hydrogen bond term dH. of the Hansen solubility parameter (HSP value) of the above aqueous solvent (A))
[2] The antibacterial and antiviral composition according to [1], which contains:
30 to 89.5% by mass of the aqueous solvent (A),
5 To 35% by mass of the metal compound (B),
5 To 40% by mass of the organic solvent (C), and
The surfactant (D) is 0.5 to 10 mass%.
[3] An antibacterial and antiviral composition comprising a core-shell structure comprising:
A core part containing a metal compound (B) which shows poor solubility in an aqueous solvent (A) having a hydrogen bond term dH of 18.0 or more with respect to a Hansen solubility parameter (HSP value) and an organic solvent (C) which shows solubility in the metal compound (B), and
A shell portion containing a surfactant (D) having an HLB value within a range of 11 to 18,
The antibacterial and antiviral composition satisfies the following formula (1).
/dHC-dHA/≥3O.O (1)
(In the above formula (1), dHC represents a hydrogen bond term dH of the Hansen solubility parameter (HSP value) of the above organic solvent (C), dHA represents a hydrogen bond term dH. of the Hansen solubility parameter (HSP value) of the above aqueous solvent (A))
[4] The antibacterial and antiviral composition according to [1] or [2], which comprises a core-shell structure comprising:
a core part containing the metal compound (B) and the organic solvent (C), and
A shell portion containing the surfactant (D).
[5] The antibacterial/antiviral composition according to any one of [1] to [4], wherein the metal compound (B) is 1 or more selected from fatty acid metal salts, metal complexes of ligands containing hetero atoms and metal ions, and metal complexes of ligands containing hetero atoms and fatty acid metal salts, and the metal of the fatty acid metal salts, the metal of the metal complexes of ligands containing hetero atoms and metal ions, and the metal of the metal complexes of ligands containing hetero atoms and fatty acid metal salts are each independently 1 or 2 or more selected from magnesium, manganese, cobalt, yttrium, lead, bismuth, and lanthanoid metals.
[6] The antibacterial/antiviral composition according to any one of [1] to [5], wherein the metal amount of the metal compound (B) is 0.01 to 50% by mass relative to the total solid content of the antibacterial/antiviral composition.
[7] An antibacterial and antiviral coating composition comprising an aqueous resin dispersion and the antibacterial and antiviral composition according to any one of [1] to [6 ].
[8] An antibacterial and antiviral fabric comprising a fabric and a coating layer comprising the antibacterial and antiviral coating composition of [7] as a raw material, which is attached to the fabric.
[9] An antibacterial antiviral film comprising a base film and a coating layer comprising the antibacterial antiviral coating composition of [7] provided on at least one surface of the base film.
[10] The antibacterial antiviral film according to [9], which has a difference in haze value from a blank film containing no metal compound (B) contained in the antibacterial antiviral composition according to [1] or [2] of 10% or less.
Effects of the invention
The present disclosure provides an antibacterial/antiviral composition, an antibacterial/antiviral fabric, and an antibacterial/antiviral film, each of which has excellent emulsion stability, excellent compatibility, high antibacterial/antiviral properties, and suppresses a decrease in transparency of an article to be coated.
Detailed Description
Hereinafter, embodiments of the present disclosure (hereinafter, referred to as "the present embodiments") will be described in detail, and the present disclosure is not limited to the following description, and can be implemented by various modifications within the scope of the gist thereof.
[ Antibacterial antiviral composition ]
The antibacterial and antiviral composition of the present disclosure must contain an aqueous solvent (a) having a hansen solubility parameter with a hydrogen bond term dH of 18.0 or more, a metal compound (B), an organic solvent (C) that is soluble in the metal compound (B), and a surfactant (D) having an HLB value in the range of 11 to 18. The aqueous solvent (a) in which the hydrogen bond term dH of the metal compound (B) with respect to hansen solubility parameter is 18.0 or more shows poor solubility. In addition, the antibacterial and antiviral composition of the present disclosure satisfies the following formula (1).
/dHC-dHA/≥3O.O (1)
(In the above formula (1), dHC represents a hydrogen bond term dH (HSP value) of the Hansen solubility parameter of the above organic solvent (C), dHA represents a hydrogen bond term dH (HSP value) of the Hansen solubility parameter of the above aqueous solvent (A))
The antibacterial and antiviral composition of the present disclosure preferably contains a core-shell structure having a core portion containing the metal compound (B) and the organic solvent (C), and a shell portion containing the surfactant (D).
This suppresses the decrease in transparency of the article to be coated, and exhibits excellent emulsion stability, excellent compatibility, high antibacterial and antiviral properties. If the antibacterial and antiviral composition is a liquid composition containing the aqueous solvent (a), a coating layer of the antibacterial and antiviral composition can be easily formed on the object.
As another specific method of the antibacterial and antiviral composition of the present disclosure, the antibacterial and antiviral composition of [3] may be used instead of the antibacterial and antiviral composition of [1 ]. Specifically, the antibacterial and antiviral composition of the present disclosure contains an aqueous solvent (a) (hereinafter, abbreviated as aqueous solvent (a)) having a hydrogen bond term dH of 18.0 or more (for example, 30 to 89.5 mass%), a metal compound (B) (hereinafter, abbreviated as metal compound (B)) showing poor solubility with respect to the aqueous solvent (a) (for example, 5 to 35 mass%), an organic solvent (C) (hereinafter, abbreviated as organic solvent (C)) showing solubility with respect to the metal compound (B) (for example, 5 to 40 mass%), and a surfactant (D) (hereinafter, abbreviated as surfactant (D)) having an HLB value in the range of 11 to 18 (for example, 0.5 to 10 mass%), and satisfies the following formula (1) in the antibacterial and antiviral composition.
/dHC-dHA/≥3O.O (1)
(In the above formula (1), dHC represents a hydrogen bond term dH (HSP value) of the Hansen solubility parameter of the above organic solvent (C), dHA represents a hydrogen bond term dH (HSP value) of the Hansen solubility parameter of the above aqueous solvent (A))
Or the antibacterial/antiviral composition of the present disclosure has a core-shell structure comprising a core portion containing a metal compound (B) which shows poor solubility in an aqueous solvent (a) having a hydrogen bond term dH of 18.0 or more with respect to hansen solubility parameters (HSP value) and an organic solvent (C) which shows solubility with respect to the metal compound (B), and a shell portion containing a surfactant (D) having an HLB value in the range of 11 to 18, and satisfies the above formula (1).
This suppresses the decrease in transparency of the article to be coated, and exhibits excellent emulsion stability, excellent compatibility, high antibacterial and antiviral properties. In particular, by having a core-shell structure, more excellent emulsion stability and compatibility can be exhibited.
(Hansen solubility parameter (HSP value))
In this embodiment, as shown in the above formula (1), the absolute value of the difference between the hydrogen bond term dHA of hansen solubility parameter of the aqueous solvent (a) and the hydrogen bond term dHC of hansen solubility parameter of the organic solvent (C) is 30.0 or more, more preferably 32.0 or more, still more preferably 32.0 or more and 42.3 or less, still more preferably 35.0 or more and 42.3 or less, and particularly preferably 40.0 or more and 42.3 or less.
When the absolute value of the difference between the hydrogen bond term dHA of hansen solubility parameter of the aqueous solvent (a) and the hydrogen bond term dHC of hansen solubility parameter of the organic solvent (C) is 30 or more, excellent emulsion stability is exhibited, for example, the core-shell structure is easily stabilized or the metal compound (B) is not easily dissolved into the aqueous solvent (a).
Hansen solubility parameters (Hansen solubility parameter, HSP) are values that can be used to predict the solubility of a substance. HSPs are based on the consideration that "2 substances with similar intermolecular interactions are easily dissolved each other". Hansen solubility parameters (HSP values) [ unit: (J/cm 3)1/2) consists of the following 3 parameters.
D: energy based on intermolecular dispersion forces;
dP: energy based on intermolecular dipole interactions (dipole interaction term);
dH: energy based on intermolecular hydrogen bonds (hydrogen bond term).
The above 3 parameters (D, dP, dH) can be regarded as coordinates in three-dimensional space (hansen space), and hansen solubility parameters (HSP values) of the respective substances are set as D [ units: when the HSP values of the 2 substances are placed in the Hansen space, the closer the distance between the 2 points (Ra value) is, the more easily the substances dissolve in each other.
The Ra value represents the inter-HSP distance between 2 species obtained from the dispersion force term (d), the polarity term (dP) and the hydrogen bond term (dH) in hansen solubility parameters. When the dispersion force term of the aqueous solvent (a) is dA, the polarity term is dPA, the hydrogen bond term is dHA, the dispersion force term of the organic solvent (C) is dC, the polarity term is dPC, and the hydrogen bond term is dHC, the distance (Ra value) between the HSP value of the organic solvent (C) and the HSP value of the aqueous solvent (a) can be obtained by the following formula (2).
(Ra)2=4(dA-dC)2+(dPA-dPC)2+(dHA-dHC)2 (2)
In the present disclosure, it was found that the difference in hydrogen bond terms (dH) in hansen solubility parameters has a large effect on excellent emulsion stability.
The hansen solubility parameter of the surfactant (C) in the present embodiment can be calculated by, for example, the following methods (i) and (ii).
(I) A transparent screw vial (screw vial, capacity: 20cm 3) was charged with 50mg (0.05 g) of the surfactant (C) to be measured and 9.95g (concentration of the surfactant (C: 0.5 mass%) of an organic solvent having a known Hansen solubility parameter, mixed by shaking for 30 minutes with a high-speed shaker (CUTE MIXER), and then allowed to stand at 25℃for 24 hours.
(Ii) When the total dissolution of the surfactant (C) can be confirmed by visual observation after 24 hours of standing, the organic solvent is determined to be "good solvent", and when the total dissolution cannot be confirmed such as the presence of dissolution residue, the organic solvent is determined to be "poor solvent".
The organic solvent and the result of the determination "good solvent" or "poor solvent" corresponding thereto are input into hansen solubility parameter 4th Edition (Hansen Solubility PARAMETERS IN PRACTICE th Edition) 4.1.07 (hsPIP) "in the practice of computer software, and hansen solubility parameter of the surfactant (C) to be measured is calculated.
The hansen solubility parameter of the organic solvent used in the calculation of the hansen solubility parameter of the surfactant (C) can be directly the value recorded in the above computer software "hansen solubility parameter 4 th edition 4.1.07 (hsPIP)" in practice, and thus, the hansen solubility parameter may be known.
The hansen solubility parameter of the aqueous solvent (a) of the present embodiment can be directly as recorded in the above computer software "hansen solubility parameter in practice 4 th edition 4.1.07 (hsPIP)". When the aqueous solvent (a) is a mixture, 3 parameters of HSP values of known components can be regarded as unit vectors, and can be calculated as a synthetic vector based on the composition ratio. Furthermore, the solubility parameter using the hildebrand method (including the hansen method) can be calculated by a known method such as a method based on drawing (plot) hansen balls, for example, including: step (I): a dissolution test is performed, and a sample to be tested is added to a solvent having a known SP value to determine whether or not the sample is dissolved in the solvent having a known SP value. Step (II): next, the SP value of the solvent subjected to the dissolution test of step (I) was three-dimensionally plotted (plot). Step (III): the operations of step (I) and step (II) are carried out with 15 to 20 solvents. Step (IV): a sphere containing the coordinates of the solvent in which the sample was dissolved and not containing the coordinates of the solvent in which the sample was not dissolved was calculated, and thus the center coordinates of the sphere represent the SP value of Hansen (Hansen), and the distance from the origin represents the SP value of Hildebrand (Hildebrand).
Similarly, the hansen solubility parameter of the organic solvent (C) of the present embodiment can be directly used as the value recorded in the above computer software "hansen solubility parameter in practice 4 th edition 4.1.07 (hsPIP)". In the case where the organic solvent (C) is a mixture, 3 parameters of HSP values of known components are regarded as unit vectors, and calculated as a synthetic vector based on the composition ratio, similarly to the case where the aqueous solvent (a) is a mixture. Other known methods can be used as well for calculation.
(Core-shell Structure)
The core-shell structure of the present embodiment has a polymer micelle structure in which polymer chains constituting a plurality of surfactants (D) are associated with each other with a hydrophobic portion as a core, thereby forming particles having a predetermined particle diameter (for example, about 0.1 μm to 50 μm), and the metal compound (B) and the organic solvent (C) are enclosed in the hydrophobic portion as the inside.
The component (metal compound (B) or the like) exhibiting antibacterial and antiviral ability contained in the antibacterial and antiviral composition of the present embodiment has such a polymer micelle structure, and thus exhibits higher compatibility in various resins and various polar solvents. Further, it is considered that the core portion is blocked from the external atmosphere by the polymeric micelle structure, and therefore, elution of the metal in the metal compound (B) and chemical reaction are unlikely to occur, and as a result, high antibacterial and antiviral ability can be maintained for a long period of time.
When the antibacterial and antiviral composition of the present embodiment contains a core-shell structure having a core portion containing the metal compound (B) and the organic solvent (C) and a shell portion containing the surfactant (D), the average primary particle diameter of the core-shell structure is preferably 0.1 to 50 μm, more preferably 0.2 to 30 μm, still more preferably 0.24 to 20 μm, still more preferably 0.28 to 10 μm, still more preferably 0.3 to 5 μm, and still more preferably 0.5 to 3 μm.
When the average primary particle diameter of the core-shell structure is within the above range, the core-shell structure is less likely to settle, and therefore, more excellent compatibility is exhibited. As a method of controlling the average primary particle diameter of the core-shell structure to the above range, the weight average molecular weight (Mw) of the surfactant (D), the kind of the organic solvent (C), the compatibility of the surfactant (D) with the organic solvent (C), and the like may be adjusted.
