WO2024128107A1

WO2024128107A1 - Masterbatch, resin composition, molded article, and methods for producing same

Info

Publication number: WO2024128107A1
Application number: PCT/JP2023/043751
Authority: WO
Inventors: 悠太山岡; 洋輝後藤; 幸介藤田; 宏明中野
Original assignee: Dic株式会社
Priority date: 2022-12-13
Filing date: 2023-12-07
Publication date: 2024-06-20

Abstract

Provided are a molded article having excellent antibacterial and antiviral activities and a method for producing the same with good processability, a masterbatch which makes it possible to provide the molded article and the production method, a thermoplastic resin composition, and methods for producing the same. More specifically, provided are: a masterbatch which contains an antibacterial/antiviral agent which is at least one selected from the group consisting of a fatty acid metal salt, a metal complex of a hetero-atom-containing ligand and a metal ion, and a metal complex of a hetero-atom-containing ligand and a fatty acid metal salt, wherein the metal in each of the fatty acid metal salt, the metal complex of a hetero-atom-containing compound ligand and a metal ion, and the metal complex of a hetero-atom-containing compound ligand and a fatty acid metal salt is independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper; a resin composition prepared by melt-kneading the masterbatch with a thermoplastic resin; a molded article produced by melt-molding the resin composition; and methods for producing the same.

Description

Masterbatch, resin composition, molded article and method for producing same

This disclosure relates to masterbatches, resin compositions, molded articles, and methods for producing the same.

The spread of COVID-19 has led to a rapid increase in people's awareness of hygiene. There is also a growing global need for "antibacterial and antiviral" products for daily necessities to reduce the possibility of infection with pathogens and viruses. For example, there is a strong demand for antibacterial and antiviral properties on surfaces such as the exteriors of smartphones, smartphone touch panels, handrails, doorknobs, washbasins, elevator buttons and other push buttons, and the interiors of public transportation, as these are expected to be used multiple times throughout the day.

Silver carriers, particularly silver-loaded zirconium phosphate, are known as antibacterial and antiviral agents (see, for example, Patent Document 1), and are known to be used in combination with plastics such as polyester and polystyrene.

International Publication No. 2005/037296

However, there is room for improvement in the compatibility of silver-loaded particles with thermoplastic resins, and the transparency is not sufficiently maintained when the resin composition is made by melt kneading. In addition, particle aggregation can cause defects in the appearance of molded products, and there is a risk of reduced processability due to an increase in filter pressure during melt processing. As a result, shear heating occurs when kneading with the particles, and the material deteriorates, which can lead to poor processability and a decrease in physical properties.

The problem that the invention aims to solve is to provide a molded article that combines excellent antibacterial and antiviral properties, transparency and surface appearance, a thermoplastic resin composition that can provide the molded article and has excellent processability, and a method for producing them. The second problem that the invention aims to solve is to provide a masterbatch that can provide the thermoplastic resin composition, and a method for producing the masterbatch.

As a result of intensive research by the inventors to solve the above problems, they discovered that a thermoplastic resin composition containing a specific fatty acid metal salt or metal complex can provide a molded article that combines excellent antibacterial properties, antiviral properties, transparency, and surface appearance, thereby solving the above problems. In addition, they discovered that a thermoplastic resin composition produced using a masterbatch containing a thermoplastic resin and a specific fatty acid metal salt or metal complex can provide a molded article that combines excellent antibacterial properties, antiviral properties, transparency, and surface appearance, thereby solving the above problems.

That is,
[1] The present disclosure provides a masterbatch containing a thermoplastic resin and an antibacterial and antiviral agent,
The antibacterial and antiviral agent is contained in an amount of 0.03 to 90 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch, or the content of the metal derived from the antibacterial and antiviral agent is contained in an amount of 0.0015 to 45 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch,
The present invention relates to a master batch characterized in that the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure also provides a masterbatch containing a thermoplastic resin and an antibacterial and antiviral agent,
The antibacterial and antiviral agent is contained in an amount of 0.03 to 90 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure also provides a masterbatch containing a thermoplastic resin and an antibacterial and antiviral agent,
the content of the metal derived from the antibacterial and antiviral agent is in the range of 0.0015 to 45 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

[2] The present disclosure relates to the masterbatch described in [1], in which the metal of the fatty acid metal salt, the metal of the metal complex of the heteroatom-containing compound ligand and a metal ion, and the metal of the metal complex of the heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, or magnesium.

[3] The present disclosure relates to a masterbatch according to any one of [1] to [2], in which the fatty acid metal salt is a metal salt of a fatty acid having 2 to 31 carbon atoms.

[4] The present disclosure relates to a masterbatch according to any one of [1] to [3], in which the fatty acid metal salt is a metal salt of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, or melissic acid.

[5] The present disclosure relates to a masterbatch according to any one of [1] to [5], wherein the heteroatom-containing ligand is one 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, 2,2'-bipyridyl and its derivatives, and 2,2'-[propane-1,2-diylbis(azanylylidenemethanylylidene)]diphenol and its derivatives.

[6] The present disclosure provides a method for producing a masterbatch, comprising a step of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
blending an antibacterial and antiviral agent in an amount within the range of 0.03 to 90 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch, or blending an antibacterial and antiviral agent such that the content of metal derived from the antibacterial and antiviral agent is within the range of 0.0015 to 45 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch;
The present invention relates to a method for producing a master batch, wherein the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure also provides a method for producing a masterbatch, the method comprising the steps of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
the content of the antibacterial and antiviral agent is in the range of 0.03 to 90 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure also provides a method for producing a masterbatch, the method comprising the steps of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
the antibacterial and antiviral agent is blended so that the content of the metal derived from the antibacterial and antiviral agent falls within the range of 0.0015 to 45 parts by mass per 100 parts by mass in total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

[7] The present disclosure provides a thermoplastic resin composition containing a thermoplastic resin and an antibacterial and antiviral agent,
The antibacterial and antiviral agent is contained in an amount of 0.01 to 30 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition, or the antibacterial and antiviral agent is contained so that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition;
The present invention relates to a thermoplastic resin composition, characterized in that the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure provides a thermoplastic resin composition comprising a thermoplastic resin and an antibacterial and antiviral agent,
The antibacterial and antiviral agent is contained in an amount of 0.01 to 30 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure also provides a thermoplastic resin composition comprising a thermoplastic resin and an antibacterial and antiviral agent,
the content of the metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

[8] The present disclosure also provides a method for producing a thermoplastic resin composition, comprising the steps of blending a thermoplastic resin as a diluting resin with the masterbatch according to any one of [1] to [5] above, and melt-kneading the blend,
The present invention relates to a method for producing a thermoplastic resin composition, characterized in that a master batch and a diluent resin are blended together so that the antibacterial and antiviral agent is in the range of 0.01 to 30 parts by mass per 100 parts by mass of the thermoplastic resin, antibacterial and antiviral agent, and diluent resin in the master batch, or the master batch and a diluent resin are blended together so that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the thermoplastic resin, antibacterial and antiviral agent, and diluent resin in the master batch.

