Vinyl chloride resin composition, molded body and molded article

Abstract

To provide a polyvinyl chloride resin composition that can produce a molding capable of exhibiting excellent antibacterial or antiviral performance and having excellent surface nature, color tone and impact resistance.SOLUTION: A polyvinyl chloride resin composition comprises a polyvinyl chloride resin, an antibacterial agent or antiviral agent, and a Ca-Zn conjugate as an antibacterial aid. Relative to 100 pts.mass of the polyvinyl chloride resin, the Ca-Zn conjugate is 3.5 pts.mass to 4.5 pts.mass.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an antibacterial or antiviral vinyl chloride resin composition containing a Ca-Zn complex compound as an antibacterial auxiliary, as well as a molded body thereof and a molded article including the same. [Background technology]

[0002] It is known that vinyl chloride resin compositions are inexpensive and have excellent physical properties such as moldability (e.g., extrusion moldability, injection moldability, etc.), adhesion, flame retardancy, heat resistance, etc. Therefore, molded articles (or molded bodies) of vinyl chloride resin compositions are widely used as various components such as building materials such as interior undercoats and exterior materials, home appliance components, and vehicle components.

[0003] On the other hand, in recent years, the problem of contamination by various bacteria and viruses has been widely raised. For this reason, many vinyl chloride resin compositions having antibacterial and / or antiviral properties, in which antibacterial agents and / or antiviral agents are added to vinyl chloride resin, and molded articles thereof have been developed.

[0004] For example, Patent Document 1 describes an antibacterial vinyl chloride resin composition comprising an organotin compound as a stabilizer, a silver-based inorganic antibacterial agent, and a vinyl chloride resin, in which the content of the sulfur-containing organotin compound is 0 to 1 part by weight per 100 parts by weight of the antibacterial vinyl chloride resin composition. It describes that the antibacterial vinyl chloride resin composition can reliably exert the inherent excellent antibacterial properties of the silver-based inorganic antibacterial agent in a molded product. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 9-302184 Summary of the Invention [Problem to be solved by the invention]

[0006] Usually, in order to make a vinyl chloride resin composition and a molded article thereof exhibit antibacterial or antiviral properties, it is necessary to add a sufficient amount of an antibacterial agent or an antiviral agent according to the type and use of the molded article. However, a molded article made of a vinyl chloride resin composition to which a large amount of an antibacterial agent or an antiviral agent has been added may have problems with the surface properties (presence or absence of unevenness) or color tone (presence or absence of dullness) and / or may have reduced impact resistance.

[0007] On the other hand, when the amount of antibacterial or antiviral agent added to the polyvinyl chloride resin is reduced, no problems arise in the physical properties such as impact resistance and rigidity, or in the surface properties and color tone of the molded article, but the desired sufficient antibacterial or antiviral properties cannot be obtained.

[0008] In the antibacterial vinyl chloride resin composition of Patent Document 1, the antibacterial agent is limited to a case where a silver-based inorganic antibacterial agent is contained, and the concentration of the sulfur-containing organotin compound is suppressed, thereby ensuring that the molded article exhibits excellent antibacterial properties. However, for the purpose of applying the vinyl chloride resin composition to molded articles for a wider range of uses, there is a demand for the development of a new vinyl chloride resin composition that can ensure better antibacterial or antiviral properties even when other types of antibacterial or antiviral agents are used.

[0009] Therefore, an object of the present invention is to provide a vinyl chloride resin composition that is capable of exhibiting excellent antibacterial or antiviral performance and from which molded articles having good surface properties, color tone and impact resistance can be produced. [Means for solving the problem]

[0010] The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention. That is, the present invention includes the following preferred embodiments.

[0011] A vinyl chloride resin composition according to a first aspect of the present invention comprises a vinyl chloride resin, an antibacterial agent or an antiviral agent, and a Ca-Zn-based composite compound as an antibacterial auxiliary, The Ca-Zn composite compound is contained in an amount of 3.5 to 4.5 parts by mass relative to 100 parts by mass of the vinyl chloride resin.