Examples of the method for measuring the average primary particle diameter of the core-shell structure in the present specification include Dynamic Light Scattering (DLS) and microscopic observation, and in the present specification, calculation is performed using a particle size distribution analyzer (SZ-100, manufactured by shimadzu corporation) based on a photon correlation method which is one of the dynamic light scattering methods.
Specifically, the antibacterial and antiviral composition was diluted to 10 times with water, the refractive index of the solvent was set to water (1.333), the refractive index of the sample was set to polystyrene (1.590 to 0.000 i) (japanese megaly), and the particle size distribution was measured, with the median particle diameter as the average primary particle diameter.
In the embodiment in which the antibacterial/antiviral composition of the present disclosure contains the aqueous solvent (a), the metal compound (B), the organic solvent (C), and the surfactant (D), the total amount of the aqueous solvent (a), the metal compound (B), the organic solvent (C), and the surfactant (D) is preferably 60 to 100% by mass, more preferably 70 to 99% by mass, still more preferably 80 to 99% by mass, still more preferably 85 to 99% by mass, and particularly preferably 90 to 99% by mass, relative to the total amount (100% by mass) of the antibacterial/antiviral composition.
In the embodiment in which the antibacterial and antiviral composition of the present disclosure contains the metal compound (B), the organic solvent (C), and the surfactant (D), the total amount of the metal compound (B), the organic solvent (C), and the surfactant (D) is preferably 5% by mass or more, more preferably 5 to 90% by mass, still more preferably 5 to 80% by mass, still more preferably 8 to 80% by mass, and particularly preferably 10 to 75% by mass, relative to the total amount (100% by mass) of the antibacterial and antiviral composition.
In the embodiment in which the antibacterial and antiviral composition of the present disclosure contains the metal compound (B) and the surfactant (D), the total amount of the metal compound (B) and the surfactant (D) is preferably 3% by mass or more, more preferably 3 to 70% by mass, still more preferably 3 to 60% by mass, still more preferably 3 to 50% by mass, and particularly preferably 3 to 45% by mass, relative to the total amount (100% by mass) of the antibacterial and antiviral composition.
In the embodiment in which the antibacterial and antiviral composition of the present disclosure contains the aqueous solvent (a), the metal compound (B), the organic solvent (C), the surfactant (D) and the optional additive component (E), the total amount of the aqueous solvent (a), the metal compound (B), the organic solvent (C), the surfactant (D) and the optional additive component (E) is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to the total amount (100% by mass) of the antibacterial and antiviral composition.
In the embodiment in which the antibacterial and antiviral composition of the present disclosure contains the metal compound (B), the organic solvent (C), the surfactant (D) and the optional additive component (E), the total amount of the metal compound (B), the organic solvent (C), the surfactant (D) and the optional additive component (E) is preferably 5% by mass or more, more preferably 5 to 95% by mass, still more preferably 5 to 85% by mass, still more preferably 8 to 85% by mass, and particularly preferably 10 to 80% by mass, relative to the total amount (100% by mass) of the antibacterial and antiviral composition.
In the embodiment in which the antibacterial and antiviral composition of the present disclosure contains the metal compound (B), the surfactant (D) and the optional additive component (E), the total amount of the metal compound (B), the surfactant (D) and the optional additive component (E) is preferably 3% by mass or more, more preferably 3 to 75% by mass, still more preferably 3 to 65% by mass, still more preferably 3 to 55% by mass, and particularly preferably 3 to 50% by mass, relative to the total amount (100% by mass) of the antibacterial and antiviral composition.
In the embodiment in which the antibacterial and antiviral composition of the present disclosure contains the metal compound (B) and the organic solvent (C), the total amount of the metal compound (B) and the organic solvent (C) is preferably 3% by mass or more, more preferably 3 to 75% by mass, still more preferably 3 to 65% by mass, still more preferably 3 to 55% by mass, and particularly preferably 3 to 50% by mass, relative to the total amount (100% by mass) of the antibacterial and antiviral composition.
Hereinafter, after the terms used in the present specification are described, the components that can be contained in the antibacterial and antiviral composition of the present embodiment, that is, the aqueous solvent (a), the metal compound (B), the organic solvent (C), the surfactant (D), and optionally the additive component (E) are described.
(Terminology)
The term "antibacterial" in the present disclosure is intended to include an effect of reducing the number of bacteria, an effect of inhibiting the proliferation of bacteria, and the like. Similarly, in the present invention, "antiviral" is meant to include an effect of reducing the number of viruses, an effect of inactivating viruses, an effect of reducing the infectivity of viruses, and the like.
In the present disclosure, the bacteria to be an antibacterial object are not particularly limited, and may be any of bacteria and fungi. Examples of the bacteria include gram-negative bacteria such as Escherichia coli, pseudomonas aeruginosa, salmonella, moraxella and Legionella; gram positive bacteria such as Staphylococcus aureus and Clostridium bacteria. Examples of fungi include yeasts such as candida, rhodotorula and baker's yeast; and mould fungus such as rhodomyces and black myces.
In the present disclosure, viruses to be antiviral are not particularly limited, and may be any of well-known enveloped viruses (viruses having an envelope) and non-enveloped viruses (viruses having no envelope).
Examples of the enveloped virus include coronavirus, influenza virus, rubella virus, ebola virus, measles virus, varicella/zoster virus, herpes virus, mumps virus, arbovirus, RS virus, SARS virus, hepatitis virus (for example, hepatitis a virus, hepatitis b virus, hepatitis c virus, hepatitis delta virus, hepatitis e virus, etc.), yellow fever virus, aids virus, rabies virus, hantavirus, dengue virus, nipah virus, and lisa virus.
Examples of the non-enveloped virus include adenovirus, norovirus, rotavirus, human papilloma virus, poliovirus, enterovirus, coxsackievirus, human parvovirus, encephalomyocarditis virus, polyomavirus, BK virus, rhinovirus, and feline calicivirus.
In the present disclosure, "showing solubility with respect to the metal compound (B)" is referred to as "showing solubility with respect to the metal compound (B)" when 1g of the metal compound (B) is dissolved in 10ml or less of a solvent by the method for evaluating solubility described in the examples section described later. In the present disclosure, "showing poor solubility in the aqueous solvent (a)" is referred to as "showing poor solubility in the aqueous solvent (a)" when 100ml or more of the aqueous solvent (a) is required to dissolve 1g of a substance by the method for evaluating solubility described in the example column described below.
When the antibacterial and antiviral composition of the present embodiment is used as a so-called coating composition in which a coating layer is formed on the surface of a fabric or a substrate, the antibacterial and antiviral composition is referred to as an antibacterial and antiviral coating composition. The antibacterial and antiviral coating composition of the present disclosure must contain an aqueous solvent (a), a metal compound (B), an organic solvent (C), a surfactant (D), and an aqueous resin dispersion described later. Since the solvent is volatilized in the coating layer using the antibacterial and antiviral coating composition as a raw material, the coating layer contains the metal compound (B) and the surfactant (D).
When the antibacterial/antiviral composition of the present embodiment is used as a so-called curing composition in which a cured product or a molded article is formed from the antibacterial/antiviral composition, the antibacterial/antiviral composition is referred to as an antibacterial/antiviral curing composition. The antibacterial and antiviral curing composition of the present disclosure must contain an aqueous solvent (a), a metal compound (B), an organic solvent (C), a surfactant (D), and an aqueous resin dispersion described later. Since the solvent is volatilized in the cured product or molded article obtained from the antibacterial and antiviral curable composition, the cured product or molded article contains the metal compound (B) and the surfactant (D).
(Aqueous solvent (A))
The aqueous solvent (a) in the present specification means water or a solvent containing water as a main component. Therefore, the aqueous solvent (a) may contain water and components other than water (organic solvents, buffer solutions, salts, etc.). The "solvent containing water as a main component" may be any solvent as long as the water content in the aqueous solvent (a) is 50 mass% or more relative to the total amount of the aqueous solvent (a).
The aqueous solvent (a) of the present embodiment is water or an aqueous solution containing water, and is selected according to the relationship with the organic solvent (C). Specifically, the aqueous solvent (a) may be selected so as to satisfy the following formula (1).
/dHC-dHA/≥3O.O (1)
(In the above formula (1), dHC represents a hydrogen bond term dH of the Hansen solubility parameter (HSP value) of the above organic solvent (C), dHA represents a hydrogen bond term dH. of the Hansen solubility parameter (HSP value) of the above aqueous solvent (A))
Examples of water that can be used as the aqueous solvent (a) of the present embodiment include pure water, ultrapure water, RO water (water having passed through a reverse osmosis membrane), deionized water (water having ions removed by an ion exchange resin or the like), distilled water (water distilled by a distiller), and the like.
In addition, as a non-limiting example, the components contained in the aqueous solvent (A) of the present embodiment other than water, examples thereof include water-compatible organic solvent mixtures such as ketones having 1 to 3 carbon atoms such as acetone, lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol and isopropanol, nitriles having 2 to 3 carbon atoms such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, diethyl ether and cyclopentylmethyl ether, aqueous solutions of bis (oxalic acid) potassium trihydroxide, aqueous solutions of potassium hydrogen phthalate, aqueous solutions of potassium dihydrogen phosphate/disodium hydrogen phosphate, aqueous solutions of sodium tetraborate and aqueous solutions of sodium bicarbonate/sodium carbonate, buffers such as sodium chloride, potassium chloride, ammonium chloride, sodium bromide and potassium bromide inorganic/organic salt aqueous solutions such as ammonium bromide, aqueous saccharide solutions including allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, xylose, lyxose, erythrose, threose, allose, fructose, sorbose, tagatose, fucose, deoxysugar, amino sugar, uronic acid, thiosugar, alditol (alditol), cyclic polyol (cyclitol), ketose (ulose), branched sugar, glucose, starch, monosaccharides such as heparin and heparan sulfate, aqueous saccharide solutions of oligosaccharides, polysaccharides, aqueous protein solutions, DNA, RNA solutions, liquid culture media, and mixtures thereof. Further, the aqueous solvent (a) may contain a substance which is insoluble and dispersed therein, and examples thereof include minerals such as clay, metal microparticles such as gold nanoparticles, polymer microparticles such as polystyrene beads and latex particles, animal cells, plant cells, microorganisms, viruses, and the like, or mixtures thereof.
When the antibacterial and antiviral composition of the present embodiment contains the aqueous solvent (a), the upper limit of the content of the aqueous solvent (a) is preferably in the order of 95 mass% or less, 93 mass% or less, 90 mass% or less, 89.5 mass% or less, 88 mass% or less, and 87 mass% or less with respect to the total amount (100 mass%) of the antibacterial and antiviral composition. The lower limit of the content of the aqueous solvent (a) is preferably 20 mass% or more, 22 mass% or more, 24 mass% or more, 25 mass% or more, 26 mass% or more, and 30 mass% or more with respect to the total amount (100 mass%) of the antibacterial/antiviral composition.
The upper limit and the lower limit of the content of the aqueous solvent (a) may be arbitrarily combined.
When the content of the aqueous solvent (a) is in the range of 25 to 80 mass%, it is preferable from the viewpoint of storage stability of the aqueous emulsion.
In the antibacterial/antiviral composition of the present embodiment, the lower limit is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, further preferably 40 parts by mass, and the upper limit is preferably 89.5 parts by mass or less, more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, based on 100 parts by mass of the total of the aqueous solvent (a), the metal compound (B), the organic solvent (C), and the surfactant (D), with respect to the content of the aqueous solvent (a).
The pH of the aqueous solvent (a) of the present embodiment is preferably 3 to 11, more preferably 4 to 9, and even more preferably 6 to 8.
In the method for measuring pH in the present specification, measurement is performed using a glass electrode pH meter (for example, the product name "desktop pH meter F-72", manufactured by horiba, inc.).
If necessary, an acid or a base may be added to adjust the pH of the aqueous solvent (a). Examples of the acid used for adjusting the pH include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and the like, and organic acids such as formic acid, acetic acid, trichloroacetic acid, propionic acid, methanesulfonic acid, and p-toluenesulfonic acid. On the other hand, as the base for adjusting the pH, for example, any of an organic base (e.g., ammonia, triethylamine, pyridine, etc.) or an inorganic base may be used. Examples of the inorganic base used for adjusting the pH include sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium monohydrogen phosphate, sodium dihydrogen phosphate, and sodium phosphate.
The hydrogen bond term dH of hansen solubility parameter of the aqueous solvent (a) of the present embodiment is preferably 30 to 42.3 (J/cm 3)1/2, more preferably 32 to 42.3 (J/cm 3)1/2, still more preferably 40.0 to 42.3 (J/cm 3)1/2).
When the hydrogen bond term dH of the hansen solubility parameter of the aqueous solvent (a) is within the above range, the absolute value of the difference between the hydrogen bond term dHA of the hansen solubility parameter of the aqueous solvent (a) and the hydrogen bond term dHC of the hansen solubility parameter of the organic solvent (C) can be sufficiently obtained, and excellent emulsion stability is exhibited, and for example, it is preferable from the viewpoint that the core-shell structure is easily stabilized or the metal compound (B) is not easily dissolved into the aqueous solvent (a).
(Metal Compound (B))
The metal compound (B) of the present embodiment shows poor solubility with respect to the aqueous solvent (a). Specifically, the expression "poorly soluble in the aqueous solvent (A)" means that the amount of water at 20℃required for dissolving 1g of the metal compound (B) is 10ml or more. Further, whether or not the metal compound (B) is dissolved is determined based on the following criteria: as shown in the examples column, 1g of solute was put into a prescribed amount of solvent, and mixed with vigorous shaking at 20.+ -. 5 ℃ for 30 seconds every 5 minutes, to a degree of dissolution within 30 minutes. The term "melted" as used herein means that no residue can be visually confirmed.
The metal compound (B) exhibits poor solubility in the aqueous solvent (a), and thus, the metal compound (B) is easily transferred into the organic solvent (C) phase.