The present disclosure also provides a method for producing a thermoplastic resin composition, comprising the steps of blending a thermoplastic resin as a diluting resin with the masterbatch according to any one of [1] to [5] above, and melt-kneading the blend,
The master batch and a diluent resin may be blended so that the antibacterial and antiviral agent is in the range of 0.01 to 30 parts by mass per 100 parts by mass in total of the thermoplastic resin and the antibacterial and antiviral agent in the master batch, and the diluent resin.

The present disclosure also provides a method for producing a thermoplastic resin composition, comprising the steps of blending a thermoplastic resin as a diluting resin with the masterbatch according to any one of [1] to [5] above, and melt-kneading the blend,
The master batch and a diluent resin may be blended so that the content of the metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass in total of the thermoplastic resin and the antibacterial and antiviral agent in the master batch, and the diluent resin.

[9] The present disclosure also provides a method for producing a thermoplastic resin composition, comprising a step of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
blending an antibacterial and antiviral agent in an amount within the range of 0.01 to 30 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition, or blending a thermoplastic resin and an antibacterial and antiviral agent such that the content of metal derived from the antibacterial and antiviral agent is within the range of 0.0005 to 15 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition;
The present invention relates to a method for producing a thermoplastic resin composition, wherein the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure also provides a method for producing a thermoplastic resin composition, the method comprising a step of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
blending the antibacterial and antiviral agent in an amount of 0.01 to 30 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The present disclosure also provides a method for producing a thermoplastic resin composition, the method comprising a step of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
blending a thermoplastic resin and an antibacterial and antiviral agent so that the content of a metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition;
The antibacterial and antiviral agent may be one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt may each independently be a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

[10] The present disclosure relates to a molded article obtained by molding the thermoplastic resin composition described in [7] above.

[11] The present disclosure relates to a method for producing a molded article, comprising a step of melt-molding the resin composition described in [7] above.

According to the present disclosure, it is possible to provide a molded article having excellent antibacterial and antiviral properties, transparency, and surface appearance, a thermoplastic resin composition capable of providing the molded article and having excellent processability, and a method for producing the same. In addition, according to the present disclosure, it is possible to provide a masterbatch capable of providing the thermoplastic resin composition, and a method for producing the same.

Thermoplastic resin The thermoplastic resin used in the present disclosure is not particularly limited as long as it does not impair the effects of the present disclosure, and examples thereof include polyolefin resins, polycarbonate resins, polystyrene resins, acrylic resins, polyoxymethylene resins, polyester resins, vinyl chloride resins, cycloolefin polymers (COP), and thermoplastic elastomers. The thermoplastic resin used in the present disclosure may be one type or a mixture of two or more types. When two or more types are mixed, it is preferable to use a combination of resins with high compatibility.

The polyolefin resin is a polyolefin resin obtained by polymerizing at least one kind of olefin, and may be a homopolymer or a copolymer.
Examples of such olefins include α-olefins having 4 to 12 carbon atoms, including ethylene, propylene, isobutylene, and isobutene (1-butene), butadiene, isoprene, (meth)acrylic acid esters, (meth)acrylic acid, (meth)acrylamide, vinyl alcohol, vinyl acetate, vinyl chloride, styrene, and acrylonitrile.

Examples of α-olefins having 4 to 12 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl These include 1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.

Polyolefin resins are not particularly limited, but examples include polyethylene resins, polypropylene resins, polymethylpentene resins, polyisobutylene resins, polyisobutene resins, polyisoprene resins, polybutadiene resins, etc. Of these resins, polyethylene resins, polypropylene resins, and polymethylpentene resins are preferred.

When classified by density or shape, examples include high density polyethylene (HDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and ultra-high molecular weight polyethylene (UHMW-PE), of which high density polyethylene, linear low density polyethylene, and low density polyethylene are preferred.

Polycarbonate resins include polycarbonate (PC), etc. Polystyrene resins include polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymer (SAN) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, etc.

Acrylic resins include polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate, etc. Polyoxymethylene resins include polyoxymethylene (POM), etc. Polyester resins include aromatic polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and polybutylene naphthalate.

Vinyl chloride resins include polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer resin, etc. Thermoplastic elastomers include polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, styrene thermoplastic elastomers, olefin thermoplastic elastomers, etc.

Antibacterial and Antiviral Agent The antibacterial and antiviral agent used in the present disclosure is one or more selected from the group consisting of fatty acid metal salts, metal complexes of heteroatom-containing ligands and metal ions, and metal complexes of heteroatom-containing ligands and fatty acid metal salts, wherein the metals in the fatty acid metal salts, the metal complexes of heteroatom-containing compound ligands and metal ions, and the metal complexes of heteroatom-containing compound ligands and fatty acid metal salts are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.

The antibacterial and antiviral agent used in this disclosure takes the form of a fatty acid metal salt or metal complex, and due to the antibacterial and antiviral properties of the metal and the high compatibility of the fatty acid or complex ligand with organic matter, when blended with a thermoplastic resin, it is believed to impart antibacterial and antiviral properties to the resulting thermoplastic resin composition while reducing the impact on appearance, such as the loss of transparency caused by the antibacterial and antiviral agent.

In this disclosure, "antibacterial" means the effect of reducing the number of bacteria, the effect of suppressing the increase in the number of bacteria, etc. Similarly, in this disclosure, "antiviral" means the effect of reducing the number of viruses, the effect of inactivating viruses, the effect of reducing the infectivity of viruses, etc. In this disclosure, "antibacterial and antiviral agent" means a substance that exerts both "antibacterial" and "antiviral" effects.

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

In this disclosure, the viruses that are the subject of antiviral treatment are not particularly limited, and may be any of the known enveloped viruses (viruses that have an envelope) and non-enveloped viruses (viruses that do not have an envelope).

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

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

The antibacterial and antiviral agents used in this disclosure are described below.

(Fatty acid metal salts)
The antibacterial and antiviral agent used in the present disclosure may be a fatty acid metal salt. The fatty acid metal salt is a metal salt of a fatty acid, and the metals constituting the metal salt may each independently be lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper. Note that lanthanoid is an element belonging to group 3A of the periodic table, and is a general term for 15 elements with atomic numbers 57 to 71, that is, lanthanum to lutetium.
Among these metals, lanthanoids, bismuth, and magnesium are preferred from the viewpoint of making it difficult for coloration to occur due to the addition of an antibacterial and antiviral agent. Among the lanthanoids, lanthanum, praseodymium, neodymium, samarium, and gadolinium are particularly preferred.