[0012] The vinyl chloride resin composition preferably contains 0.1 to 0.7 parts by mass of the antibacterial agent relative to 100 parts by mass of the vinyl chloride resin.

[0013] In the vinyl chloride resin composition described above, the antibacterial agent is more preferably a zinc-based antibacterial agent.

[0014] Alternatively, the vinyl chloride resin composition preferably contains 5 parts by mass to 10 parts by mass of the antiviral agent per 100 parts by mass of the vinyl chloride resin.

[0015] In the vinyl chloride resin composition described above, the antiviral agent is more preferably an organic-inorganic hybrid antiviral agent.

[0016] A molded article according to a second aspect of the present invention is made of the vinyl chloride resin composition according to the first aspect of the present invention.

[0017] A molded article according to a third aspect of the present invention comprises a substrate and a surface layer formed on a surface of the substrate, the surface layer being made of the vinyl chloride resin composition according to the first aspect of the present invention. Effect of the Invention

[0018] Effects of the Invention According to the present invention, it is possible to provide a vinyl chloride resin composition which is capable of exhibiting excellent antibacterial or antiviral performance and which can produce a molded article having good surface properties, color tone and impact resistance. [Brief description of the drawings]

[0019] [Figure 1] FIG. 1 is a schematic cross-sectional view of an example of a molded article in this embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present inventors have conducted extensive research into vinyl chloride resin compositions that can exhibit excellent antibacterial or antiviral performance even when a small amount of antibacterial or antiviral agent is added. They have focused on the use of a Ca-Zn complex compound as an antibacterial auxiliary in a specific range of blending ratio, and have completed the present invention. In this specification, the term "antibacterial auxiliary" also includes the meaning of "antiviral auxiliary".

[0021] Hereinafter, the embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[0022] 1. Vinyl chloride resin composition The vinyl chloride resin composition in this embodiment contains a vinyl chloride resin, an antibacterial or antiviral agent, and a Ca-Zn-based complex compound as an antibacterial auxiliary, and contains 3.5 parts by mass to 4.5 parts by mass of the Ca-Zn-based complex compound per 100 parts by mass of the vinyl chloride resin.

[0023] According to the vinyl chloride resin composition of the present embodiment, even when the amount of the antibacterial agent or antiviral agent added is small, sufficient antibacterial or antiviral properties can be exhibited due to the function of the Ca-Zn composite compound contained in a specific range of compounding ratio as an antibacterial auxiliary. In addition, since the amount of the antibacterial agent or antiviral agent added can be reduced, the surface properties, color tone, and impact resistance of the molded article made of the vinyl chloride resin composition can be improved at the same time.

[0024] The function of each component and its blending amount, as well as the method for preparing (or manufacturing) the vinyl chloride resin composition in this embodiment will be described in detail below.

[0025] <Vinyl chloride resin> In this specification, vinyl chloride resin is defined as -CH 2It means all polymers having a group represented by -CHCl-. Specifically, examples of the vinyl chloride resin contained in the vinyl chloride resin composition in the present embodiment include homopolymers of vinyl chloride; copolymers of vinyl chloride and vinyl acetate, vinyl chloride and (meth)acrylic acid copolymers, vinyl chloride and methyl (meth)acrylate copolymers, vinyl chloride and ethyl (meth)acrylate copolymers, vinyl chloride and maleic acid ester copolymers, vinyl chloride and ethylene copolymers, vinyl chloride and propylene copolymers, vinyl chloride and styrene copolymers, vinyl chloride and isobutylene copolymers, vinyl chloride and vinylidene chloride copolymers, vinyl chloride and styrene and maleic anhydride terpolymers, vinyl chloride and styrene and acrylonitrile terpolymers, vinyl chloride and butadiene copolymers, vinyl chloride and isoprene copolymers, vinyl chloride and chlorinated propylene copolymers, vinyl chloride and vinylidene chloride and vinyl acetate terpolymers, vinyl chloride and acrylonitrile copolymers, and vinyl chloride and various vinyl ether copolymers; and polymers obtained by modifying vinyl chloride homopolymers and vinyl chloride copolymers, such as post-chlorinated vinyl copolymers. These vinyl chloride resins may be used alone or in combination of two or more thereof. Specifically, the resin may be appropriately selected depending on the type, application, shape, etc. of the molded article or molded product.