The metal compound (B) of the present embodiment is preferably a compound containing a metal having antibacterial or antiviral properties. The metal compound (B) is preferably a metal compound having a metal and a ligand coordinated to the metal. Thus, oxygen atoms and the like will not easily bond to the dangling bond (dangling bond) of the metal in the metal compound (B), and therefore, the antibacterial or antiviral performance will not easily be degraded by oxidation and the like.
The metal of the metal compound (B) of the present embodiment is preferably 1 or 2 or more selected from magnesium, manganese, cobalt, yttrium, lead, bismuth and lanthanoid metals, and more preferably 1 or 2 or more selected from magnesium, manganese, cobalt, yttrium, lead, bismuth, lanthanum, praseodymium, neodymium, samarium and gadolinium. If the metal is exemplified above, it has antibacterial or antiviral properties.
In the present embodiment, the ligand coordinated to the metal in the metal compound (B) may be a low molecule or a high molecule having a functional group having affinity for 1 metal selected from magnesium, manganese, cobalt, yttrium, lead, bismuth, and lanthanoid metal. The functional group having affinity is not particularly limited, but is preferably a group containing 1 element selected from nitrogen, oxygen, sulfur and phosphorus. Examples thereof include organic sulfur groups, organic phosphorus groups, pyrrolidone groups, pyridine groups, amino groups, amide groups, isocyanate groups, carbonyl groups, hydroxyl groups, and the like, and ligands having carboxylic acid, hydroxyl groups, or amino groups at the terminal end are preferable.
For example, a ligand having a carboxylic acid or a hydroxyl group as a terminal functional group, specifically, selected from 1, 3-propanediol octanoate/dicaprate; 10-undecylenic acid; 1-tridecyl alcohol; 1-heptadecanol; 1-icosadecanol; 2-ethylhexanol; androstane; eicosanoids; arachidonic acid; arachidyl alcohol; behenic acid; behenyl alcohol; capmul MCM C10; capric acid; decyl alcohol; octanol; octanoic acid; esters of saturated aliphatic alcohols C12 to C18 with caprylic/capric acid; caprylic/capric triglyceride; caprylic/capric triglyceride; ceramide phosphorylcholine (sphingomyelin, SPH); ceramide phosphoethanolamine (sphingomyelin, cer-PE); Ceramide phosphoglycerides; hexacosanoic acid (ceroplastic acid); wax acid; wax acid; a wax alcohol; cetostearyl alcohol (cetearyl alcohol); cetyl polyether-10; cetyl alcohol; a cholane; cholestane; cholesterol; cis-11-eicosenoic acid; cis-11-octadecenoic acid; cis-13-docosenoic acid; octacosanol; coenzyme Q10 (CoQ 10); dihomo-gamma-linolenic acid (dihomo-gamma-linolene); docosahexaenoic acid; lecithin; eicosapentaenoic acid; eicosenoic acid; Elaidic acid; linolen (elaidolinolenyl alcohol); linoleyl alcohol (elaidolinoleyl alcohol); oleyl alcohol (elaidyl alcohol); erucic acid; erucyl alcohol (erucyl alcohol); estrane; ethylene Glycol Distearate (EGDS); tritetradecanoic acid (GEDDIC ACID); tritetradecanol (geddyl alcohol); glycerol distearate (type I) EP (preprol ATO 5); tricaprylin/caprin; tricaprylin/caprin (CAPTE X (registered trademark) 355 EP/NF); glycerol monocaprylate (Capmul MCM C8 EP); triacetin; glycerol trioctanoate; tricaprylin/caprate/laurate; glycerol tricaprylate/tricaprate; tripalmitin (tripalmitin ); triundecanoic acid (henatriacontylic acid); di-undecanol; di-undecanoic acid; heptadecanoic acid; heptadecanoic acid; heptadecanol; hexacosanoic acid (Hexatriacontylic Acid); Isostearic acid; isostearyl alcohol; tridodecanoic acid (lacceroic acid); lauric acid; lauryl alcohol; wood wax acid; wood wax alcohol (lignoceryl alcohol); elaidic acid (linoelaidic acid); linoleic acid; linolenic alcohol; linoleyl alcohol; heptadecanoic acid; a midic acid; melissac acid; beeswax alcohol (melissyl alcohol); montanic acid; octacosanol (montanyl alcohol); melissa alcohol (myricyl alcohol); myristic acid; myristoleic acid (myristoleic acid); myristyl alcohol; neodecanoic acid; neoheptanoic acid; neononanoic acid; nervonic acid; icosahedonic acid; nonadecanol; nonadecanoic acid; nonadecanoic acid; oleic acid; oleyl alcohol; palmitic acid; palmitoleic acid (palmitoleic acid); palm oleyl alcohol (palmitoleyl alcohol); pelargonic acid; nonanol; cyclopentadecanoic acid; pentadecanol; pentadecanoic acid; phosphatidic acid (phosphatidate, PA); phosphatidylcholine (lecithin, PC); phosphatidylethanolamine (cephalin, PE); phosphatidylinositol (PI); phosphatidylinositol diphosphate (PIP 2); phosphatidylinositol phosphate (PIP); Phosphatidylinositol triphosphate (PIP 3); phosphatidylserine (PS); polyglycerol-6-distearate; pregnanes; propylene glycol dicaprate; propylene glycol dicaprylate/caprate; propylene glycol dicaprylate/caprate; phyllosilicic acid (PSYLLIC ACID); ricinoleic acid; ricinoleic alcohol; hexadecenoic acid (SAPIENIC ACID); soybean lecithin; stearic acid; stearidonic acid (stearidonic acid); stearyl alcohol; ditridecanoic acid; tridecyl alcohol; tridecanoic acid; glycerol trioleate (triolein); undecanol; undecylenic acid; Undecanoic acid; iso-oleic acid; alpha-linolenic acid; gamma-linolenic acid; 10-undecylenic acid, adapalene, arachidic acid, arachidonic acid, behenic acid, butyric acid, capric acid, caprylic acid, cerotic acid, cis-11-eicosenoic acid, cis-11-octadecenoic acid, cis-13-docosenoic acid, docosahexaenoic acid, eicosapentaenoic acid, elaidic acid, erucic acid, heneicosanoic acid, heptadecanoic acid, isostearic acid, lauric acid, cerotic acid, elaidic acid, linoleic acid, montanic acid, myristic acid, neodecanoic acid, neoheptanoic acid, neononanoic acid, nonadecanoic acid, oleic acid, palmitic acid, palmitoleic acid, nonanoic acid, eicosanoic acid, pentadecanoic acid, ricinoleic acid, Hexadecenoic acid (SAPIENIC ACID), stearic acid, tricosanoic acid, tridecanoic acid, undecylenic acid, undecanoic acid, isooleic acid (VACCENIC ACID), valeric acid, alpha-linolenic acid, gamma-linolenic acid; And any combination thereof.
In addition, as the ligand having an amino group as a terminal functional group, specifically, dodecylamine, tetradecylamine, 1-aminotridecane, 1-aminopentadecane, hexadecylamine, 1-aminopentadecane, stearylamine, heptadecane-9-amine, oleylamine, 1-aminononadecane, 2-n-octyl-1-dodecylamine are preferable.
The metal compound (B) of the present embodiment is preferably 1 or more selected from the group consisting of a fatty acid metal salt, a metal complex of a heteroatom-containing ligand and a metal ion, and a metal complex of a heteroatom-containing ligand and a fatty acid metal salt.
Thus, since the metal compound (B) has a fatty acid or a ligand containing a heteroatom as a ligand, the ligand is less likely to be eluted than when a metal ion is used alone, and is reduced to form a metal or the like, so that stability is improved, and the ligand is formed into a complex, whereby a specific characteristic which cannot be seen when a metal (ion) is used is easily exhibited. In addition, it is considered that dispersibility is improved.
In addition, when the metal compound (B) is a fatty acid metal salt or a metal complex, the antibacterial and antiviral properties of the metal and the high compatibility with organic substances of the fatty acid or the complex ligand are used, and thus when the metal compound (B) is added to an antibacterial and antiviral coating composition containing an aqueous resin dispersion described later, the antibacterial and antiviral properties can be imparted to the obtained coating layer, and at the same time, the decrease in transparency of the coating layer can be suppressed by the antibacterial and antiviral coating composition.
The preferable metal compound (B) of the present embodiment is 1 or more selected from the group consisting of a fatty acid metal salt, a metal complex of a heteroatom-containing ligand and a metal ion, and a metal complex of a heteroatom-containing ligand and a fatty acid metal salt, and the metal of the fatty acid metal salt, the metal of the heteroatom-containing ligand and a metal complex of a metal ion, and the metal of the heteroatom-containing ligand and a metal complex of a fatty acid metal salt are each independently preferably Mg, mn, co, Y, pb, bi, la, pr, nd, sm or Gd.
< Fatty acid Metal salt >
The metal compound (B) of the present embodiment is preferably a fatty acid metal salt.
The fatty acid metal salt of the present embodiment is preferably a compound represented by the following general formula (3), for example.
(In the above general formula (3), R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, n 1 represents an integer in the range of 1 to 4, and M 1 represents 1 or2 or more selected from magnesium, manganese, cobalt, yttrium, lead, bismuth and a lanthanoid metal.)
In the above general formula (3), when n 1 is an integer of 2 or more, a plurality of R 1 may be the same or different from each other. The alkyl group having 1 to 21 carbon atoms in R 1 may be a linear alkyl group, a branched alkyl group, or an alicyclic structure.
In the above general formula (3), the hydrogen atom of R 1 or the alkyl group having 1 to 21 carbon atoms corresponds to a carboxylic acid residue obtained by removing the carboxyl group (COOH) from the carboxylic acid having 1 to 22 carbon atoms represented by R 1 COOH used in the production of the fatty acid metal salt. Examples of the carboxylic acid residue include a formic acid residue, an acetic acid residue, a propionic acid residue, a butyric acid residue, a valeric acid residue, a caproic acid residue, a 2-ethylbutyric acid residue, a heptanoic acid residue, a caprylic acid residue, an acrylic acid residue, a methacrylic acid residue, a 2-ethylhexanoic acid residue (caprylic acid residue), a neodecanoic acid residue, a naphthenic acid residue, an isononanoic acid residue, a tung oil acid residue, a tall oil (tall oil) fatty acid residue, a coconut oil fatty acid residue, a soybean oil fatty acid residue, a linseed oil fatty acid residue, a safflower oil fatty acid residue, a dehydrated castor oil fatty acid residue, a tung oil fatty acid residue, a lauric acid residue, a myristic acid residue, a palmitic acid residue, a stearic acid residue, an isostearic acid residue, and an oleic acid residue.
In the above general formula (3), the alkyl group having 1 to 21 carbon atoms in R 1 is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 11 carbon atoms, from the viewpoint of adhesion to a substrate, which will be described later. R 1 is preferably a formic acid residue, an acetic acid residue, a propionic acid residue, a butyric acid residue, a valeric acid residue, a caproic acid residue, a 2-ethylbutyric acid residue, a heptanoic acid residue, a caprylic acid residue, a 2-ethylhexanoic acid residue, an isononanoic acid residue, a neodecanoic acid residue, a naphthenic acid residue, a stearic acid residue or an oleic acid residue.
In the above general formula (3), M 1 is more preferably 1 or 2 or more selected from magnesium, manganese, cobalt, yttrium, lead, bismuth, lanthanum, praseodymium, neodymium, samarium and gadolinium.
In the present specification, the lanthanoid metal means 1 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 1 is a value determined by the ionic valence of the metal atom of M1, for example, if M 1 is cobalt, n 1 becomes 2.
The fatty acid metal salt of the present embodiment also includes a fatty acid boric acid metal salt. The fatty acid metal borate is, for example, a compound represented by the following general formula (4).
(In the above general formula (4), R 2 is each independently a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, and M 2 is each independently magnesium, manganese, cobalt, yttrium, lead, bismuth, or a lanthanoid metal.)
In the general formula (4), the alkyl group having 1 to 21 carbon atoms in R 2 is the same as the alkyl group having 1 to 21 carbon atoms in R 1 in the general formula (3). Similarly, in the above general formula (4), a preferable metal of M 2 is the same as that of M 1 of the above general formula (3).
When a fatty acid metal salt is used as the metal compound (B) of the present embodiment, the fatty acid metal salt used may be 1 species alone, or 2 or more fatty acid metal salts having different structures may be used. The fatty acid metal salt may be produced by a known method, or may be commercially available.
< Metal Complex >
The metal compound (B) of the present embodiment is preferably 1 or 2 or more selected from the group consisting of a metal complex of a ligand containing a heteroatom and a metal ion, and a metal complex of a ligand containing a heteroatom and a fatty acid metal salt.
The metal complex of the heteroatom-containing ligand and the metal ion and the metal complex of the heteroatom-containing ligand and the fatty acid metal salt are compounds in which a complex is formed by a coordination bond between a metal ion or a fatty acid metal salt and a heteroatom-containing ligand.
As the metal ion, an ion of the same metal as the preferable metal of the fatty acid metal salt can be used. As the fatty acid metal salt of which the ligand containing a heteroatom forms a metal complex, the same substance as the fatty acid metal salt can be used.