It is preferable that the fatty acid is a fatty acid having 2 to 31 carbon atoms. The fatty acid may also include a linear, branched, or alicyclic structure.

Fatty acids having 2 to 31 carbon atoms have a carboxy group (COOH) and a fatty acid residue (carboxylic acid residue) having 1 to 30 carbon atoms. Examples of such fatty acids include fatty acids such as saturated fatty acids and unsaturated fatty acids. More specifically, examples of saturated fatty acids include saturated fatty acids with a straight chain structure such as acetic acid, propionic acid, butanoic acid, pentanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid, and saturated fatty acids with a branched or alicyclic structure such as octylic acid (2-ethylhexanoic acid), neodecanoic acid, isostearic acid, naphthenic acid, and isononanoic acid. Examples of unsaturated fatty acids include monounsaturated fatty acids such as acrylic acid, methacrylic acid, palmitoleic acid, oleic acid, elaidic acid, paccenic acid, and erucic acid, and polyunsaturated fatty acids derived from vegetable oils such as tung oil 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, and tung oil fatty acid.

Among the fatty acids having 2 to 31 carbon atoms, from the viewpoint of ease of handling of the compound and the ability to suppress thermal degradation such as burning and scorching of the agent and the resulting contamination with foreign matter when processed into a master batch or pellets of a thermoplastic resin composition (hereinafter referred to as "thermal degradation suppression"), fatty acids having 11 to 31 carbon atoms are more preferred, and most preferred are capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, etc.

More specifically, the fatty acid metal salt used as the antibacterial and antiviral agent in the present disclosure is preferably, for example, a compound represented by the following general formula (1):

(In the general formula (1),
R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms;
n1 is an integer ranging from 1 to 4;
^M1 is a lanthanide, bismuth, manganese, magnesium, lead, yttrium, cobalt or copper.

In the general formula (1), when n1 is an integer of 2 or more, multiple R ^1s may be the same or different.

The hydrocarbon group having 1 to 30 carbon atoms for R ¹ may be a straight-chain hydrocarbon group, a branched hydrocarbon group, or may contain an alicyclic structure.

The hydrocarbon group having 1 to 30 carbon atoms represented by ^R1 corresponds to a fatty acid residue (carboxylic acid residue) obtained by removing a carboxy group (COOH) from a carboxylic acid having 2 to 31 carbon atoms represented by ^R1COOH used in the production of a fatty acid metal salt. Accordingly, examples of the fatty acid residue (carboxylic acid residue) include residues obtained by removing a carboxy group from the fatty acids listed above.

The hydrocarbon group having 1 to 30 carbon atoms for ^R1 is preferably an alkyl group having 10 to 30 carbon atoms, more preferably a capric acid residue, a lauric acid residue, a myristic acid residue, a palmitic acid residue, a stearic acid residue, an arachidic acid residue, a behenic acid residue, a lignoceric acid residue, a cerotic acid residue, a montanic acid residue, a melissic acid residue, or the like, from the viewpoint of ease of handling the compound and of suppressing thermal degradation when the thermoplastic resin composition is processed into a master batch or pellets.

^M1 is a lanthanide, bismuth, manganese, magnesium, lead, yttrium, cobalt or copper.

n1 is a numerical value determined by the ionic valence of the metal atom of ^M1 . For example, if ^M1 is neodymium, n1 is 3, and if ^M1 is cobalt, n1 is 2.

The fatty acid metal salt, which is the antibacterial and antiviral agent of the present disclosure, may also be in the form of a fatty acid metal borate. An example of such a fatty acid metal borate is a compound represented by the following general formula (2).

(In the general formula (2),
^R2 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms;
^M2 is a lanthanide, bismuth, manganese, magnesium, lead, yttrium, cobalt or copper.

In the general formula (2), the hydrocarbon group having 1 to 30 carbon atoms for ^R2 is the same as the hydrocarbon group having 1 to 30 carbon atoms for ^R1 in the general formula (1). Similarly, in the general formula (2), the metal for ^M2 is the same as the metal for ^M1 in the general formula (1).

When a fatty acid metal salt is used as the antibacterial and antiviral agent used in this disclosure, a single type of fatty acid metal salt may be used, or two or more types of fatty acid metal salts having different structures may be used.

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

(Metal Complex)
The antibacterial and antiviral agent used in the present disclosure may be 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, which may be a compound in which a metal ion or a fatty acid metal salt and a heteroatom-containing ligand form a complex via a coordinate bond.

As the metal ion with which the heteroatom-containing ligand forms a metal complex, the same metal ion as the metal of the fatty acid metal salt explained as the antibacterial and antiviral agent used in the present disclosure can be used.
As the fatty acid metal salt in which the heteroatom-containing ligand forms a metal complex, the same fatty acid metal salts described as the antibacterial and antiviral agent used in the present disclosure can be used.

The heteroatom-containing ligand that forms the metal complex may be a ligand that has one or more heteroatoms selected from the group consisting of 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 (DICY), tri-n-butylamine, dimethylbenzylamine, butylamine, 1,2-propanediamine, 1,2-cyclohexanediamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylbenzylamine, butylamine, 1,2-propanediamine, 1,2-cyclohexanediamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylbenzylamine, dimethyl ... amine, 2-[[(2-dimethylamino)ethyl]methylamino]ethanol, picolinic acid, 2,2'-[propane-1,2-diylbis(azanylylidenemethanylylidene)]diphenol, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3 amine compounds such as -(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, 8-quinolinol, 5-chloro-8-quinolinol, 2,2'-bipyridyl and its derivatives, 2,2'-[propane-1,2-diylbis(azanylylidenemethanylylidene)]diphenol and its derivatives, and 2,2'-methylenebis[6-(2h-benzotriazol-2-yl)-4-tert-octylphenol]; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; Phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; and sulfur-based compounds such as thiolactic acid, 2-aminothiophenol, and 2,2'-dithiodianiline.

The heteroatom-containing ligand is preferably one 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, 2,2'-bipyridyl and its derivatives, and 2,2'-[propane-1,2-diylbis(azanylylidenemethanylylidene)]diphenol and its derivatives.

The heteroatom-containing ligand that forms the metal complex may be of one type alone or of two or more types that are different in structure.

In the metal complex, the ratio (molar ratio) of the metal ion or fatty acid metal salt to the heteroatom-containing ligand is, for example, in the range of 0.1 to 12 moles of the heteroatom-containing ligand per mole of metal atom of the metal ion or fatty acid metal salt, preferably in the range of 0.3 to 10 moles, and more preferably in the range of 0.5 to 10 moles.