[0026] Of these, the vinyl chloride resin is preferably a homopolymer of vinyl chloride from the viewpoint of good moldability.

[0027] The average degree of polymerization of the vinyl chloride resin is preferably 700 to 2000. When the average degree of polymerization of the vinyl chloride resin is 700 or more, the mechanical strength of a molded article produced from the vinyl chloride resin composition can be improved. When the average degree of polymerization of the vinyl chloride resin is 2000 or less, the molding processability of the vinyl chloride resin composition can be improved. The average degree of polymerization of the vinyl chloride resin is more preferably 800 or more, and further preferably 1000 or more. In addition, the average degree of polymerization of the vinyl chloride resin is more preferably 1500 or less, and further preferably 1300 or less.

[0028] In this specification, the average degree of polymerization of the vinyl chloride resin means the average degree of polymerization calculated from the specific viscosity measured in accordance with 4.1 of Appendix of JIS K 6720-2:1999.

[0029] <Antibacterial agent> In this specification, the term "antibacterial agent" refers to an agent that prevents the growth of bacteria, mold, etc., or an agent that kills or reduces bacteria. The target bacteria is not particularly limited, but examples thereof include bacteria or molds such as Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus, Streptococcus pneumoniae, Haemophilus influenzae, Bordetella pertussis, Salmonella enteritidis, Klebsiella pneumoniae, Pseudomonas aeruginosa, Vibrio, Pseudomonas aeruginosa, MRSA, Bacillus cereus, and Klebsiella pneumoniae.

[0030] As such an antibacterial agent, for example, an inorganic antibacterial agent, an organic antibacterial agent, or a composite material thereof (organic-inorganic hybrid antibacterial agent) can be used. Of these antibacterial agents, the inorganic antibacterial agent is preferable from the viewpoints that it is effective against a wide range of bacteria, molds, and yeasts, and that its effect is not significantly affected even at high resin molding temperatures.

[0031] The inorganic antibacterial agent is not particularly limited as long as it is any known inorganic antibacterial agent, but examples thereof include zinc-based antibacterial agents, silver-based antibacterial agents, copper-based antibacterial agents, iron-based antibacterial agents, bismuth-based antibacterial agents, gold-based antibacterial agents, platinum-based antibacterial agents, titanium-based antibacterial agents, etc. Specifically, these antibacterial agents include various metals such as zinc, silver, copper, iron, bismuth, gold, platinum, titanium, etc., these metal compounds (metal oxides, metal sulfides, metal sulfates, metal halides, etc.), and antibacterial agents in which these metals, metal compounds, or metal ions are supported on a carrier such as zeolite, apatite, zirconia, etc.

[0032] Of these, the antibacterial agent is preferably a zinc-based or silver-based antibacterial agent from the viewpoint of being able to exert high antibacterial properties. Furthermore, from the viewpoint of being able to avoid the risk of discoloration of the surface of the molded body over time, the antibacterial agent is more preferably a zinc-based antibacterial agent. Specifically, when a silver-based antibacterial agent is used as the antibacterial agent, there is no problem with the color of the surface for a while after molding of the molded body, and high antibacterial properties can be exerted. However, there is a risk that the surface of the molded body will discolor due to the generation of silver oxide over time.