The heteroatom-containing ligand forming the metal complex may be a ligand having 1 or more heteroatoms selected from nitrogen, oxygen, sulfur and phosphorus in the molecule. Examples of the heteroatom-containing ligand include N-methylmorpholine, pyridine, 1, 8-diazabicyclo [5.4.0] undecene-7 (DBU), 1, 5-diazabicyclo [4.3.0] nonene-5 (DBN), 1, 4-diazabicyclo [2.2.2] octane (DABCO), 4-Dimethylaminoamine (DMAP), dicyandiamide (dic), tri-N-butylamine, dimethylbenzylamine, butylamine, 1, 2-propylenediamine, 1, 2-cyclohexanediamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, 2- [ [ (2-dimethylamino) ethyl ] methylamino ] ethanol, picolinic acid, 2'- [ propane-1, 2-diylbis (nitrilomethyl) ] diphenol (japanese: 2,2' - [ i ] 2-1, 2-ridge ] ridge, and a second component of ridge; imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2, 4-dimethylimidazole, 1, 4-diethylimidazole 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- (N-phenyl) aminopropyl trimethoxysilane, 3- (2-aminoethyl) aminopropyl methyl dimethoxysilane, tetramethylammonium hydroxide, amine compounds such as 8-quinolinol, 5-chloro-8-quinolinol, 2' -bipyridine and its derivatives, 2' - [ propane-1, 2-diylbis (nitrilo-methine) ] diphenol and its derivatives, and 2,2' -methylenebis [ 6- (2 h-benzotriazol-2-yl) -4-t-octylphenol ]; quaternary ammonium salts such as trioctylmethyl ammonium chloride and trioctylmethyl ammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethyl phosphonium chloride, tetraethyl phosphonium chloride, tetrapropyl phosphonium chloride, tetrabutyl phosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium chloride, triphenyl phosphonium chloride, benzyl phosphonium chloride and the like; thio compounds such as thiolactic acid, 2-aminothiophenol and 2,2' -dithiodiphenylamine.
The above-mentioned heteroatom-containing ligand is preferably 1 or more amine ligands selected from picolinic acid, 2- { [ (2-dimethylamino) ethyl ] methylamino } ethanol, 1, 2-propanediamine, 1, 2-cyclohexanediamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2, 4-dimethylimidazole, 1, 4-diethylimidazole, 8-quinolinol, 5-chloro-8-quinolinol, 2 '-bipyridine and derivatives thereof, and 2,2' - [ propane-1, 2-diylbis (nitrilo-methine) ] diphenol and derivatives thereof.
The above-mentioned ligands having hetero atoms forming the metal complex may be 1 kind alone or may be 2 or more kinds different from each other in structure.
In the metal complex of the present embodiment, the ratio (molar ratio) of the metal ion or the fatty acid metal salt to the heteroatom-containing ligand is, for example, in the range of 0.1 to 12 moles, preferably in the range of 0.3 to 10 moles, and more preferably in the range of 0.5 to 10 moles, relative to 1 mole of the metal atom of the metal ion or the fatty acid metal salt.
In this embodiment, the metal complex of the heteroatom-containing ligand and the metal ion, and the metal complex of the heteroatom-containing ligand and the fatty acid metal salt may be produced by a known method, or may be produced by reacting a metal monomer or a fatty acid metal salt with the heteroatom-containing ligand. In addition, the metal complex may be commercially available.
In the antibacterial and antiviral composition of the present embodiment, the upper limit of the content of the metal compound (B) is preferably in the order of 60 mass% or less, 50 mass% or less, 45 mass% or less, 40 mass% or less, 37 mass% or less, and 35 mass% or less with respect to the total amount (100 mass%) of the antibacterial and antiviral composition. The lower limit of the content of the metal compound (B) is preferably in the order of 0.5 mass% or more, 1 mass% or more, 1.5 mass% or more, 2 mass% or more, 3 mass% or more, and 5 mass% or more with respect to the total amount (100 mass%) of the antibacterial and antiviral composition.
The upper and lower limits of the content of the above-mentioned metal compound (B) may be arbitrarily combined.
When the content of the metal compound (B) is in the range of 8 to 35 mass%, it is preferable from the viewpoint of storage stability of the aqueous emulsion.
In the antibacterial/antiviral composition of the present embodiment, the lower limit of the content of the metal compound (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass, and the upper limit of the content of the metal compound (B) is preferably 35 parts by mass or less, more preferably 32 parts by mass or less, further preferably 30 parts by mass or less, based on 100 parts by mass of the total of the aqueous solvent (a), the metal compound (B), the organic solvent (C), and the surfactant (D).
In the metal compound (B) of the present embodiment, the upper limit of the content of the metal contained in the metal compound (B) is preferably in the order of 55 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, and 30 mass% or less with respect to the total amount (100 mass%) of the metal compound (B).
The lower limit of the content of the metal contained in the metal compound (B) is preferably in the order of 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, and 3 mass% or more with respect to the total amount (100 mass%) of the metal compound (B).
The upper and lower limits of the content of the above metals may be arbitrarily combined.
When the content of the metal contained in the metal compound (B) is in the range of 1 to 40 mass%, it is preferable from the viewpoint of easy production and handling of the metal compound.
In the antibacterial and antiviral composition of the present embodiment, the upper limit of the content of the metal in the metal compound (B) is preferably in the order of 50 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, 9.5 mass% or less, and 9 mass% or less with respect to the total amount (100 mass%) of the solid components of the antibacterial and antiviral composition. The lower limit of the content of the metal compound (B) is preferably in the order of 0.01 mass% or more, 0.1 mass% or more, 0.2 mass%, 0.4 mass% or more, and 0.7 mass% or more with respect to the total amount (100 mass%) of the antibacterial and antiviral composition.
The upper and lower limits of the content of the above-mentioned metal compound (B) may be arbitrarily combined.
When the content of the metal compound (B) is in the range of 0.01 to 20 mass%, it is preferable from the viewpoint of easy production and handling of the metal compound.
(Organic solvent (C))
The organic solvent (C) of the present embodiment is selected according to the relationship with the aqueous solvent (a). Specifically, the organic solvent (C) may be selected to satisfy the following formula (1).
/dHC-dHA/≥3O.O (1)
(In the above formula (1), dHC represents a hydrogen bond term dH of the Hansen solubility parameter (HSP value) of the above organic solvent (C), dHA represents a hydrogen bond term dH. of the Hansen solubility parameter (HSP value) of the above aqueous solvent (A))
The hydrogen bond term dHC of the Hansen solubility parameter (HSP value) of the organic solvent (C) of the present embodiment is preferably 0 to 12.3 (J/cm 3)1/2, more preferably 0.1 to 10 (J/cm 3)1/2, still more preferably 0.3 to 1 (J/cm 3)1/2).
When the hydrogen bond term dH of the hansen solubility parameter (HSP value) of the organic solvent (C) is in the above range, it is preferable from the following viewpoints: the absolute value of the difference between the hydrogen bond term dHA of hansen solubility parameter of the aqueous solvent (a) and the hydrogen bond term dHC of hansen solubility parameter of the organic solvent (C) can be sufficiently obtained, and excellent emulsion stability is exhibited, for example, the core-shell structure is easily stabilized, or the metal compound (B) is not easily eluted into the aqueous solvent (a).
The metal compound (B) of the present embodiment shows solubility with respect to the organic solvent (C). Specifically, the references shown in the examples column described later are applied.
The metal compound (B) exhibits solubility with respect to the organic solvent (C), whereby the metal compound (B) will be easily transferred into the organic solvent (C) phase.
In the antibacterial and antiviral composition of the present embodiment, the upper limit of the content of the organic solvent (C) is preferably in the order of 60 mass% or less, 55 mass% or less, 45 mass% or less, and 40 mass% or less with respect to the total amount (100 mass%) of the antibacterial and antiviral composition. The lower limit of the content of the organic solvent (C) is preferably in the order of 0.5 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, and 5 mass% or more with respect to the total amount (100 mass%) of the antibacterial and antiviral composition.
The upper and lower limits of the content of the above-mentioned organic solvent (C) may be arbitrarily combined.
When the content of the organic solvent (C) is in the range of 3 to 40 mass%, it is preferable from the viewpoint of easy production and handling of the metal compound.
In the antibacterial/antiviral composition of the present embodiment, the lower limit of the content of the organic solvent (C) is preferably 5 parts by mass or more, more preferably 6 parts by mass or more, further preferably 8 parts by mass, and the upper limit of the content of the organic solvent (C) is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, further preferably 30 parts by mass or less, based on 100 parts by mass of the total of the aqueous solvent (a), the metal compound (B), the organic solvent (C), and the surfactant (D).
The organic solvent (C) of the present embodiment is preferably a hydrocarbon solvent selected from the group consisting of ketones, esters, alcohols, fatty acids, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum hydrocarbons and waxes; a silicone-based solvent; a chlorine-based solvent; and 1 or 2 or more kinds of fluorine-based solvents.
Examples of the ketones include ketones having 4 to 20 carbon atoms, and preferably ketones having 9 to 20 carbon atoms. Specifically, diisobutyl ketone, acetophenone, propiophenone, benzophenone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and the like are exemplified.
Examples of the esters include esters having 4 to 20 carbon atoms, and esters having 6 to 20 carbon atoms are preferable. Specifically, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, allyl acetate, isoamyl propionate, benzyl propionate, ethyl phenylacetate, dimethyl malonate, diethyl malonate, and the like can be mentioned.
Examples of the alcohols include linear or branched saturated alcohols having 5 to 22 carbon atoms and linear or branched unsaturated alcohols having 12 to 22 carbon atoms, and linear or branched saturated alcohols having 8 to 22 carbon atoms and linear or branched unsaturated alcohols having 16 to 22 carbon atoms are preferable. Specifically, oleyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, linoleyl alcohol (Linoleyl alcohol), amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol and the like can be mentioned.
The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group, a branched alkyl group, or an alicyclic structure.
Examples of the fatty acids include saturated fatty acids having 5 to 22 carbon atoms and unsaturated fatty acids having 12 to 22 carbon atoms, and examples of the fatty acids include valeric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, caprylic acid, acrylic acid, methacrylic acid, 2-ethylhexanoic acid (caprylic acid), neodecanoic acid, naphthenic acid residues, isononanoic acid, eleostearic acid, tall oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, dehydrated castor oil fatty acid, tung oil fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, and the like. The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group, a branched alkyl group, or an alicyclic structure.
The aromatic hydrocarbon includes aromatic hydrocarbons having 6 to 20 carbon atoms, and specifically includes benzene, toluene, xylene, styrene, mesitylene, cumene, indene, naphthalene, anthracene, triphenylene (TRIPHENYLENE), and the like.
The aliphatic hydrocarbon may be a saturated or unsaturated aliphatic hydrocarbon having 5 to 18 carbon atoms, and specifically, pentane, hexane, heptane, octane, tridecane, tetradecane, pentadecane, 2, 4-heptadiene, and the like.
The alicyclic hydrocarbon includes alicyclic hydrocarbons having 6 to 20 carbon atoms (cycloalkane-based saturated hydrocarbons), and specifically includes cyclohexane, cyclohexene, methylcyclohexane, cyclooctane, cyclodecane, and the like.
Examples of the petroleum-based hydrocarbon include mineral spirits (MINERAL SPIRIT), gasoline, coal tar naphtha (coal TAR NAPHTHA), petroleum ether (petroleum ether), naphtha (petroleum naphtha), petroleum spirits (petroleum benzine), and turpentine (turpentine).
Examples of the waxes include plant waxes (smoke tree waxes (japanese; zee ), lacquer waxes (japanese; zee ), animal waxes (beeswax, spermaceti, etc.), mineral waxes (montan waxes, etc.), petroleum waxes (paraffin waxes, etc.), synthetic waxes, etc.
The silicone-based solvent includes general silicone oils (Straight siliconeoil) such as dimethyl silicone, methyl hydrogen silicone, methyl phenyl silicone, cyclic dimethyl silicone, fluoroalkyl-modified silicone, carboxyl-modified silicone, and modified silicone oils, and in the case of modified silicone oils, side chain-type modified silicone oils, both terminal-type modified silicone oils, single terminal-type modified silicone oils, and both terminal-type modified silicone oils may be mentioned.
Examples of the chlorine-based solvent include 1, 2-dichloroethylene, trichloroethylene, tetrachloroethylene, and the like.
Examples of the fluorine-based solvent include a Hydrofluorocarbon (HFC) -based solvent, a Hydrofluoroether (HFE) -based solvent, a Perfluorocarbon (PFC) -based solvent, and a Hydrochlorofluorocarbon (HCFC) -based solvent.
Further, as another mode of the organic solvent (C) of the present embodiment, for example, there may be mentioned ester solvents such as γ -butyrolactone, γ -valerolactone, δ -valerolactone, γ -caprolactone, ε -caprolactone, α -methyl- γ -butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate, carbonate solvents such as ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, triethylene glycol, glycol solvents such as triethylene glycol dimethyl ether, phenol, m-cresol, p-cresol, o-cresol, 3-chlorophenol, 4-chlorophenol, ketone solvents such as cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone, ether solvents such as tetrahydrofuran, 1, 4-dioxane, dimethoxyethane, diethoxyethane, dibutyl ether, aromatic hydrocarbon solvents such as benzene, toluene, xylene, trimethylbenzene, naphthalene, ethylbenzene and tetrahydronaphthalene, N-heptane, N-hexane, N-octane, cycloalkane (for example, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane), methylpentane, 2-ethylpentane, isoparaffin, liquid paraffin, decane, undecane, dodecane, and other hydrocarbon solvents, N-methyl-2-pyrrolidone (NMP) as another general solvent, and acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, propylene glycol methyl acetate, ethyl cellosolve butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, chloroform, butanol, ethanol, chlorobenzene, turpentine (Japanese, i.e., tartan), mineral spirits, and naphtha solvents may be used alone or in combination of 2 or more.
(Surfactant (D))
As the surfactant (D) of the present embodiment, as long as the HLB value shows a range of 11 to 18, both ionic (including anionic, cationic and amphoteric) and nonionic (nonionic) surfactants can be used, but an anionic surfactant (D1) showing anionic properties, a nonionic surfactant (D2) showing nonionic properties or a cationic surfactant (D3) showing cationic properties are preferable.
The HLB value of the surfactant (D) of the present embodiment is 11 to 18. The upper limit of the HLB value is preferably 18, 17.5, 17 or 16. On the other hand, the lower limit of the HLB value is preferably 11, 11.5, 12 or 12.5. The upper and lower limits mentioned above may be combined arbitrarily.
If the HLB value of the surfactant (D) is less than 11, a defect occurs in the ease of producing the aqueous emulsion. On the other hand, if the HLB value of the surfactant (D) is more than 18, a defect occurs in the storage stability of the aqueous emulsion.