The melting points of the fatty acid metal salt, the metal complex of the heteroatom-containing compound ligand and metal ion, and the metal complex of the heteroatom-containing compound ligand and fatty acid metal salt contained in the antibacterial and antiviral agent used in the present disclosure are not particularly limited, but from the viewpoint of the ease of handling of the compounds and the suppression of thermal degradation when processed into a master batch or a pellet of a thermoplastic resin composition, it is preferable that the compounds are solid in the working environment (0°C to 45°C), and more preferably have a melting point of 50°C or higher, even more preferably 60°C or higher, and particularly preferably 70°C or higher. The upper limit is not particularly limited, but may be 250°C or lower.

The content of the metal derived from the fatty acid metal salt, the metal complex of the heteroatom-containing compound ligand and a metal ion, and the metal complex of the heteroatom-containing compound ligand and a fatty acid metal salt (hereinafter sometimes referred to as "metal derived from the antibacterial and antiviral agent" or simply "metal") contained in the antibacterial and antiviral agent used in the present disclosure is not particularly limited, but is preferably 5 parts by mass or more, more preferably 7.5 parts by mass or more, and particularly preferably 10 parts by mass or more, relative to 100 parts by mass of the antibacterial and antiviral agent. Also, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.

The antibacterial and antiviral agent used in the present disclosure is preferably a water-insoluble antibacterial and antiviral agent. The water-insoluble antibacterial and antiviral agent has excellent durability of antibacterial and antiviral properties even when exposed to water such as rain.
In the present application, "water-insoluble" means that the amount of water required to dissolve 1 g of the antibacterial and antiviral agent at 20°C is 10 ml or more.

The antibacterial and antiviral agents, that is, the metal complex of a heteroatom-containing ligand and a metal ion and the metal complex of a heteroatom-containing ligand and a fatty acid metal salt, can be produced by known methods, and can be produced by reacting a metal alone or a fatty acid metal salt with a heteroatom-containing ligand. In addition, the metal complex may be a commercially available product.

・Master batch (Master batch)
The masterbatch of the present disclosure contains a thermoplastic resin and an antibacterial and antiviral agent.
The masterbatch of the present disclosure contains an antibacterial, antiviral agent in a range of 0.03 to 90 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial, antiviral agent in the masterbatch, or contains the antibacterial, antiviral agent such that the content of metal derived from the antibacterial, antiviral agent is in the range of 0.0015 to 45 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial, antiviral agent in the masterbatch.

More specifically, the composition ratio of the thermoplastic resin and the antibacterial and antiviral agent contained in the masterbatch of the present disclosure is preferably 0.03 parts by mass or more, more preferably 0.15 parts by mass or more, and even more preferably 0.3 parts by mass or more per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch in order to impart excellent dispersibility and antiviral properties to the molded article obtained via the masterbatch, but is preferably in the range of 90 parts by mass or less, more preferably 75 parts by mass or less, and even more preferably 60 parts by mass or less, taking into consideration the suppression of thermal degradation during processing into the masterbatch and the cost benefits during transportation.

The content of the metal derived from the antibacterial and antiviral agent contained in the master batch of the present disclosure is not particularly limited, but can be calculated taking into consideration the content of the metal contained in the antibacterial and antiviral agent and the composition ratio of the antibacterial and antiviral agent contained in the master batch. That is, the content of the metal is preferably 0.0015 parts by mass or more, more preferably 0.0075 parts by mass or more, and even more preferably 0.015 parts by mass or more, and preferably 45 parts by mass or less, more preferably 37.5 parts by mass or less, and even more preferably 30 parts by mass or less, relative to a total of 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent contained in the master batch. If the content of the metal contained in the master batch is within the above range, the molded body obtained via the master batch can be imparted with excellent dispersibility, transparency, and antibacterial and antiviral properties.

In addition to the thermoplastic resin and antibacterial and antiviral agent components described above, the master batch of the present disclosure may also contain various known additives as optional components within a range that does not impair the effects of the present disclosure. Examples of optional additives include antiblocking agents such as silica, flame retardants such as halogen-based flame retardants, nitrogen-based flame retardants, phosphate ester-based flame retardants, inorganic flame retardants such as metal hydroxides and oxides, and silicone-based flame retardants, antioxidants such as hindered phenol compounds, hydroquinone compounds, phosphite compounds, and their substitutes, weather resistance agents such as resorcinol compounds, salicylate compounds, benzotriazole compounds, benzophenone compounds, and hindered amine compounds, release agents or lubricants such as aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisurea compounds, and polyethylene wax, pigments such as phthalocyanine and carbon black, dyes such as nigrosine and aniline black, talc, silica, kaolin, clay, and the like. Examples of such antistatic agents include crystal nucleating agents such as octyl p-oxybenzoate and N-butylbenzenesulfonamide, plasticizers such as octyl p-oxybenzoate and N-butylbenzenesulfonamide, antistatic agents such as alkyl sulfate-type anionic antistatic agents, quaternary ammonium salt-type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, and betaine-type amphoteric antistatic agents, as well as various particulate, needle-like, and plate-like fillers such as graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, iron, stainless steel, bentonite, montmorillonite, and synthetic mica, and reinforcing materials such as glass fiber, glass flakes, carbon fiber, boron nitride, potassium titanate, and aluminum borate.

When various additives are added as optional components, their composition ratio is not particularly limited as long as it does not impair the effects of the present disclosure, but the desired function can be freely adjusted by adjusting the type and amount of these additives, preferably within the range of 0.01 parts by mass or more and 300 parts by mass or less per 100 parts by mass of the thermoplastic resin and antibacterial and antiviral agent in the master batch.

(Masterbatch manufacturing method)
The method for producing a masterbatch according to the present disclosure includes a step of blending a thermoplastic resin and an antibacterial and antiviral agent as essential components, and melt-kneading the blend.

The method for producing a masterbatch disclosed herein involves blending an antibacterial and antiviral agent in the range of 0.03 to 90 parts by mass per 100 parts by mass of the thermoplastic resin and antibacterial and antiviral agent in the masterbatch, or blending the antibacterial and antiviral agent so that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0015 to 45 parts by mass per 100 parts by mass of the thermoplastic resin and antibacterial and antiviral agent in the masterbatch.

More specifically, when producing the masterbatch of the present disclosure, the compounding ratio may be, for example, adjusted and compounded so that the antibacterial and antiviral agent is preferably 0.03 parts by mass or more, more preferably 0.15 parts by mass or more, and even more preferably 0.3 parts by mass or more, and preferably 90 parts by mass or less, more preferably 75 parts by mass or less, and even more preferably 60 parts by mass or less, per 100 parts by mass of the total of the thermoplastic resin and antibacterial and antiviral agent in the masterbatch.