[0033] Such inorganic antibacterial agents may be commercially available products. Examples of commercially available products include zinc-based antibacterial agents such as "Novalon (registered trademark) VZ100" manufactured by Toagosei Co., Ltd., "MICRO ZINC OXIDE MZ-500" manufactured by Teika Corporation, and "Bactekiller BM-102VT" manufactured by Fuji Chemical Co., Ltd., copper-based antibacterial agents such as "Cufitec (registered trademark)" manufactured by NBC Meshtec Co., Ltd., and silver-based antibacterial agents such as "Novalon (registered trademark) AGZ330" manufactured by Toagosei Co., Ltd., "Novalon (registered trademark) AG300" manufactured by Toagosei Co., Ltd., "Novalon (registered trademark) AG1100" manufactured by Toagosei Co., Ltd., and "Zeomic (registered trademark)" manufactured by Sinanen Zeomic Co., Ltd.

[0034] The organic antibacterial agent is not particularly limited as long as it is any known organic antibacterial agent, and examples thereof include imidazole antibacterial agents, pyrithione antibacterial agents, sulfone antibacterial agents, N-haloalkylthio compounds, anilide derivatives, pyrrole antibacterial agents, quaternary ammonium salts, pyridine compounds, triazine compounds, thiazoline antibacterial agents (e.g., benzoisothiazoline compounds, isothiazoline compounds), and the like.

[0035] Such organic antibacterial agents may be commercially available products, and examples of commercially available products include "Amorden" manufactured by Yamato Chemical Industry Co., Ltd. and "Marucicide" manufactured by Osaka Kasei Co., Ltd.

[0036] The organic-inorganic hybrid antibacterial agent is an antibacterial agent in which the inorganic antibacterial agent and the organic antibacterial agent described above are combined, and any known organic-inorganic hybrid antibacterial agent can be used. Commercially available products of such organic-inorganic hybrid antibacterial agents include "Bactekiller TZA-206" manufactured by Fuji Chemical Co., Ltd., "Rasap" manufactured by Rasa Kogyo Co., Ltd., and "Hybrid Ion Pure" manufactured by Ishizuka Glass Co., Ltd.

[0037] The blending ratio of the antibacterial agent is preferably 0.1 to 0.7 parts by mass per 100 parts by mass of vinyl chloride resin. By including 0.1 parts by mass or more of the antibacterial agent per 100 parts by mass of vinyl chloride resin, a molded article exhibiting excellent antibacterial performance can be produced. By including 0.7 parts by mass or less of the antibacterial agent per 100 parts by mass of vinyl chloride resin, a molded article having good surface properties, color tone, and impact resistance can be produced.

[0038] The blend ratio of the antibacterial agent is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, per 100 parts by mass of the vinyl chloride resin, and more preferably 0.6 parts by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the vinyl chloride resin.

[0039] <Antiviral agents> In the present specification, the term "antiviral agent" refers to an agent that partially inactivates a virus, specifically, an agent that suppresses the viral infectivity. The target viruses are not particularly limited, but examples thereof include rhinovirus, poliovirus, rotavirus, foot and mouth disease virus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, influenza A, B or C virus, parainfluenza virus, mumps virus, measles virus, human metapneumovirus, respiratory syncytial virus, Nipah virus, Hendra virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, hepatitis B or C virus, eastern and western equine encephalitis virus, Onyong-nyong virus, rubella virus, Lassa virus, Funinwi virus, and the like. Examples of viruses that can cause infection include rabies, rabies virus ...

[0040] As such an antiviral agent, for example, an inorganic antiviral agent, an organic antiviral agent, or a composite material thereof (an organic-inorganic hybrid antiviral agent) can be used, similar to the above-mentioned antibacterial agent. Of these antiviral agents, from the viewpoint of being able to exhibit high antiviral properties, the antiviral agent is preferably an organic-inorganic hybrid antiviral agent.

[0041] The inorganic antiviral agent is not particularly limited as long as it is any known inorganic antiviral agent, and examples thereof include zinc-based antiviral agents, silver-based antiviral agents, copper-based antiviral agents, iron-based antiviral agents, bismuth-based antiviral agents, gold-based antiviral agents, platinum-based antiviral agents, titanium-based antiviral agents, etc. Specifically, these antiviral agents include various metals such as zinc, silver, copper, iron, bismuth, gold, platinum, titanium, etc., metal compounds thereof (metal oxides, metal sulfides, metal sulfates, metal halides, etc.), and antiviral agents in which these metals, metal compounds, or metal ions are supported on a carrier such as zeolite, apatite, or zirconia.