In the present specification, HLB (hydrophile-lipophilic balance) is a value obtained by the Griffin formula, and as shown in examples described later, the case where 1 surfactant alone is used as the surfactant (D) means the individual HLB value of the surfactant (D) itself, and the case where 2 or more surfactants (D) are used in combination means the value of the HLB of the entire of these various surfactants obtained based on the Griffin formula and the respective contents. The HLB value of the mixture of surfactants (D) was a weighted average of the HLB values of the individual surfactants (surfactant toilet, siderurgica et al, industrial book, inc., 1960, p.309).
In the antibacterial and antiviral composition of the present embodiment, the upper limit of the content of the surfactant (D) is preferably in the order of 20 mass% or less, 15 mass% or less, 12.5 mass% or less, and 10 mass% or less with respect to the total amount (100 mass%) of the antibacterial and antiviral composition. The lower limit of the content of the surfactant (D) is preferably in the order of 0.5 mass% or more, 1 mass% or more, 2 mass% or more, and 3 mass% or more with respect to the total amount (100 mass%) of the antibacterial and antiviral composition.
The upper and lower limits of the content of the above surfactant (D) may be arbitrarily combined.
When the content of the surfactant (D) is in the range of 2 to 10 mass%, the content is in the range of not less than the critical micelle concentration, and therefore, a core-shell structure is easily formed, and the durability of the final processed product is not lowered, which is preferable from the above point of view.
In the antibacterial/antiviral composition of the present embodiment, the lower limit of the content of the surfactant (D) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass, and the upper limit of the content of the surfactant (D) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 5 parts by mass or less, based on 100 parts by mass of the total of the aqueous solvent (a), the metal compound (B), the organic solvent (C), and the surfactant (D).
"Anionic surfactant (d 1)") "
Examples of the anionic surfactant (d 1) of the present embodiment include carboxylic acid-based anionic surfactants such as N-acyl amino acid salts, fatty acid salts, alkyl ether carboxylates, fatty acid amide ether carboxylic acids, and acyl lactylates; phosphate-based anionic surfactants such as alkyl phosphates, polyoxyethylene alkyl ether phosphates, alkylaryl ether phosphates, and fatty acid amide ether phosphates; sulfonic acid-based anionic surfactants such as alkane sulfonate, α -olefin sulfonate, α -sulfofatty acid methyl ester salt, acyl isethionate, alkyl glycidyl ether sulfonate, alkyl sulfosuccinate, alkyl sulfoacetate, alkylbenzenesulfonate, alkyl naphthalene sulfonate, and N-acyl methyl taurate; sulfuric acid-based anionic surfactants such as alkyl sulfate, alkyl ether sulfate, alkyl aryl ether sulfate, fatty acid alkanolamide sulfate and fatty acid monoglyceride sulfate.
"Nonionic surfactant (d 2)") "
The nonionic surfactant (d 2) of the present embodiment may be any of ester type, ether type, ester/ether type, and others, and examples thereof include polyoxyalkylene polyol ether, polyoxyalkylene polyol fatty acid ester, polyoxyalkylene aliphatic alcohol ether, fatty acid ester of polyalkylene glycol, and polyol fatty acid ester.
< Polyoxyalkylene polyol ether >
The polyoxyalkylene polyol ether may be a compound having a structure in which an alkylene oxide having 1 to 8 carbon atoms such as ethylene oxide, propylene oxide or butylene oxide is added to a polyol.
The polyhydric alcohol is preferably at least one selected from the group consisting of ethylene glycol, glycerin, trimethylolpropane, trimethylolethane, erythritol, pentaerythritol, diglycerol, sorbitan, sorbitol, ditrimethylolpropane, ditrimethylolethane, dipentaerythritol and sucrose.
The addition mole number of the alkylene oxide is preferably 3 to 87, more preferably 4 to 70, and still more preferably 5 to 60. The proportion of ethylene oxide in the alkylene oxide is preferably 50 mol% or more, and more preferably 80 mol% or more.
The weight average molecular weight (Mw) of the polyoxyalkylene polyol ether is preferably 300 to 10000, more preferably 400 to 8000, still more preferably 500 to 5000.
Examples of the polyoxyalkylene polyol ether include polyethylene glycol, glycerin ethylene oxide adduct, trimethylolpropane ethylene oxide adduct, pentaerythritol ethylene oxide adduct, diglycerin ethylene oxide adduct, sorbitan ethylene oxide adduct, sorbitol anhydride ethylene oxide propylene oxide adduct, sorbitol ethylene oxide propylene oxide adduct, ditrimethylolpropane ethylene oxide adduct, dipentaerythritol ethylene oxide adduct, sucrose ethylene oxide adduct, and the like, but are not limited thereto.
< Polyoxyalkylene polyol fatty acid ester >
The polyoxyalkylene polyol fatty acid ester may be a compound having a structure in which a fatty acid and a compound having an alkylene oxide having 1 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide or the like are bonded together by an ester bond to a polyol.
The polyol is the same as the polyol described in the above < polyoxyalkylene polyol ether > column.
Examples of the fatty acid include lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, isocetylic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachic acid, eicosenoic acid, behenic acid, isobehenic acid, erucic acid, lignoceric acid, isolignoceric acid, and the like.
The number of addition moles of the alkylene oxide is the same as the number of addition moles described in the above < polyoxyalkylene polyol ether > column.
The weight average molecular weight (Mw) of the polyoxyalkylene polyol fatty acid ester is preferably 300 to 7000, more preferably 500 to 5000, and still more preferably 700 to 3000.
Examples of the polyoxyalkylene polyol fatty acid ester include, but are not limited to, glycerol ethylene oxide adduct monolaurate, glycerol ethylene oxide adduct dilaurate, glycerol ethylene oxide adduct trilaurate, trimethylolpropane ethylene oxide adduct trilaurate, sorbitan ethylene oxide adduct monooleate, sorbitan ethylene oxide adduct dioleate, sorbitan ethylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide adduct monooleate, sorbitan ethylene oxide propylene oxide adduct dioleate, sorbitan ethylene oxide propylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide adduct trilaurate, sucrose ethylene oxide adduct trilaurate, and the like.
< Polyoxyalkylene aliphatic alcohol Ether >
The polyoxyalkylene aliphatic alcohol ether may be a compound having a structure in which an alkylene oxide having 1 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide or the like is added to an aliphatic monohydric alcohol.
The number of addition moles of the alkylene oxide is preferably 1 to 90 moles, more preferably 2 to 80 moles, and still more preferably 3 to 55 moles. The proportion of ethylene oxide to the entire alkylene oxide is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% or more.
Examples of the polyoxyalkylene aliphatic alcohol ether include alkylene oxide adducts of aliphatic alcohols such as octanol, 2-ethylhexanol, decanol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol.
< Fatty acid ester of polyalkylene glycol >
The fatty acid ester of the polyalkylene glycol may be a compound having a structure in which polyethylene glycol and/or polyethylene polyoxypropylene glycol and a fatty acid are bonded by an ester bond. The weight average molecular weight (Mw) of the polyalkylene glycol is preferably 100 to 1000, more preferably 150 to 800, and even more preferably 200 to 700.
Examples of the polyalkylene glycol fatty acid ester include polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene polypropylene glycol monolaurate, polyethylene polypropylene glycol dilaurate, polyethylene polypropylene glycol monooleate, and polyethylene polypropylene glycol dioleate, but are not limited thereto.
< Polyol fatty acid ester >
The polyol fatty acid ester may be a compound having a structure in which a polyol and a fatty acid are bonded by an ester bond.
The polyol is the same as the polyol described in the above < polyoxyalkylene polyol ether > column.
The fatty acid is the same as the fatty acid described in the above < polyoxyalkylene polyol fatty acid ester > column.
The polyol fatty acid ester has at least 1 or2 or more hydroxyl groups. The weight average molecular weight (Mw) of the polyol fatty acid ester is preferably 100 to 1200, more preferably 220 to 1000, and even more preferably 300 to 800.
Examples of the fatty acid ester include glycerol monolaurate, glycerol dilaurate, glycerol monooleate, glycerol dioleate, sorbitan monooleate, sorbitan dioleate, sucrose monolaurate and sucrose dilaurate.
< Preferred nonionic surfactant (d 2) >)
The nonionic surfactant (d 2) which is preferable in the present embodiment is specifically, for example, one or more nonionic surfactants selected from the group consisting of polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene alkyl ethers, glycerol fatty acid esters, sorbitan fatty acid esters, polyglycerol fatty acid esters, and sucrose fatty acid esters. Among these, nonionic surfactants (d 2) having an ethylene oxide chain are preferable. Particularly preferably 1 or 2 or more selected from polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkyl ethers and polyoxyethylene hydrogenated castor oils.
When a nonionic surfactant (D2) having an ethylene oxide chain is used as the surfactant (D) of the present embodiment, the number of moles of ethylene oxide added is preferably 4 to 250, more preferably 20 to 160, and still more preferably 20 to 80. The number of carbon atoms of the fatty acid moiety and the alkyl moiety of the nonionic surfactant (d 2) is preferably 8 to 24, more preferably 12 to 22.
"Cationic surfactant (d 3)") "
Examples of the cationic surfactant (d 3) include di-long-chain alkyl dimethyl ammonium salts such as distearyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, and dicarbamyl dimethyl ammonium chloride; mono-long alkyl trimethylammonium salts such as behenyl trimethylammonium chloride, behenyl trimethylammonium methylsulfate, stearyl trimethylammonium chloride, stearyl trimethylammonium bromide, cetyl trimethylammonium bromide and the like; long-chain alkoxyalkyl trimethylammonium salts such as stearoxy propyl trimethylammonium chloride.
"Preferred surfactant (D)".
The surfactant (D) in the present embodiment may be preferably 1 or 2 or more kinds of surfactants (D) selected from the group consisting of nonionic surfactants (D1), anionic surfactants (D2) and cationic surfactants (D3).
The preferable surfactant (D) of the present embodiment may be a solution-type surfactant (D), and specifically, may be a surfactant mixture obtained by mixing 1 or 2 or more surfactants selected from the group consisting of nonionic surfactants (D1), anionic surfactants (D2) and cationic surfactants (D3) with the above-mentioned aqueous solvent (a) and/or the above-mentioned organic solvent (C). If necessary, a thickener may be added to the surfactant mixture. The addition of the thickener is preferable from the viewpoints of storage stability of the processing agent (suppression of separation) and workability in coating formulation.
When a mixed solution is used as the surfactant (D), the solid content in the mixed solution is preferably 0.5 to 95% by mass, more preferably 0.5 to 50% by mass.
As the thickener, a material known for use in an aqueous paint can be used. For example, associative thickeners, cellulose thickeners, (meth) acrylic thickeners, urethane thickeners, polyacrylamide thickeners, vinyl ether thickeners, mineral thickeners, polysaccharide thickeners, and the like can be cited.
Examples of the thickener include the UH series of ADEKA NOL (registered trademark) manufactured by ADEKA, the SN THICKENER series of SAN NOPCO (manufactured by Santa Classification), the Aron (Japanese: A-II) (registered trademark) thickener series manufactured by Tokyo, and the OPTIFLO series of BYK corporation.
The content of the thickener is 0.01 to 10 parts by mass per 100 parts by mass of the solid content of the surfactant mixture. The above thickeners may be used singly or in combination of 1 or more than 2.
(Optional additional Components)
The antibacterial and antiviral composition of the present embodiment may contain an additive component (E) such as a dispersing aid, a pH adjuster, a preservative, a mold inhibitor, an anticorrosive agent, a viscosity adjuster, a chelating agent, an antifoaming agent, or an antioxidant, within a range that does not impair the effects of the present invention.
Examples of the dispersant include polymeric dispersants such as polycarboxylic acids, naphthalene sulfonic acid formaldehyde condensates and salts thereof. Examples of the dispersion aid include condensed phosphates such as pyrophosphates and hexametaphosphates. Examples of the preservative include sodium hypochlorite. As examples of the above-mentioned mildew preventive, oxazolines such as oxazolidine-2, 5-dione and the like can be given. Examples of the anticorrosive agent include amines, pyridines, tetraphenylphosphonium salts, benzotriazoles, triazoles, tetrazoles, and benzoic acid. Examples of the thickener include aluminum silicate hydrate, dimethyl octadecyl salt of montmorillonite clay (montmorillonite clay), alkali-soluble acrylic polymer, colloidal silica, alumina sol, heavy metal soap, polyvinyl alcohol, carboxymethyl cellulose, xanthan gum, and the like. As examples of the above viscosity modifier.
Examples of the chelating agent include carboxylic acid chelating agents such as gluconic acid; amine chelating agents such as ethylenediamine, diethylenetriamine and trimethyltetramine, polyaminopolycarboxylic acid chelating agents such as ethylenediamine tetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediamine triacetic acid, triethylenetetramine hexaacetic acid and diethylenetriamine pentaacetic acid; organic phosphonic acid chelating agents such as 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediamine tetra (methylenephosphonic acid), diethylenetriamine penta (methylenephosphonic acid), ethane-1, 1-diphosphonic acid, ethane-1, 2-triphosphonic acid, methane-hydroxyphosphonic acid, 1-phosphonobutane-2, 3, 4-tricarboxylic acid, and phenol derivatives; 1, 3-diketones, and the like.
When the additive component (E) is repeated with the components (A) to (D), the additive component (E) is used as the components, and the additive component (E) is not out of the range.
In the antibacterial and antiviral composition of the present embodiment, the content of the additive component (E) is preferably 0.1 to 20 mass% relative to the total amount (100 mass%) of the antibacterial and antiviral composition.
In the antibacterial/antiviral composition of the present embodiment, the additive component (E) is an optional component, and the lower limit is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.5 part by mass, and the upper limit is preferably 25 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, relative to 100 parts by mass of the total of the aqueous solvent (a), the metal compound (B), the organic solvent (C), and the surfactant (D) in the case of adding the additive component.