The amount of metal contained in the master batch of the present disclosure is not particularly limited, but the antibacterial and antiviral agent can be blended in consideration of the amount of metal contained in the antibacterial and antiviral agent and the composition ratio of the antibacterial and antiviral agent contained in the master batch. That is, the thermoplastic resin and the antibacterial and antiviral agent may be blended in such a way that the amount of metal contained in the master batch is preferably 0.0015 parts by mass or more, more preferably 0.0075 parts by mass or more, and even more preferably 0.015 parts by mass or more, and preferably 45 parts by mass or less, more preferably 37.5 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent contained in the master batch in total.

More specifically, the above-mentioned components are premixed as necessary using a mixer such as a V-type blender, ribbon blender, or Henschel mixer, and then melt-kneaded using a known mixer such as a single-screw extrusion type kneader, open roll mixer, pressure kneader, Banbury mixer, or twin-screw extrusion type kneader, with the resin set temperature set to above the melting point. Among these, twin-screw extrusion type kneaders are preferred in terms of kneading ability and productivity. After melt-kneading, the mixture is processed into pellets or the like according to conventional methods to obtain the master batch of the present disclosure.

Thermoplastic resin composition (thermoplastic resin composition)
The thermoplastic resin composition of the present disclosure contains a thermoplastic resin and an antibacterial and antiviral agent.
The thermoplastic resin composition of the present disclosure contains an antibacterial and antiviral agent in a range of 0.01 to 30 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent, or contains the antibacterial and antiviral agent such that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition.

More specifically, the composition ratio of the thermoplastic resin and the antibacterial and antiviral agent contained in the thermoplastic resin composition of the present disclosure is preferably in the range of 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, to preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition in total, from the viewpoint of imparting excellent dispersibility and antiviral properties to a molded article obtained using the thermoplastic resin composition of the present disclosure.

The content of the metal derived from the antibacterial and antiviral agent contained in the thermoplastic resin composition of the present disclosure is not particularly limited, but can be calculated taking into consideration the content of the metal contained in the antibacterial and antiviral agent and the composition ratio of the antibacterial and antiviral agent contained in the thermoplastic resin composition. That is, the content of the metal is preferably 0.0005 parts by mass or more, more preferably 0.0025 parts by mass or more, and even more preferably 0.005 parts by mass or more, and preferably 15 parts by mass or less, more preferably 12.5 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent contained in the thermoplastic resin composition. If the content of the metal contained in the thermoplastic resin composition is within the above range, the finally obtained molded body can be imparted with excellent dispersibility, transparency, and antibacterial and antiviral properties.

(Method for producing thermoplastic resin composition)
The method for producing a thermoplastic resin composition according to the present disclosure includes a step of blending a thermoplastic resin for dilution (hereinafter sometimes referred to as a "dilution resin") with the masterbatch and melt-kneading the blend. By obtaining a thermoplastic resin composition via a masterbatch in this manner, the antibacterial and antiviral agent can be stably and uniformly dispersed and can also be added at a high concentration, so that an excellent antibacterial and antiviral effect can be imparted to a molded article.

The thermoplastic resin in the master batch and the thermoplastic resin in the diluent resin used in this disclosure may be the same type of resin or different types of resin depending on the purpose, but it is preferable to use the same type of resin from the standpoint of compatibility.

The manufacturing method of the thermoplastic resin composition disclosed herein involves blending an antibacterial and antiviral agent in an amount ranging from 0.01 to 30 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent combined, or blending an antibacterial and antiviral agent such that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent combined in the thermoplastic resin composition.

More specifically, when producing the thermoplastic resin composition of the present disclosure from the masterbatch of the present disclosure, the blending ratio may be, for example, such that the masterbatch of the present disclosure and the diluent resin are prepared and blended such that the antibacterial and antiviral agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the total of the thermoplastic resin and antibacterial and antiviral agent in the masterbatch, and the diluent resin.

The content of the metal contained in the thermoplastic resin composition of the present disclosure is not particularly limited, but the master batch and the diluent resin may be blended in consideration of the content of the metal contained in the antibacterial and antiviral agent and the composition ratio of the antibacterial and antiviral agent contained in the thermoplastic resin composition. That is, the master batch and the diluent resin may be blended in such a way that the content of the metal is preferably 0.0005 parts by mass or more, more preferably 0.0025 parts by mass or more, and even more preferably 0.005 parts by mass or more, and preferably 15 parts by mass or less, more preferably 12.5 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the master batch, and the diluent resin.

The thermoplastic resin composition of the present disclosure is preferably produced by blending and melt-kneading the master batch of the present disclosure with a diluent resin as described above, since this allows the antibacterial and antiviral agent to be stably and uniformly dispersed, can be added at high concentrations, and provides the molded article with excellent transparency and surface appearance, but it can also be produced without using a master batch.

That is, when the thermoplastic resin composition of the present disclosure is produced without using a master batch, the method for producing the thermoplastic resin composition of the present disclosure includes a step of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent as raw materials so that they have a predetermined composition ratio. When the thermoplastic resin composition of the present disclosure is produced without using a master batch, the blending ratio is, for example, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, relative to a total of 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition. The thermoplastic resin and the antibacterial and antiviral agent can also be blended in consideration of the content of metal contained in the antibacterial and antiviral agent and the composition ratio of the antibacterial and antiviral agent contained in the thermoplastic resin composition. That is, the thermoplastic resin and the antibacterial and antiviral agent may be blended so that the content of the metal is preferably in the range of 0.0005 parts by mass or more, more preferably 0.0025 parts by mass or more, and even more preferably 0.005 parts by mass or more, and preferably 15 parts by mass or less, more preferably 12.5 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition.

In the method for producing the thermoplastic resin composition disclosed herein, the melt-kneading method is not particularly limited, and for example, a method similar to the method for producing the master batch can be adopted. The thermoplastic resin composition obtained by melt-kneading can then be temporarily processed into pellets or the like according to a conventional method.

In addition to the above-mentioned thermoplastic resin and antibacterial and antiviral agent components, the thermoplastic resin composition of the present disclosure may also contain various known additives as optional components within a range that does not impair the effects of the present disclosure. Examples of the various additives that can be added as optional components include the same additives that can be added to the above-mentioned master batch. Of these, from the viewpoint of blocking inhibition, it is preferable to further add an antiblocking agent such as silica.