[0042] Such inorganic antiviral agents may be commercially available products. Examples of commercially available products include, for example, silver-based antiviral agents such as "Novalon (registered trademark) IV1000" manufactured by Toagosei Co., Ltd. and "Neosynthol AV-18f" manufactured by Sumika Environmental Science Co., Ltd., and zinc-based antiviral agents such as "SEABIO" manufactured by Newlyme Corporation.

[0043] The organic antiviral agent is not particularly limited as long as it is any known organic antiviral agent, and examples thereof include imidazole antiviral agents, pyrithione antiviral agents, sulfone antiviral agents, N-haloalkylthio compounds, anilide derivatives, pyrrole antiviral agents, quaternary ammonium salts, pyridine compounds, triazine compounds, thiazoline antiviral agents (e.g., benzoisothiazoline compounds, isothiazoline compounds), and the like.

[0044] Such organic antiviral agents may be commercially available products, and examples of commercially available products include "FC-V20S" manufactured by Fuji Chemical Co., Ltd. and "Wiltaker" manufactured by Sekisui Material Solutions Co., Ltd.

[0045] The organic-inorganic hybrid antiviral agent is an antiviral agent in which the above-mentioned inorganic antiviral agent and the above-mentioned organic antiviral agent are combined, and any known organic-inorganic hybrid antibacterial agent can be used.

[0046] Examples of commercially available products of such organic-inorganic hybrid antiviral agents include, for example, "N-Clear AVPVC" manufactured by Nitto Denko Corporation and "Wilmish" manufactured by DIC Corporation.

[0047] The compounding ratio of the antiviral agent is preferably 5 to 10 parts by mass of the antiviral agent with respect to 100 parts by mass of the vinyl chloride resin. By containing 5 parts by mass or more of the antiviral agent with respect to 100 parts by mass of the vinyl chloride resin, a molded article exhibiting excellent antiviral performance can be produced. By containing 10 parts by mass or less of the antiviral agent with respect to 100 parts by mass of the vinyl chloride resin, a molded article having good surface properties, color tone, and impact resistance can be produced.

[0048] In the compounding ratio of the antiviral agent, it is more preferable to contain 6 parts by mass or more of the antiviral agent with respect to 100 parts by mass of the vinyl chloride resin, and further preferably 7 parts by mass or more. Also, it is more preferable to contain 9 parts by mass or less of the antiviral agent with respect to 100 parts by mass of the vinyl chloride resin, and further preferably 8 parts by mass or less.

[0049] <Ca-Zn based composite compound> The vinyl chloride resin composition in the present embodiment contains 3.5 to 4.5 parts by mass of the Ca-Zn based composite compound with respect to 100 parts by mass of the vinyl chloride resin. When the amount of the Ca-Zn based composite compound with respect to 100 parts by mass of the vinyl chloride resin is less than 3.5 parts by mass, the fluidity of the resin composition becomes too high and it becomes difficult to form a molded article. Also, when the amount of the Ca-Zn based composite compound with respect to 100 parts by mass of the vinyl chloride resin exceeds 4.5 parts by mass, burning or blooming occurs during the molding of the molded article, and it becomes difficult to mold the molded article.

[0050] The compounding ratio of the Ca-Zn-based composite compound is preferably 3.6 parts by mass or more, more preferably 3.7 parts by mass or more, per 100 parts by mass of the vinyl chloride resin, and is preferably 4.4 parts by mass or less, more preferably 4.3 parts by mass or less, per 100 parts by mass of the vinyl chloride resin.