(Physical Properties of antibacterial and antiviral composition)
The viscosity of the antibacterial/antiviral composition of the present embodiment in the form of a solution is preferably 10 to 100,000mpa·s, more preferably 100 to 50,000mpa·s, from the viewpoints of dispersion stability and handleability. The temperature of the antibacterial and antiviral composition in the form of a solution was adjusted to 25℃and the viscosity was measured using a Brookfield viscometer (B8L viscometer, manufactured by Corp. Tokimec).
When the antibacterial and antiviral composition of the present embodiment is a solution-form antibacterial and antiviral composition containing the aqueous solvent (a), the pH of the antibacterial and antiviral composition of the solution is preferably 3 to 11, more preferably 4 to 10, and even more preferably 4.5 to 9.5.
[ Method for producing antibacterial/antiviral composition ]
The method of producing the antibacterial and antiviral composition of the present disclosure is not particularly limited, and a method capable of uniformly mixing the above-described aqueous solvent (a), metal compound (B), organic solvent (C), and surfactant (D) can be suitably employed.
Specifically, for example, in the case of forming an oil-in-water emulsion, there may be mentioned a method in which the metal compound (B), the organic solvent (C), and the surfactant (D) are mixed uniformly, then the aqueous solvent (a) is added and mixed, and preferably, the metal compound (B) is added to the organic solvent (C) and mixed uniformly, then the surfactant (D) is added, and then the mixture is completely dispersed by using an emulsifying and dispersing machine, and then the aqueous solvent (a) is added and mixed.
The emulsifying and dispersing machine used in the present embodiment may be appropriately selected and used according to the type of raw material, the state of emulsion, the target fineness, etc., and specifically, emulsifying and dispersing machines such as a homogenizer (homogenizer), a homomixer (homomixer), a stirrer (agitator), a disperser (japanese) a planetary mixer, an Adi homomixer (japanese) a real-time device, a universal mixer, an ultrasonic disperser, a grinder (attritor), a sand grinder, a bead grinder (japanese), a Glen grinder (japanese) a lycra (japanese), dai Nuomo (japanese) a ball mill, a colloid mill (colloid mill), etc. may be used. 1 or 2 or more of them may be selected.
[ Antibacterial antiviral coating composition ]
The antibacterial and antiviral coating composition of the present disclosure contains the antibacterial and antiviral composition of the present embodiment (hereinafter, antibacterial and antiviral composition) and an aqueous resin dispersion. More specifically, the antibacterial and antiviral coating composition of the present disclosure must contain an aqueous solvent (a), a metal compound (B), an organic solvent (C), a surfactant (D), and an aqueous resin dispersion.
Thus, the antibacterial antiviral coating composition of the present disclosure has high compatibility with respect to the aqueous resin dispersion, and therefore, the coating layer obtained from the antibacterial antiviral coating composition containing the antibacterial antiviral composition can reduce the influence on the appearance such as the deterioration of transparency. In addition, the antibacterial and antiviral coating composition can exhibit an adhesion promoting effect with the substrate, and since the antibacterial and antiviral coating composition contains the antibacterial and antiviral composition, the obtained coating layer can exhibit high adhesion with the substrate. Therefore, the laminate of the substrate and the coating layer formed on the substrate exhibits antibacterial and antiviral properties, and the substrate and the coating layer can exhibit high adhesion.
The content of the antibacterial/antiviral composition contained in the antibacterial/antiviral coating composition of the present embodiment is not particularly limited, and for example, the metal derived from the antibacterial/antiviral curing composition is preferably contained in a range of 0.01 to 30 parts by mass per 100 parts by mass of the resin solid content, the metal derived from the antibacterial/antiviral curing composition is preferably contained in a range of 0.01 to 15 parts by mass per 100 parts by mass of the resin solid content, the metal derived from the antibacterial/antiviral curing composition is more preferably contained in a range of 0.01 to 10 parts by mass per 100 parts by mass of the resin solid content, and the metal derived from the antibacterial/antiviral curing composition is more preferably contained in a range of 0.1 to 10 parts by mass per 100 parts by mass of the resin solid content.
The term "resin solid component" as used herein refers to the total amount of solid components such as an aqueous resin dispersion contained in the antibacterial and antiviral curable composition.
The antibacterial and antiviral composition contained in the antibacterial and antiviral coating composition of the present embodiment may be 1 or 2 or more types.
The aqueous resin dispersion contained in the antibacterial and antiviral coating composition of the present embodiment is not particularly limited, and any of emulsion-based resins, latex-based resins, thermosetting resins, and active energy ray-curable resins may be used.
The aqueous resin dispersion may be any of an aqueous resin and a water-insoluble resin (solvent-based resin). In the present specification, the term "water-soluble resin" means that the amount of water required to dissolve 1g of resin at 20℃is less than 10m1. The term "water-insoluble resin" refers to a resin other than the "water-soluble resin" described above.
Specific examples of the aqueous resin dispersion include acrylic resins, vinyl acetate resins, styrene resins, vinyl chloride resins, olefin resins, urethane resins, urea resins, urethane urea resins, acrylic urethane resins, epoxy resins, melamine resins, phenolic resins, polyester resins, alkyd resins, silicone resins, polyphenylene sulfide resins, acrylonitrile/styrene copolymer resins, acrylonitrile/butadiene copolymer resins, and acrylonitrile/butadiene/styrene copolymer (AB S) resins.
The aqueous resin dispersion also includes a modified resin obtained by modifying the above-exemplified resin, and for example, if it is a phenolic resin, it also includes the meaning of rosin-modified phenolic resin.
The aqueous resin dispersion contained in the antibacterial antiviral curing composition of the present embodiment may be 1 kind alone or 2 or more kinds.
The content of the aqueous resin dispersion in the antibacterial and antiviral coating composition of the present embodiment is not particularly limited, and is preferably set in a range of 10 to 100 mass% relative to the total mass of the resin solid components of the antibacterial and antiviral coating composition, for example.
The antibacterial/antiviral coating composition of the present embodiment may contain the antibacterial/antiviral composition and the aqueous resin dispersion, and may further contain a dispersion medium. The dispersion medium is added for the purpose of adjusting the viscosity of the antibacterial and antiviral curing composition, and may be any of an aqueous medium and an oily medium.
Specific examples of the dispersion medium include water, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propanol, and monofunctional alcohols such as isopropanol, various diols, and polyhydric alcohols such as glycerin, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, and 1, diols such as 12-dodecanediol, propylene glycol, 1, 2-butanediol, 3-methyl-1, 3-butanediol, 1, 2-pentanediol, 2-methyl-1, 3-propanediol, 1, 2-hexanediol, dipropylene glycol, diethylene glycol and the like, aromatic diols as adducts of bisphenol A, alkylene oxides having 2 or 3 carbon atoms of bisphenol A (average addition mole number of 1 or more and 16 or less), alicyclic diols such as hydrogenated bisphenol A polyoxypropylene-2, 2-bis (4-hydroxyphenyl) propane, polyoxyethylene-2, 2-bis (4-hydroxyphenyl) propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, gamma-butyrolactone, various fatty acids, and the like. The dispersion medium may be used alone or in combination of 1 or more than 2.
The content of the dispersion medium in the antibacterial and antiviral coating composition of the present embodiment is not particularly limited, and is preferably set so that the solid content concentration of the antibacterial and antiviral coating composition is in the range of 30 to 80 mass%, for example.
The antibacterial and antiviral coating composition of the present embodiment may further contain a plasticizer. By adding a plasticizer to the antibacterial and antiviral coating composition, flexibility can be imparted to the obtained coating layer, and the tracking property with respect to the substrate can be improved.
The plasticizer is not particularly limited, and examples thereof include phthalic acid esters, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphoric acid esters, trimellitic acid esters, chlorinated paraffins, hydrocarbon-based oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, and the like, and phthalic acid esters are preferable. Specific examples of the plasticizer include dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, and benzyl epoxystearate. The plasticizer may be used alone or in combination of 1 or more than 2.
The content of the plasticizer in the antibacterial and antiviral coating composition of the present embodiment is not particularly limited, and is preferably set appropriately in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin solid content of the antibacterial and antiviral coating composition.
The antibacterial and antiviral coating composition of the present embodiment may contain the antibacterial and antiviral composition, the aqueous resin dispersion, and optionally a dispersion medium and/or a plasticizer, and may contain other additives within a range that does not impair the effects of the present invention. Examples of the other additives include pigments, matting agents, curing accelerators, defoaming agents, dispersants, leveling agents, thickeners, antioxidants, weather-resistant agents, flame retardants, antistatic agents, lubricants, and preservatives.
The antibacterial and antiviral coating composition of the present embodiment can be applied to a substrate surface to form a coating layer by applying a curing method (heat curing, active energy ray curing, etc.) suitable for an aqueous resin dispersion to the obtained coating film.
The method of applying the antibacterial and antiviral coating composition may be any known and commonly used method, and examples thereof include roll coater, electrostatic coating, bar coater, gravure coater, knife coater, dip coating, and spray coating. The antibacterial and antiviral coating composition of the present disclosure has a low VOC, and thus can improve coating workability and reduce adverse effects on the human body. Therefore, the present invention is particularly suitable for a case of spraying the surface of an arbitrary object in a room or the like.
The substrate to be coated is not particularly limited, and examples thereof include paper, synthetic paper, steel sheet, aluminum foil, glass, wood, woven fabric, knitted fabric, nonwoven fabric, gypsum board, wooden board, resin substrate, and the like.
Specific examples of the resin substrate include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polycarbonate film, polyethylene terephthalate film, polymethyl methacrylate film, polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose resin film, polyvinyl alcohol film, ABS resin film, norbornene resin film, cyclic olefin resin film, polyimide resin film, polyvinyl fluoride resin film, polyvinylidene fluoride resin film, ethylene-vinyl acetate copolymer film, and the like. The resin substrate to be used may be subjected to a surface treatment such as corona treatment.
(Antibacterial antiviral fabric)
The antibacterial antiviral fabric of the present embodiment includes a fabric and a coating layer attached to the fabric and made of an antibacterial and antiviral coating composition. In other words, the antibacterial/antiviral fabric of the present embodiment includes a fabric and a coating layer attached to the fabric, and the coating layer contains the metal compound (B) and the surfactant (D).
The method for producing an antibacterial antiviral fabric according to the present embodiment includes the steps of: step (I) of preparing an aqueous coating agent comprising 0.01 to 5 parts by mass of a paste such as ethyl cellulose for adjusting the viscosity/tackiness of a coating material, 0.01 to 20 parts by mass of an aqueous resin dispersion such as an aqueous acrylic resin, 1 to 60 parts by mass of the above-mentioned antibacterial/antiviral composition, and 15 to 99 parts by mass of an aqueous solvent added as required; step (II) of mixing 1 to 50 parts by mass of the aqueous varnish and 50 to 99 parts by mass of an aqueous solvent (A) added as needed to prepare an aqueous processing liquid; a step (III) of immersing a substrate (for example, a fabric) in the aqueous processing liquid or applying the aqueous processing liquid to the substrate (for example, a fabric); and (IV) drying the fabric to which the aqueous processing liquid is added at 20 to 180 ℃ for 1 minute to 48 hours. As the type of the aqueous solvent to be added as needed, the same type of the aqueous solvent (a) can be used.
The average coating amount of the coating layer may be appropriately set, but is preferably 0.01 to 10g/m 2 in terms of the metal amount of the metal compound (B).
As the paste, a water-soluble polymer can be used. The water-soluble polymer may be a natural polymer or a synthetic polymer. Examples of the above-mentioned aqueous polymer include known natural aqueous polymers such as starch substances such as corn and wheat, cellulose-based substances such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxyethyl cellulose, polysaccharides such as sodium alginate, gum arabic, locust bean gum, tragacanth gum, guar gum and tamarind seed, protein substances such as gelatin and casein, tannin-based substances and lignin-based substances.
Examples of the synthetic aqueous polymer include a known polyvinyl alcohol compound, a known polyethylene oxide compound, a known acrylic aqueous polymer, and a known maleic anhydride aqueous polymer. Among these, polysaccharide-based polymers and cellulose-based polymers are preferable.
(Antibacterial antiviral film)
The antibacterial and antiviral film of the present embodiment comprises a base film and a coating layer provided on at least one surface of the base film, the coating layer being made of an antibacterial and antiviral coating composition.
In other words, the antibacterial and antiviral film of the present embodiment comprises a base film and a coating layer attached to the base film, wherein the coating layer contains the metal compound (B) and the surfactant (D).
The method for producing the antibacterial antiviral film according to the present embodiment comprises the following steps: step (I) of preparing an aqueous paint obtained by mixing 1 to 99 parts by mass of an aqueous resin dispersion such as an aqueous acrylic resin, 1 to 50 parts by mass of the antibacterial/antiviral composition, and 0 to 98 parts by mass of an aqueous solvent added as needed; a step (II) of applying the aqueous coating agent to a substrate (for example, a substrate film such as a PET film); and (III) drying the substrate coated with the aqueous paint at 20 to 180 ℃ for 1 minute to 48 hours. As the type of the aqueous solvent to be added as needed, the same type of the aqueous solvent (a) can be used.
The average thickness of the coating layer may be appropriately set, but is generally preferably 1 to 50. Mu.m.
The haze value of the coating layer is preferably 10% or less, more preferably 7% or less, further preferably 5% or less, and most preferably 3% or less. The haze value was measured according to JIS K7136 as described in examples below: 2000 standard.
In a preferred embodiment of the antibacterial and antiviral film of the present embodiment, the difference between the haze value of the blank film having the base film and the reference coating layer provided on one surface of the base film and the haze value of the antibacterial and antiviral film having the base film and the coating layer provided on one surface of the base film is preferably 10% or less.
The reference coating layer may be formed from a reference composition from which the metal compound (B) is removed from the antibacterial and antiviral coating composition.