When various additives are added as optional components, their composition ratio is not particularly limited as long as it does not impair the effects of the present disclosure, but the desired function can be freely adjusted by adjusting the type and amount of these additives, preferably in the range of 0.01 parts by mass or more to 300 parts by mass or less per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition. For example, when an antiblocking agent is further added, it is preferably added in the range of 0.01 parts by mass or more to 3 parts by mass or less per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition.

・Molded body (molded body)
The molded article of the present disclosure has extremely excellent antiviral and antibacterial properties, and can be used in applications where these activities are required. For this reason, the molded article of the present disclosure can be suitably used for applications such as films, sheets, fibers, and tubes, and can be laminated to form a multilayer film or sheet by laminating multiple films or sheets, or can be made into a fabric with woven fibers. In addition, known molding methods such as injection molding, compression molding, extrusion molding, pultrusion molding, blow molding, and transfer molding can also be applied. Furthermore, it is also possible to mold a three-dimensional object using fused deposition molding (FDM), stereolithography (STL), selective laser sintering (SLS), inkjet method, inkjet powder lamination method, etc. For example, a molding material based on the resin composition of the present disclosure can be melted at a high temperature equal to or higher than the melting temperature of the resin, and the molten molding material can be extruded from a nozzle in the head to form a shape, which can then be stacked in multiple layers to form a three-dimensional object.

The fabric may be in any form, such as woven fabric, knitted fabric, nonwoven fabric, etc. If necessary, the fabric may be colored with disperse dyes, acid dyes, direct dyes, reactive dyes, pigments, etc. The fabric of the present disclosure can be used in a variety of textile products, such as clothing for general use, innerwear, sports, medical use, etc., bedding materials such as duvet covers and sheets, interior goods such as curtains, carpets, chairs, cushion covers, wallpaper, etc., industrial materials such as tent sheets, flags, curtains, etc., sheet materials for transportation vehicles such as automobiles, aircraft, and railway cars, sanitary materials, textile materials for air treatment, textile materials for water treatment, etc.

In addition, the molded articles can be processed and used in products that are easily touched by human hands, such as food packaging containers, bathtubs, building fixtures, and housings for cash registers, computers, and smartphones, but they can also be used for medical purposes, such as stents, coil obturators, catheter tubes, syringes (needles and bodies), shunt tubes, drain tubes, and implant medical devices.

The diameter (number average fiber diameter) of the fiber obtained by melt spinning the resin composition of the present disclosure varies depending on the application, and can be any diameter. However, since the smaller the fiber diameter, the better the antiviral activity, it is preferably 100 μm or less, more preferably 40 μm or less, even more preferably 20 μm or less, and particularly preferably 10 μm or less. The lower limit is not limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more. Of these, ultrafine fibers such as fibers in the range of 8 μm or less (referred to as microfibers in this disclosure) are particularly preferred because they tend to have a large surface area and high antiviral activity. The fiber length is also not limited, and may be a long fiber length, so-called filament (long fiber), or a short fiber length, so-called staple (short fiber).

The thickness of the sheet or film obtained by forming the resin composition of the present disclosure into a sheet or film varies depending on the application, and can be any thickness, but is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, and particularly preferably 10 μm or more, and preferably 200 μm or less, more preferably 150 μm or less. The terms sheet and film in this disclosure are not used to strictly distinguish between sheets and films, but are used to clarify that they include both, and as long as they have the characteristics of the present disclosure, sheets and films can be interpreted as broadly as possible, and the term sheet includes what is called a plate or board, as long as it has the characteristics of the present disclosure. If it is still necessary to distinguish between sheets and films, within the above range, sheets are usually used when the thickness exceeds about 0.5 mm, and films are usually used when the thickness is up to about 500 μm.

　The molded article obtained by melt molding the resin composition of the present disclosure, particularly the film, sheet, or fiber formed into a sheet, film, or fiber, is produced by first forming the antibacterial and antiviral agent into a master batch with a thermoplastic resin, and then blending a diluting resin to produce a thermoplastic resin composition and a molded article thereof. This allows the antibacterial and antiviral agent to be dispersed stably at a high concentration and with good uniformity, resulting in not only excellent antiviral and antibacterial activity, but also long-lasting effects, significantly improved washability, excellent safety to the human body, heat resistance, weather resistance, and water resistance, as well as suppressing the generation of coarse particles (lumps), and by increasing the specific surface area of the particles of the antibacterial and antiviral agent, the activity of the particle surface can be effectively utilized while improving the surface appearance and surface smoothness of the molded article of the particles, and further suppressing film or sheet tearing in the case of a film or sheet, and suppressing thread breakage in the case of fibers.

(Method for producing molded body)
The method for producing a molded article of the present disclosure includes a step of subjecting the thermoplastic resin composition, either directly as a molten product or after being processed into pellets or the like in a conventional manner, to a melt molding machine and melt mixing or melt kneading at a resin set temperature equal to or higher than the melting point. The thermoplastic resin composition melted in the melt molding machine is then molded into a molded article using various known molding methods such as extrusion molding, injection molding, calendar molding, blow molding, vacuum molding, pressure molding, melt spinning, sheet molding, and film molding.

The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples.

Synthesis Example 1 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°C, and then dehydrated under reduced pressure at 130°C. After that, 306.9 parts by mass of cyclohexane were added to obtain 570.0 parts by mass of a neodymium neodecanoate solution. The solvent of the obtained solution was distilled off at 130°C to obtain neodymium neodecanoate (sometimes referred to as "fatty acid metal salt (Nd)"). The neodymium content in the obtained neodymium neodecanoate was 18.7% by mass. The obtained neodymium neodecanoate had a melting point of less than -30°C (not solid at 0 to 45°C). The melting point was measured using a DSC6220 (trade name) manufactured by SII Nanotechnology Co., Ltd., and 10 mg of the sample was weighed in an aluminum container, and the temperature was measured at a heating rate of 10°C/min in the range of -30°C to 200°C, and the temperature was the apex temperature of the melting peak.

Synthesis Example 2 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°C and then dehydrated under reduced pressure at 130°C, to obtain 439.5 parts by mass of a bismuth 2-ethylhexanoate solution (sometimes referred to as "fatty acid metal salt (Bi)"). The bismuth content in the obtained fatty acid metal salt (Bi) was 25% by mass. The melting point of bismuth 2-ethylhexanoate in the fatty acid metal salt (Bi) was less than -30°C (not solid at 0 to 45°C).