[0051] The Ca-Zn-based complex compound functions as a stabilizer in the vinyl chloride resin composition and also functions as an antibacterial auxiliary. Therefore, by including the Ca-Zn-based complex compound in the vinyl chloride resin composition in the above-mentioned specific range of compounding ratio, even if the amount of the antibacterial agent or antiviral agent added is small (for example, the amount of the antibacterial agent is 0.1 to 0.7 parts by mass or the amount of the antiviral agent is 5 to 10 parts by mass relative to 100 parts by mass of vinyl chloride resin), the molded body can exhibit excellent antibacterial or antiviral properties. On the other hand, Pb-based stabilizers (hereinafter also referred to as "Pb-based compounds"), Sd-based stabilizers (hereinafter also referred to as "Sd-based compounds"), etc. have also been conventionally used as stabilizers for vinyl chloride resins, but when these are included in the vinyl chloride resin composition in the same specific range of compounding ratio as a substitute for the Ca-Zn-based complex compound, the molded body cannot exhibit sufficient antibacterial or antiviral properties even if an equivalent amount of the antibacterial agent or antiviral agent is added.

[0052] Examples of the Ca-Zn based complex compound include organic acid Ca-Zn complex salts containing Ca, Zn and an organic acid.

[0053] Examples of organic acids include fatty acids such as stearic acid, palmitic acid, lauric acid, linoleic acid, ricinoleic acid, octanoic acid, 2-ethylhexyl acid, and oleic acid; phosphorous acid esters; and aromatic carboxylic acids such as benzoic acid. In the Ca-Zn-based composite compound, these organic acids can be used alone or in combination of two or more kinds.

[0054] As the Ca-Zn based complex compound, commercially available products may be used, such as "RX-218" manufactured by ADEKA Corporation, "LTX-9" manufactured by Daikyo Chemical Industry Co., Ltd., and "LTX-10" manufactured by Daikyo Chemical Industry Co., Ltd.

[0055] <Other additives> The vinyl chloride resin composition in the present embodiment may contain various additives that are generally used in vinyl chloride resin compositions, as necessary, within ranges that do not impair the effects of the present embodiment, such as antibacterial performance or antiviral performance, as well as surface properties, color tone, and impact resistance.

[0056] For example, a plasticizer may be included as an additive. By including a plasticizer, the flexibility of a molded body (or molded product) made of a vinyl chloride resin composition can be adjusted, and the molded body can be given a desired flexibility according to its application, shape, etc. The plasticizer is not particularly limited, but examples thereof include phthalate ester plasticizers, trimellitate ester plasticizers, pyromellitate ester plasticizers, adipate ester plasticizers, itaconate ester plasticizers, citrate ester plasticizers, cyclohexane dicarboxylate plasticizers, and epoxy plasticizers.

[0057] Further, examples of other additives include heat stabilizers, lubricants, antioxidants, light stabilizers, colorants, ultraviolet absorbers, anti-fogging agents, plate-out inhibitors, antistatic agents, flame retardants, weather resistance agents, surfactants, impact resistance agents, foaming agents, and various fillers (e.g., calcium carbonate, clay, talc, etc.).

[0058] In the vinyl chloride resin composition of the present embodiment, these additives can be contained in an amount of, for example, about 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the vinyl chloride resin.

[0059] In this way, the vinyl chloride resin composition in the present embodiment contains the Ca-Zn-based composite compound, which also functions as an antibacterial auxiliary, in a specific range of blending ratio, and therefore even if the amount of antibacterial agent or antiviral agent added is small, it is possible to produce a molded article made of the vinyl chloride resin composition that exhibits excellent antibacterial or antiviral performance and has good surface properties, color tone, and impact resistance.

[0060] <Method for preparing (or producing) vinyl chloride resin composition> The preparation method (or production method) of the vinyl chloride resin composition in this embodiment is not particularly limited, and the composition can be produced by any known method.