In more detail, the base composition as a raw material of the base coating layer must contain water and an aqueous resin dispersion. The content of the aqueous resin dispersion in the reference composition can refer to a numerical range of the content of the aqueous resin dispersion in the composition for antibacterial and antiviral coating.
Molded body "
The antibacterial and antiviral curing composition of the present disclosure contains an antibacterial and antiviral composition and a resin. The antibacterial and antiviral curing composition can be used not only for coating purposes, but also by curing and molding the antibacterial and antiviral curing composition itself, a molded article exhibiting antibacterial and antiviral properties can be formed.
The resin contained in the antibacterial and antiviral curable composition of the present disclosure may be the same as the aqueous resin dispersion contained in the antibacterial and antiviral coating composition of the present disclosure. The antibacterial and antiviral curing composition of the present invention may contain the same components as the antibacterial and antiviral coating composition of the present invention can contain.
The molding method of the antibacterial and antiviral curable composition of the present invention may be a molding method compatible with the resin used, and examples thereof include melt molding methods such as injection molding, extrusion molding, compression molding (press molding), pressure molding, and vacuum molding, and casting methods.
The coated article having a coating layer obtained using the antibacterial and antiviral coating composition of the present invention and the molded article obtained using the antibacterial and antiviral curing composition of the present invention can be suitably used as a material having antibacterial and antiviral activity in a position touched by a human hand. As applications, the present invention can be applied to a wide range of applications such as smart phone covers, personal computer covers, touch panels, armrests, door handles, wash stands, buttons such as elevator buttons, interior decorations (wallpaper, floor, etc.), various packaging materials, various fiber products, and medical devices (medical gloves, medical glasses, etc.).
(Methods of expressing antibacterial and antiviral properties)
The coated article having a coating layer obtained using the composition for antibacterial and antiviral coating of the present disclosure and the molded article obtained using the composition for antibacterial and antiviral curing of the present disclosure can exhibit sufficient antibacterial and antiviral properties by exposure to light such as light irradiation of LEDs (light emitting diodes) such as fluorescent lamps, incandescent lamps, halogen lamps, white, blue, green, etc., semiconductor lasers, electroluminescent light sources, etc., sunlight (natural light), that is, inhibit or reduce proliferation of bacteria and viruses, and can also exhibit sufficient antibacterial and antiviral properties irrespective of light and shade by standing in an environment where no light is irradiated, for example.
Examples
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the examples. In the following, unless otherwise specified, "parts" and "%" are mass references.
(Evaluation method)
(1) < Evaluation of solubility >
1G of a solute was put into a solvent in accordance with JIS K8001, and when mixed with vigorous shaking at 20.+ -. 5 ℃ for 30 seconds every 5 minutes, the degree of dissolution was evaluated within 30 minutes.
The term "solubility in the metal compound (B)" refers to a case where 1g of the metal compound (B) is dissolved in 10ml or less of the solvent, the term "solubility in the aqueous solvent (a)" refers to a case where 1g of the metal compound (B) is not soluble in the aqueous solvent (a), and the term "solubility in the aqueous solvent (a)" refers to a case where 100ml or more of the aqueous solvent (a) is required to dissolve 1g of the substance or 1ml of the solvent. The term "melted" as used herein means that no residue can be visually confirmed.
(2) < Evaluation of emulsion stability >
The respective antibacterial and antiviral compositions produced in examples and comparative examples were placed in 200ml screw bottles, and the viscosities immediately after production of the respective antibacterial and antiviral compositions and the viscosities after standing the respective antibacterial and antiviral compositions at 40℃for 7 days were measured and evaluated according to the following criteria. The temperature of the antibacterial and antiviral composition in the form of a solution was adjusted to 25℃and the viscosity was measured using a Brookfield viscometer (B8L viscometer, manufactured by Corp. Tokimec).
The viscosity of the product (… …) after 7 days at 40 ℃ is within 0.5-2 times of that of the product just after manufacturing;
The viscosity of x … … after 7 days at 40 ℃ is less than 0.5 times or more than 2 times as compared with the viscosity just after manufacture.
(3) < Evaluation of compatibility >
The antibacterial and antiviral compositions prepared in examples and comparative examples were placed in 200ml screw bottles, allowed to stand at 25℃and visually evaluated according to the following criteria.
No phase separation of … …;
the X … … has phase separation and sedimentation.
(4) < Evaluation of antiviral Property >
Reference JIS R1706: 2020, film adhesion was evaluated for antiviral properties with respect to phage qβ.
The conditions for inoculating the virus on the surfaces of the blank test piece and the antibacterial and antiviral coating test piece are dark place and 25 ℃ for 4 hours. From the phage qβ infection titer after 4 hours reaction of the blank test piece and the antibacterial and antiviral coated test piece, an antiviral activity value was calculated using the following calculation formula. The results are shown in Table 1. When the antiviral activity value is 2.0 or more, the antiviral effect is evaluated.
Antiviral activity value=log (a/B) =log (a) -Log (B)
Log (a): common log values of infection titer after 4 hours of reaction for blank test strips;
Log (B): common log values of infection titer after 4 hours of reaction for antibacterial and antiviral coated test strips.
(5) < Evaluation of antibacterial Properties >
The antibacterial property was evaluated by using SAN-AI BIOCHECKER FC (manufactured by Sanai Petroleum Co., ltd.). Well water previously left at room temperature for 1 week was dropped onto the culture base surface of SAN-AI BIOCHECKER, and the resulting mixture was brought into contact with the coating layer of the antibacterial and antiviral coated test pieces prepared in examples and comparative examples, and fixed with masking tape (MASKING TAPE). The sample was cultured at 30℃for 2 days, and the colony formed in either medium was designated as "X" and the colony not formed in either medium was designated as "o".
(6) < Evaluation of transparency >
The method according to JIS K7136 was used: 2000, and antibacterial and antiviral films prepared in examples and comparative examples were measured. The haze value of a blank film produced in the same manner as in example except that the organic solvent (B), the metal compound (B) and the surfactant were not contained, was also determined in accordance with JIS K7136:2000 standard haze meter. The haze values of the antibacterial and antiviral films of examples and comparative examples were evaluated according to the following criteria with respect to the haze values of the blank films.
A haze value of ∈ … … with respect to the blank film of +10.0%;
the haze value of x … … with respect to the blank film is a value of +10.0% or more.
(7) < Measurement of average particle diameter >
The antibacterial and antiviral composition was diluted with water to 10 times, the refractive index of the solvent was set to water (1.333), the refractive index of the sample was set to polystyrene (1.590 to 0.000 i), and the particle size distribution was measured, with the median particle diameter as the average primary particle diameter.
Preparation of antibacterial and antiviral composition "
(Synthesis of Metal Compound (B))
Synthesis example 1: preparation of fatty acid Metal salt (Co)
Then, 319.0 parts by mass of 2-ethylhexanoic acid and 100.0 parts by mass of cobalt hydroxide were reacted at 130 ℃, dehydrated under reduced pressure at 130 ℃, and 134.2 parts by mass of petroleum hydrocarbon was added to obtain 502.3 parts by mass of a cobalt 2-ethylhexanoic acid solution (fatty acid metal salt (Co)). The cobalt content of the obtained fatty acid metal salt (Co) was 12 mass%.
< Synthetic example 2: preparation of fatty acid metal salt (Nd)
224.8 Parts by mass of neodecanoic acid and 60.0 parts by mass of neodymium oxide were reacted at 130 ℃, then dehydrated under reduced pressure at 130 ℃, and then 306.9 parts by mass of cyclohexane was added to obtain 570.0 parts by mass of neodecanoic acid neodymium solution. The solvent of the resulting solution was distilled off at 130 ℃ to obtain neodymium neodecanoate as a1 st fatty acid metal salt (Nd). The neodymium content of the obtained neodymium neodecanoate was 18.7 mass%.
< Synthesis example 3: preparation of fatty acid Metal salt (Bi)
330.6 Parts by mass of 2-ethylhexanoic acid and 125.0 parts by mass of bismuth oxide were reacted at 130℃and dehydrated under reduced pressure at 130℃to obtain 439.5 parts by mass of a bismuth 2-ethylhexanoate solution. The bismuth content in the obtained fatty acid metal salt (Bi) was 25 mass%.
< Synthetic example 4: preparation of fatty acid Metal salt (Mg)
Then, by reacting 461.4 parts by mass of 2-ethylhexanoic acid with 71.9 parts by mass of magnesium hydroxide and 411.4 parts by mass of petroleum hydrocarbon at 110℃and dehydrating under reduced pressure at 90℃and then adding 35.9 parts by mass of butyldiglycol, 1000 parts by mass of a magnesium 2-ethylhexanoate solution (fatty acid metal salt (Mg)) was obtained. The magnesium content in the obtained fatty acid metal salt (Mg) was 3.0 mass%.
< Synthetic example 5: preparation of fatty acid Metal salt (La)
83.1 Parts by mass of neodecanoic acid and 21.5 parts by mass of lanthanum oxide were reacted at 130℃and dehydrated under reduced pressure at 130℃and then 107.6 parts by mass of cyclohexane was added to obtain 208.5 parts by mass of a lanthanum neodecanoic acid solution (fatty acid metal salt (La)). The lanthanum content in the obtained fatty acid metal salt (La) was 8.8 mass%.
< Synthetic example 6: preparation of fatty acid Metal salt (Pr)
166.6 Parts by mass of neodecanoic acid and 45.0 parts by mass of praseodymium oxide were reacted at 130℃and dehydrated under reduced pressure at 130℃and then 220.0 parts by mass of cyclohexane was added to obtain 422.0 parts by mass of a praseodymium neodecanoate solution (fatty acid metal salt (Pr)). The praseodymium content in the obtained fatty acid metal salt (Pr) was 8.8 mass%.
< Synthetic example 7: preparation of fatty acid Metal salt (Sm)
137.1 Parts by mass of neodecanoic acid and 37.6 parts by mass of samarium oxide were reacted at 130℃and dehydrated under reduced pressure at 130℃and then 196.3 parts by mass of cyclohexane was added to obtain 364.7 parts by mass of a samarium neodecanoate solution (fatty acid metal salt (Sm)). The content of samarium in the obtained fatty acid metal salt (Sm) was 8.8 mass%.
< Synthesis example 8: preparation of fatty acid Metal salt (Gd)
149.3 Parts by mass of neodecanoic acid and 43.0 parts by mass of gadolinium oxide were reacted at 130℃and dehydrated under reduced pressure at 130℃and then 230.2 parts by mass of cyclohexane was added to obtain 415.1 parts by mass of a gadolinium neodecanoate solution (fatty acid metal salt (Gd)). The gadolinium content of the obtained fatty acid metal salt (Gd) was 8.8 mass%.
< Synthetic example 9: preparation of fatty acid metal salt (Nd)
Then, 192.8 parts by mass of cyclohexane was added to the resulting mixture, and 581.6 parts by mass of a neodymium 2-ethylhexanoate solution (fatty acid metal salt (Nd)) was obtained. The neodymium content of the obtained 2 Nd fatty acid metal salt (Nd) was 8.8 mass%.
< Synthetic example 10: preparation of Metal Complex (Mn)
To a solution of 291 parts by mass of a manganese neodecanoate solution (Mn-6.5% by mass) and 1235 parts by mass of benzyl alcohol, 50 parts by mass of 8-hydroxyquinoline was added, and a reaction was performed at 50℃for 1 hour to obtain 1576 parts by mass of a complex solution (metal complex (Mn)) of manganese neodecanoate and 8-hydroxyquinoline. The manganese content of the metal complex (Mn) obtained was 1.2 mass%.
< Synthesis example 11: preparation of fatty acid Metal salt (Zr)
173.7 Parts by mass of 2-ethylhexanoic acid and 180.0 parts by mass of zirconium carbonate were reacted at 110℃and dehydrated under reduced pressure at 90℃and then diluted with mineral spirits to obtain 445.4 parts by mass of a zirconium 2-ethylhexanoic acid solution. The zirconium content of the obtained fatty acid metal salt (Zr) was 12 mass%.
< Others >
In addition to the above, commercial products (yttrium 2-ethylhexanoate was manufactured by Fuji film and Wako pure chemical industries, ltd., lead 2-ethylhexanoate was manufactured by DIC Co., ltd., and silver 2-ethylhexanoate was manufactured by Fuji film and Wako pure chemical industries, ltd., pb) were prepared as a fatty acid metal salt of yttrium 2-ethylhexanoate, a fatty acid metal salt of lead 2-ethylhexanoate, and a fatty acid metal salt of silver 2-ethylhexanoate (Ag) were prepared, respectively.
In examples and comparative examples, the surfactant (D) used is as follows.
Surfactant (D1): NOIGEN EA-137 (HLB 13.0), manufactured by first Industrial pharmaceutical Co., ltd;
surfactant (D2): NOIGEN EA-167 (HLB 14.8), manufactured by first Industrial pharmaceutical Co., ltd;
Surfactant (D3): NOIGEN EA-177 (HLB 15.6), manufactured by first Industrial pharmaceutical Co., ltd;
surfactant (D4): NOIGEN EA-87 (HLB 10.6), manufactured by first Industrial pharmaceutical Co., ltd;
surfactant (D5): NOIGEN EA-207D (HLB 18.7), manufactured by first Industrial pharmaceutical Co.