(Synthesis Example 3) Preparation of fatty acid metal salt (La) 862.3 parts by mass of distilled water, 100.0 parts by mass of stearic acid, and 72.5 parts by mass of 20% caustic soda were charged into a flask. After saponification at 90°C for 30 minutes, 97.0 parts by mass of lanthanum chloride aqueous solution were charged and reacted at 90°C for 1 hour. In order to remove the by-product mirabilite (sodium sulfate), the mixture was filtered while washing with water. After collecting the residue on the filter paper, it was dried at 150°C for 3 hours to obtain 104.8 parts by mass of lanthanum stearate (sometimes referred to as "fatty acid metal salt (La)"). The lanthanum content in the obtained fatty acid metal salt (La) was 13.6% by mass. The melting point of lanthanum stearate was 120°C.

(Production Example 1)
A polyethylene resin ("Petrothene" manufactured by Tosoh Corporation, hereinafter abbreviated as "PE resin") and the fatty acid metal salt (Nd) prepared in Synthesis Example 1 were blended so that the metal content in the mixture was 3.0% by mass, and the mixture was melt-kneaded (set temperature 160°C) in a twin-screw kneader ("TEM" manufactured by Shibaura Machine Co., Ltd.) to obtain a molten material. The resulting molten material was extruded in the form of strands from the extruder and pelletized to obtain a master batch (1).

(Production Example 2)
A master batch (2) was obtained in the same manner as in Production Example 1, except that the fatty acid metal salt (Bi) prepared in Synthesis Example 2 was used instead of the fatty acid metal salt (Nd) prepared in Synthesis Example 1.

(Production Example 3)
A master batch (3) was obtained in the same manner as in Production Example 1, except that the fatty acid metal salt (La) prepared in Synthesis Example 3 was used instead of the fatty acid metal salt (Nd) prepared in Synthesis Example 1.

(Production Example 4)
A master batch (4) was obtained in the same manner as in Production Example 1, except for two points: "polyethylene terephthalate ("MA-2101M" manufactured by Unitika Ltd., intrinsic viscosity (IV) 0.63), hereinafter abbreviated as "PET resin") was used instead of "polyethylene resin ("Petrothene" manufactured by Tosoh Corporation)" and the set temperature of the melt kneading was changed from 160°C to 280°C.

(Comparative Production Example 1)
A comparative master batch (c1) was obtained in the same manner as in Production Example 1, except that "silver-supported zirconium phosphate (Novalon IV1000, manufactured by Toa Gosei Co., Ltd., silver ion content 10 wt%)" was added instead of "the fatty acid metal salt (Nd) prepared in Synthesis Example 1".

(Comparative Production Example 2)
A comparative master batch (c2) was obtained in the same manner as in Production Example 1, except that the "fatty acid metal salt (Nd) prepared in Synthesis Example 1" was not added.

(Comparative Production Example 3)
A comparative master batch (c3) was obtained in the same manner as in Production Example 4, except that the "fatty acid metal salt (Nd) prepared in Synthesis Example 1" was not added.

(Examples 1 to 3, Comparative Examples 1 and 2) Production of Films Masterbatches (1) to (3), comparative masterbatches (c1), and (c2) were dry-mixed with PE resin as a diluent resin so that the amount of metal in the film was 1 wt%, and then melt-kneaded with a twin-screw kneader ("TEM" manufactured by Shibaura Machine Co., Ltd.). Next, melt film-forming was performed at a film-forming temperature of 160°C using a 20 mm twin-screw extruder (manufactured by Toyo Seiki Co., Ltd., filter installed) connected to a 100 mm wide T-die, to obtain 100 μm films (1) to (3) and comparative films (c1) and (c2), respectively.

(Example 4, Comparative Example 3)
A film (4) and a comparative film (c3) were obtained in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2, except for the following three points: "Master batch (4)" was used instead of "Master batches (1) to (3) and Comparative master batches (c1) and (c2)", "PET resin" was used instead of "PE resin" as the dilution resin, and the film formation temperature was changed from 160° C. to 280° C.

Next, the resin films obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were measured and evaluated using the following methods.

(Measurement Example 1) Antibacterial Activity The film obtained above was subjected to an antibacterial activity test using Escherichia coli according to JIS Z 2801. The test bacteria culture conditions for the sample were 35° C., 90% RH, and 24 hours. After the culture, the number of bacteria in the washed-out liquid was measured, and the antibacterial activity value was calculated according to the following formula.

Formula: Antibacterial activity value = log (number of viable bacteria after incubation per ^{1 cm2} of untreated sample) - log (number of viable bacteria after incubation per ^{1 cm2} of antibacterial treated sample)

Antibacterial evaluation criteria: If the antibacterial activity value is 2.0 or greater, the antibacterial activity is rated "Good". If 2.0 > antibacterial activity value 1.0 or greater, the antibacterial activity is rated "Correct". If 1.0 or greater, the antibacterial activity is rated "Poor".

(Measurement Example 2) Antiviral Property The film obtained above was subjected to an antiviral property test using bacteriophage Qβ based on JIS R 1756. The virus inoculation conditions for the sample were a dark place at 25° C. for 4 hours. After the test, the infectivity of bacteriophage Qβ in the washed-out liquid was measured, and the antiviral activity value was calculated according to the following formula.

Formula: Antiviral activity value = log (infectivity value of untreated sample / infectivity value of antibacterial and antiviral treated sample)
Evaluation of antiviral properties: If the antiviral activity value is ≧2.0, the antiviral property is evaluated as “◯”. If the antiviral activity value is ≧2.0>≧1.0, the antiviral property is evaluated as “△”. If the antiviral activity value is ≧1.0, the antiviral property is evaluated as “×”.

Measurement Example 3: Film Transparency The film obtained above was measured for haze using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., device name "NDH 7000II") and evaluated according to the following criteria.
Evaluation of transparency: If the haze value is less than +2.0% compared to the haze value of the blank film for PE resin (c2) or the blank film for PET resin (c3), the transparency is evaluated as "○". Similarly, if the haze value is more than +2.0% and less than +3.0%, the transparency is evaluated as "△". Similarly, if the haze value is more than +3.0%, the transparency is evaluated as "×".

(Measurement Example 4) Film processability (pressure increase property)
A 50 μm filter was installed in the twin-screw extruder during melt film formation, and the pressure rise when 1 kg of film was produced was evaluated according to the following criteria. The pressure rise was measured by reading the maximum pressure during film formation from a pressure gauge (gauge pressure) attached immediately upstream of the filter.
Evaluation of pressure increase: "No pressure increase (but in the range of less than 0.5 MPa)" is rated as "○". "Pressure increase in the range of 0.5 to 2.0 MPa" is rated as "△". "Pressure increase in the range of more than 2.0 MPa" is rated as "×".

(Measurement method 5) Film surface observation (pimples)
Twenty random locations on the film obtained above were selected and observed under an optical microscope (magnification 200x). The number of agglomerated particles (equivalent circle diameter) of 50 µm or more present per ¹⁰⁰ cm2 was counted and the number average per location was calculated, and the surface appearance of the film was evaluated according to the following criteria.
Evaluation of surface appearance: 3 or less is "○", more than 3 to 6 or more is "△", and more than 6 is "×".