[0061] Specifically, for example, the vinyl chloride resin composition in this embodiment can be prepared by melt-kneading and uniformly mixing the vinyl chloride resin, the antibacterial agent or antiviral agent, the Ca-Zn composite compound as the antibacterial auxiliary in the above-mentioned specific range of blending ratio, and any additives as required using any known kneader or the like. At this time, it is preferable to melt-knead at a heating and melting temperature of 170°C to 180°C. Note that various raw materials may be dry-blended in advance before melt-kneading.

[0062] 2. Molded body The molded article in this embodiment is made of the vinyl chloride resin composition in the above-described embodiment.

[0063] The molded article in this embodiment can be molded into a desired shape by applying any known molding method, such as extrusion molding, injection molding, blow molding, calendar molding, etc.

[0064] The shape of the molded product is not particularly limited and can be appropriately designed depending on the application of the molded product, etc. Examples of the shape of the molded product include a flat plate (sheet), rod, cylinder, ring, and irregular shape.

[0065] The flat molded article can be produced, for example, by using any known extrusion molding machine. Specifically, for example, first, a dry blend mixture of each raw material of the vinyl chloride resin composition is charged into a hopper of an extrusion molding machine, and the mixture is heated, melted, and uniformly mixed in a cylinder part having a built-in screw. Subsequently, the molten vinyl chloride resin composition is supplied to a mold (die) and extruded to produce a flat molded article. Examples of the extrusion molding machine include extrusion molding machines equipped with a known single-screw or twin-screw. The heat-melting temperature, heat-melting time, mold temperature, molding time, and other extrusion molding conditions may be appropriately set according to the specific composition of the vinyl chloride resin composition, the more specific size of the molded article, its application, the desired physical properties, and the like.

[0066] The molded article in this embodiment exhibits excellent antiviral properties when the vinyl chloride resin composition contains an antiviral agent. Specifically, the molded article preferably has an antiviral activity value of 2.0 or more against influenza virus and / or feline calicivirus after being subjected to a water resistance treatment and / or a light resistance treatment as a pretreatment, as measured in accordance with ISO 21702:2019, as described in detail in the Examples below.

[0067] Furthermore, the molded article of the present embodiment exhibits excellent antibacterial properties when the vinyl chloride resin composition contains an antibacterial agent. Specifically, the molded article preferably has an antibacterial activity value of 2.0 or more against Staphylococcus aureus and / or Escherichia coli, measured in accordance with JIS Z 2801:2010 (ISO 22196:2007), as described in detail in the Examples below.

[0068] The molded article of this embodiment also has good surface properties and color tone. Specifically, as will be described in detail in the Examples below, it is preferable that the molded article has no or almost no irregularities observed on its surface, and that its color tone is completely or only partially dull. In addition, the molded article of this embodiment has excellent impact resistance. Specifically, as will be described in detail in the Examples below, the molded article has a Charpy impact strength of 7 (kJ / m 2 ) or more, and 9 (kJ / m 2 ) or more is more preferable.

[0069] In addition, specific examples of the molded body in this embodiment are similar to specific examples of the molded article in the next embodiment, and will be described collectively later.

[0070] 3. Molded products The molded article in this embodiment includes a substrate and a surface layer formed on the surface of the substrate and made of the vinyl chloride resin composition in the above-described embodiment.

[0071] A schematic cross-sectional view of an example of a molded article in this embodiment is shown in Fig. 1. In the example shown in Fig. 1, the molded article 1 includes a substrate 2 and a surface layer 3 made of a vinyl chloride resin composition, and the surface layer 3 is formed (or laminated) on the surface of the substrate 2.

[0072] The material constituting the substrate 2 is not particularly limited and can be appropriately selected depending on the application and desired physical properties of the molded article 1. Examples of the material constituting the substrate 2 include vinyl chloride resin, acrylic resin, ABS resin, ASA resin, and a resin composition containing a combination of two or more of these resins.