Example 1
The neodymium neodecanoate synthesized in synthesis example 2 above was mixed with cyclohexane as the organic solvent (B) to prepare a 52wt% cyclohexane solution of neodymium neodecanoate (neodymium content 18.7 wt%). Then, to a mixture of 45 parts by mass of ion-exchanged water and 5 parts by mass of a surfactant mixed solution (D-A) (a product obtained by dissolving 0.5 parts by mass of NOIGEN EA-137 (HLB 13.0) manufactured by the first Industrial pharmaceutical Co., ltd., 1.5 parts by mass of NOIGEN EA-167 (HLB 14.8), and 1 part by mass of ADEKA NOL UH-752, which was a thickener manufactured by the ADEKA Co., ltd., in 2 parts by mass of a methanol/water mixed solvent), 50 parts by mass of a 52wt% cyclohexane solution of neodymium neodecanoate (neodymium content: 18.7 wt%) was added, and the mixture was stirred at a high speed by using a high-speed emulsifying and dispersing machine (manufactured by Primix Co., ltd., and MARK II 2.5 type of a homogenizer) to obtain an antibacterial and antiviral composition (1). Then, regarding the antibacterial and antiviral composition (1), the emulsion stability and the presence or absence of phase separation/sedimentation were evaluated according to the procedure described in the above columns (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Example 2
An antibacterial and antiviral composition (2) was obtained in the same manner as in example 1, except that the surfactant mixture (D-B) was replaced with the surfactant "NOIGEN EA-167 (HLB 14.8)" in the surfactant mixture (D-A). Then, regarding the antibacterial and antiviral composition (2), the emulsion stability and the presence or absence of phase separation/sedimentation were evaluated according to the procedure described in the above columns (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
The composition of the surfactant mixture (D-B) was obtained by dissolving 0.5 parts by mass of NOIGEN EA-137 (HLB 13.0) manufactured by the first Industrial pharmaceutical Co., ltd., 1.5 parts by mass of NOIGEN EA-177 (HLB 15.6), and 1 part by mass of ADEKA NOL UH-752, a thickener manufactured by the ADEKA Co., ltd., in 2 parts by mass of a methanol/water mixed solvent.
Example 3
To a mixture of 45 parts by mass of ion-exchanged water and 5 parts by mass of the surfactant mixture (D-A) of example 1, 50 parts by mass of a 50wt% mineral spirits solution of zirconium 2-ethylhexanoate (zirconium content: 12.0 wt%) synthesized in synthesis example 11 was added, and the mixture was stirred at a high speed by using a high-speed emulsifying disperser (manufactured by Primix, type MARK II 2.5 homomixer) to obtain an antibacterial and antiviral composition (3). Then, regarding the antibacterial and antiviral composition (3), the emulsion stability and the presence or absence of phase separation/sedimentation were evaluated according to the procedure described in the above columns (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Example 4
To a mixture of 61.7 parts by mass of ion-exchanged water and 5 parts by mass of the surfactant mixture (D-A) of example 1, 33.3 parts by mass of the 25wt% 2-ethylhexanoic acid solution of bismuth 2-ethylhexanoate (bismuth content 25 wt%) synthesized in Synthesis example 3 was added, and the mixture was stirred at a high speed by using a high-speed emulsifying and dispersing machine (manufactured by Primix Co., ltd., homomixer MARK II type 2.5), thereby obtaining an antibacterial and antiviral composition (4). Then, regarding the antibacterial and antiviral composition (4), the emulsion stability and the presence or absence of phase separation/sedimentation were evaluated according to the procedure described in the above columns (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Reference example 1
To a mixture of 45 parts by mass of ion-exchanged water and 5 parts by mass of the surfactant mixture (D-A) of example 1, 50 parts by mass of a 52wt% benzyl alcohol solution of manganese neodecanoate (manganese content: 8.0 wt%) synthesized in synthesis example 10 was added, and the mixture was stirred at a high speed by using a high-speed emulsifying and dispersing machine (manufactured by Primix Co., ltd., homomixer MARK II 2.5 type) to obtain an antibacterial and antiviral composition (C1). Then, regarding the antibacterial and antiviral composition (C1), the emulsion stability and the presence or absence of phase separation/sedimentation were evaluated according to the procedure described in the above columns (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Comparative example 1
The neodymium neodecanoate synthesized in synthesis example 2 above was mixed with cyclohexane as the organic solvent (B) to prepare a 52wt% cyclohexane solution of neodymium neodecanoate (neodymium content 18.7 wt%). Then, 50 parts by mass of a 52wt% cyclohexane solution of neodymium neodecanoate (neodymium content: 18.7 wt%) was added to 50 parts by mass of ion-exchanged water, and the mixture was stirred at a high speed by using a high-speed emulsifying disperser (model 2.5, MARK II, manufactured by Primix Co., ltd.) to obtain comparative composition (1). Then, the comparative composition (1) was evaluated for emulsion stability and the presence or absence of phase separation/sedimentation according to the procedure described in the columns of (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Comparative example 2
Instead of the surfactant mixture (D-A) of example 1, 5 parts by mass of a surfactant mixture (D-C) (a product obtained by dissolving 2 parts by mass of NOIGEN EA-87 (HLB 10.6) manufactured by first Industrial pharmaceutical Co., ltd., 1 part by mass of a thickener UH-752 manufactured by ADEKA Co., ltd., in 2 parts by mass of a methanol/water mixed solvent) was used, and the mixture was stirred at a high speed by using a high-speed emulsifying and dispersing machine (manufactured by Primix Co., ltd., mixer MARK II type 2.5) to obtain a comparative composition (2). Then, the comparative composition (2) was evaluated for emulsion stability and the presence or absence of phase separation/sedimentation according to the procedure described in the columns of (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Comparative example 3
Instead of the surfactant mixture (D-A) of example 1, 5 parts by mass of a surfactant mixture (D-D) (a product obtained by dissolving 2 parts by mass of NOIGEN EA-207D (HLB 18.7) manufactured by first Industrial pharmaceutical Co., ltd., 1 part by mass of a thickener UH-752 manufactured by ADEKA Co., ltd., in 2 parts by mass of a methanol/water mixed solvent) was used, and a high-speed emulsification and dispersion machine (manufactured by Primix Co., ltd., homomixer MARK II type 2.5) was used, followed by stirring at a high speed to obtain a comparative composition (3). Then, the comparative composition (3) was evaluated for emulsion stability and the presence or absence of phase separation/sedimentation according to the procedure described in the columns of (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Comparative example 4
To a mixture of 45 parts by mass of ion-exchanged water and 5 parts by mass of the surfactant mixture (D-A) of example 1, 50 parts by mass of a cyclohexane solution was added, and the mixture was stirred at a high speed by using a high-speed emulsifying and dispersing machine (model MARK II 2.5, manufactured by Primix Co., ltd.) to obtain a comparative composition (4) (containing no metal compound (B)). Then, the comparative composition (4) was evaluated for emulsion stability and the presence or absence of phase separation/sedimentation according to the procedure described in the columns of (2) < evaluation of emulsion stability > and (3) < evaluation of compatibility >.
Composition for antibacterial and antiviral coating and preparation of film-coated article "
Example 5
100 Parts by mass of an aqueous urethane resin (polycarbonate urethane resin: HYDRAN WLS to 210, 35% by solid content of resin) and 2.4 parts by mass of the antibacterial/antiviral composition (metal content: 4.4% by weight) obtained in example 1 were added and stirred by a dispersing stirrer (model 2.5 of TK homodisperse (model homodisperser) manufactured by Primix) to obtain an aqueous paint having 0.3% by mass of metal relative to the solid content of resin in the entire antibacterial/antiviral coating composition. The aqueous coating composition was applied to a PET film (PANAC. Mu.m, thickness 250 μm) by a bar coater at a film thickness of 20. Mu.m, and the resultant antibacterial/antiviral film having the film coating composition was dried at 120℃for 5 minutes, whereby the antiviral property was evaluated and the transparency was evaluated.
The antibacterial and antiviral films prepared were blank test pieces of comparative examples 6 and 7, which were coated with a coating material containing substantially no antibacterial and antiviral composition, and antibacterial and antiviral film prepared in examples 5 to 7 were antibacterial and antiviral coated test pieces, and the above-described antiviral property test and antibacterial property test were performed. The results are shown in Table 2.
Example 6
An aqueous varnish having a metal content of 0.6 mass% relative to the solid content of the resin was obtained in the same manner except that 4.8 parts by mass of the antibacterial/antiviral coating composition of example 5 was added. The aqueous coating composition was applied to a PET film (PANAC. Mu.m, thickness 250 μm) with a bar coater at a film thickness of 20. Mu.m, and the film coating composition obtained by drying at 120℃for 5 minutes was evaluated for antiviral properties and appearance.
Example 7
An aqueous paint having a metal content of 1.8 mass% relative to the solid resin component was obtained in the same manner except that 14 parts by mass of the antibacterial/antiviral coating composition of example 5 was added. The aqueous coating composition was applied to a PET film (PANAC. Mu.m, thickness 250 μm) with a bar coater at a film thickness of 20. Mu.m, and the film coating composition obtained by drying at 120℃for 5 minutes was evaluated for antiviral properties and appearance.
Comparative example 5
Aqueous urethane resin (manufactured by DIC, HYDRAN WLS-210) was directly coated on PET film (manufactured by PANAC, thickness 250 μm) by a bar coater to obtain a film-coated article.
Comparative example 6
100 Parts by mass of an aqueous urethane resin (polycarbonate urethane resin: HYDRAN WLS to 210, 35% of resin solid content, manufactured by DIC Co., ltd.) and 1 part by mass of silver-supported zirconium phosphate (NOVARON AG to 1100, 11% by weight of silver ion content, manufactured by Toyama Co., ltd.) were added, and the mixture was stirred by a dispersing stirrer (TK homodisperse type 2.5, manufactured by Primix Co.) to obtain an aqueous paint having a silver content of 3.85% by mass relative to the resin solid content. The aqueous coating composition was applied to a PET film (PANAC. Mu.m, thickness 250 μm) with a bar coater at a film thickness of 20. Mu.m, and the film coating composition obtained by drying at 120℃for 5 minutes was evaluated for antiviral properties and appearance.
Composition for antibacterial and antiviral coating and production of antibacterial and antiviral fabric "
Example 8
< Preparation of aqueous fiber processing liquid and fabric >
An aqueous varnish was prepared by mixing 24 parts by mass of the antibacterial/antiviral composition (1) of example 1, 71.6 parts by mass of water, 3 parts by mass of an aqueous acrylic resin (DEXCEL HPS CLEAR CONC L-502 manufactured by DIC) and 1.4 parts by mass of ethylcellulose with stirring. The aqueous coating composition was prepared by stirring 20 parts by mass of the aqueous coating composition and 80 parts by mass of water with a dispersing mixer (model 2.5 of TK homodisperse manufactured by Primix Co., ltd.) to prepare an antibacterial/antiviral coating composition as an aqueous fiber processing liquid. The antibacterial/antiviral coating composition was impregnated into a cotton/polyester blend fabric (gray fabric quality 100g/m 2) at a ratio of 85g/m 2, and dried for 2 minutes at 120 to obtain an antibacterial/antiviral fabric.
TABLE 1
TABLE 2
From the results of table 1 above, it was confirmed that the antibacterial and antiviral composition of the present invention example was excellent in compatibility and emulsion stability as compared with the composition of the comparative example. Based on the results of table 2, it was confirmed that the antibacterial and antiviral film and the antibacterial and antiviral fabric prepared using the antibacterial and antiviral coating composition containing the antibacterial and antiviral composition of the example of the present invention were highly antibacterial and antiviral.

Claims (9)

1. An antibacterial and antiviral composition comprising:
An aqueous solvent (A) having a Hansen solubility parameter, i.e., a hydrogen bond term dH of HSP value, of 18.0 or more,
A metal compound (B) which is poorly soluble in the aqueous solvent (A),
An organic solvent (C) which exhibits solubility with respect to the metal compound (B),
A surfactant (D) having an HLB value within the range of 11 to 18,
The antibacterial and antiviral composition satisfies the following formula (1),
|dHC-dHA|≥30.0 (1)
In the formula (1), dHC represents a hydrogen bond term dH of HSP value, which is a hansen solubility parameter of the organic solvent (C), and dHA represents a hydrogen bond term dH of HSP value, which is a hansen solubility parameter of the aqueous solvent (a).
2. The antibacterial and antiviral composition according to claim 1, which contains:
30 to 89.5% by mass of the aqueous solvent (A),
5 To 35% by mass of the metal compound (B),
5 To 40% by mass of the organic solvent (C), and
And 0.5 to 10% by mass of the surfactant (D).
3. The antibacterial and antiviral composition according to claim 1 or 2, which has a core-shell structure comprising:
a core part containing the metal compound (B) and the organic solvent (C), and
A shell portion containing the surfactant (D).
4. The antibacterial and antiviral composition according to claim 1 or 2, wherein,
The metal compound (B) is 1 or more selected from fatty acid metal salts, metal complexes of ligands containing hetero atoms and metal ions, and metal complexes of ligands containing hetero atoms and fatty acid metal salts, and
The metal of the fatty acid metal salt, the metal of the metal complex of the heteroatom-containing ligand and metal ion, and the metal of the metal complex of the heteroatom-containing ligand and fatty acid metal salt are each independently 1 or 2 or more selected from magnesium, manganese, cobalt, yttrium, lead, bismuth, and lanthanide metals.
5. The antibacterial and antiviral composition according to claim 1 or 2, wherein the metal amount of the metal compound (B) is 0.01 to 50% by mass relative to the total solid content of the antibacterial and antiviral composition.
6. An antibacterial and antiviral coating composition comprising an aqueous resin dispersion and the antibacterial and antiviral composition according to claim 1 or 2.
7. An antibacterial and antiviral fabric comprising:
Fabric, and
A coating layer comprising the antibacterial and antiviral coating composition according to claim 6, which is applied to the fabric.
8. An antimicrobial antiviral film, comprising:
substrate film, and
A coating layer comprising the antibacterial and antiviral coating composition according to claim 6, provided on at least one surface of the base film.
9. The antibacterial antiviral film according to claim 8, which has a difference in haze value from a blank film not containing the metal compound (B) contained in the antibacterial antiviral composition according to claim 1 or 2 of 10% or less.
CN202311753089.4A 2022-12-21 2023-12-19 Antibacterial/antiviral composition, antibacterial/antiviral fabric, and antibacterial/antiviral film Pending CN118216520A (en)

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