The film obtained in Comparative Example 1 had an antibacterial activity value of 2.0 or more (antibacterial), indicating that it had antibacterial properties, and an antiviral activity value of 2.0 or more (antiviral properties), indicating that it had antiviral properties. However, the film obtained in Comparative Example 1 had a haze value of +3.0% or more compared to the blank film, indicating that it had poor transparency. In addition, the film obtained in Comparative Example 1 was pressurized to about 3 MPa, indicating that it had poor film processability. Furthermore, in both of the films obtained in Comparative Example 1, surface observation revealed that there were bumps, indicating that the surface appearance was poor. On the other hand, the films obtained in Comparative Examples 2 and 3 had antibacterial activity values of 1.0 or less (no antibacterial properties), indicating that they did not have antibacterial properties, and antiviral activity values of 1.0 or less (no antiviral properties), indicating that they did not have antiviral properties.

In contrast, the films obtained in Examples 1 to 4 had antibacterial activity values of 2.0 or more (antibacterial), and antiviral activity values of 2.0 or more (antiviral). The films obtained in Examples 1 to 4 also had excellent transparency, with haze values of +2.0% or less compared to the blank film. The films obtained in Examples 1 to 4 were all capable of being formed without increasing pressure, and had excellent film processability. The films obtained in Examples 1 to 4 all had excellent surface appearance, with the occurrence of bumps suppressed by surface observation. In particular, master batch (3) suppressed thermal degradation during processing compared to master batches (1) and (2), and there was less burning and scorching of the agent, foreign matter thought to result from this, and less decomposition gas.

As described above, it was revealed that the silver-loaded particles used in the comparative examples had insufficient compatibility with polyethylene resin, and did not maintain transparency when melt-kneaded to form a resin composition. It was also revealed that particle aggregation caused poor appearance of the molded product, and that filter pressure rise occurred during melt processing, resulting in reduced processability. Therefore, shear heat occurred due to kneading with the particles, which led to deterioration of the material, and there was a risk of deterioration in processability and deterioration of physical properties. In contrast, the fatty acid metal salts or metal complexes used in Examples 1 to 4 have excellent compatibility with both polar and non-polar thermoplastic resins such as polyethylene resin and PET resin, maintain transparency as a resin composition by melt kneading, suppress the generation of aggregation (particles), and do not generate bumps due to aggregation, resulting in excellent appearance of molded products, and not only suppress filter pressure rise during processing, but also suppress clogging of nozzles and dies, thereby suppressing the occurrence of thread breakage, film rupture, etc., and have excellent processability and can improve productivity. It was also revealed that suppressing filter pressure rise during processing can suppress heat generation during molding processing, suppress material deterioration, and suppress deterioration of physical properties.

Claims

A masterbatch containing a thermoplastic resin and an antibacterial and antiviral agent,
the antibacterial and antiviral agent is contained in an amount within the range of 0.03 to 90 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch, or the antibacterial and antiviral agent is contained so that the content of metal derived from the antibacterial and antiviral agent is within the range of 0.0015 to 45 parts by mass per 100 parts by mass of the total of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch;
The master batch is characterized in that the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.
The masterbatch according to claim 1, wherein the metal of the fatty acid metal salt, the metal of the metal complex of the heteroatom-containing compound ligand and metal ion, and the metal of the metal complex of the heteroatom-containing compound ligand and fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, or magnesium.
The masterbatch according to claim 1 or 2, wherein the fatty acid metal salt is a metal salt of a fatty acid having 2 to 31 carbon atoms.
The masterbatch according to claim 1 or 2, wherein the fatty acid metal salt is a metal salt of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid or melissic acid.
The masterbatch according to claim 1 or 2, wherein the heteroatom-containing ligand is one 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, 2,2'-bipyridyl and its derivatives, and 2,2'-[propane-1,2-diylbis(azanylilidenemethanylilidene)]diphenol and its derivatives.
A method for producing a masterbatch, comprising a step of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
blending an antibacterial and antiviral agent in an amount within the range of 0.03 to 90 parts by mass relative to a total of 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch, or blending an antibacterial and antiviral agent such that the content of metal derived from the antibacterial and antiviral agent is within the range of 0.0015 to 45 parts by mass relative to a total of 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the masterbatch;
A method for producing a master batch, characterized in that the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of the heteroatom-containing compound ligand and a metal ion, and the metal complex of the heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.
A thermoplastic resin composition containing a thermoplastic resin and an antibacterial and antiviral agent,
The thermoplastic resin composition contains an antibacterial and antiviral agent in an amount of 0.01 to 30 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in total, or contains an antibacterial and antiviral agent such that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in total,
The thermoplastic resin composition, characterized in that the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of a heteroatom-containing compound ligand and a metal ion, and the metal complex of a heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.
A method for producing a thermoplastic resin composition, comprising the steps of blending the masterbatch according to claim 1 with a thermoplastic resin as a diluent resin and melt-kneading the blend,
A method for producing a thermoplastic resin composition, comprising blending a masterbatch and a diluent resin so that the antibacterial and antiviral agent is in the range of 0.01 to 30 parts by mass per 100 parts by mass of the thermoplastic resin, antibacterial and antiviral agent, and diluent resin in the masterbatch combined; or blending the masterbatch and a diluent resin so that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass per 100 parts by mass of the thermoplastic resin, antibacterial and antiviral agent, and diluent resin in the masterbatch combined.
A method for producing a thermoplastic resin composition, comprising a step of blending and melt-kneading a thermoplastic resin and an antibacterial and antiviral agent,
blending an antibacterial and antiviral agent in an amount ranging from 0.01 to 30 parts by mass relative to a total of 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition, or blending a thermoplastic resin and an antibacterial and antiviral agent such that the content of metal derived from the antibacterial and antiviral agent is in the range of 0.0005 to 15 parts by mass relative to a total of 100 parts by mass of the thermoplastic resin and the antibacterial and antiviral agent in the thermoplastic resin composition;
A method for producing a thermoplastic resin composition, characterized in that the antibacterial and antiviral agent is one 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 metals in the fatty acid metal salt, the metal complex of the heteroatom-containing compound ligand and a metal ion, and the metal complex of the heteroatom-containing compound ligand and a fatty acid metal salt are each independently a lanthanoid, bismuth, manganese, magnesium, lead, yttrium, cobalt, or copper.
A molded article obtained by molding the thermoplastic resin composition according to claim 7.
A method for producing a molded product, comprising a step of melt molding the resin composition according to claim 7.