[0073] When the material constituting the substrate 2 is a resin composition, the resin composition may further contain appropriate amounts of, for example, a heat stabilizer, a lubricant, an antioxidant, a light stabilizer, a colorant, an ultraviolet absorber, an anti-fogging agent, an anti-plate-out agent, an antistatic agent, a flame retardant, a weather resistance agent, a surfactant, an impact resistance agent, a foaming agent, various fillers (e.g., calcium carbonate, clay, talc, etc.), etc., depending on the application and desired physical properties of the molded article 1.

[0074] When the material constituting the substrate 2 is a resin composition, the molded article 1 shown in Fig. 1 can be produced, for example, by co-extruding and laminating the resin composition constituting the substrate 2 and the vinyl chloride resin composition in the above-mentioned embodiment constituting the surface layer 3. Specifically, for example, using any known co-extruder, the resin composition constituting the substrate 2 and the vinyl chloride resin composition in the above-mentioned embodiment constituting the surface layer 3 are supplied to a multi-layer mold (die), extruded in a laminated state, and then cooled, whereby the molded article 1 in the form of a laminate can be produced.

[0075] The thickness of the surface layer 3 made of a vinyl chloride resin composition is not particularly limited, and can be appropriately set depending on the application of the molded article 1, the desired physical properties, the constituent material of the base material 2, the thickness of the base material 2, etc. For example, from the viewpoint that the molded article 1 can be suitably used for various applications as the molded article 1 that can exhibit good moldability, antibacterial performance, or antiviral performance even if it is thin, the thickness of the surface layer 3 is preferably 0.1 mm to 3 mm, more preferably 0.15 mm to 1 mm, and even more preferably 0.2 mm to 0.5 mm.

[0076] When the material constituting the substrate 2 is a resin composition, the thickness of the substrate 2 is not particularly limited and can be set appropriately depending on the application of the molded article 1, the desired physical properties, the type of resin contained in the substrate 2, the thickness of the surface layer 3, etc.

[0077] Moreover, the surface layer 3 does not need to be formed (or laminated) on the entire surface of the substrate 2, and may be formed on at least a portion of the surface of the substrate 2. For example, in the molded article 1, the surface layer 3 may be formed on a portion of the surface of the substrate 2 where antibacterial or antiviral properties are required. Specifically, for example, the surface layer 3 may be formed only on a portion of the surface of the molded article 1 that may be directly touched by a person, or on a portion of the surface of the molded article 1 where bacteria, viruses, etc. are likely to adhere and / or propagate. Furthermore, in FIG. 1, the surface layer 3 is formed only on one surface of the flat substrate 2, but the surface layer 3 may also be formed on the other surface of the substrate 2.

[0078] In addition, FIG. 1 shows a case where the shape of the molded article 1 is approximately flat plate-like, but as with the molded body in the above-described embodiment, the shape is not particularly limited and may be, for example, rod-like, cylindrical, annular, irregular, etc.

[0079] Specific examples of the molded body in the above-mentioned embodiment and the molded product in this embodiment include, but are not limited to, various building materials such as interior base materials and exterior materials, various components in furniture and miscellaneous goods, various home appliance components in OA equipment, and various interior and exterior materials in vehicles such as automobiles, motorcycles, and bicycles. Among these, the molded body in the above-mentioned embodiment and the molded product in this embodiment are particularly suitable for use in wet areas as interior materials such as ceiling trim materials, frame materials for ceiling or wall inspection hatches, sash frame materials, wall panels for kitchens, bathrooms, washrooms, or dressing rooms, and opening frames, from the viewpoint of excellent antibacterial or antiviral properties even when thin-walled. EXAMPLES

[0080] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0081] In the present examples, test pieces of molded articles of various vinyl chloride resin compositions were actually prepared by changing the type and / or compounding ratio of the antibacterial agent or antiviral agent, and the type and / or compounding ratio of the antibacterial auxiliary, and the performance was evaluated.

[0082] First, a method for preparing test pieces of molded articles of vinyl chloride resin compositions in each of the Examples and Comparative Examples will be described.

[0083] [Preparation of test pieces of molded vinyl chloride resin composition] The raw materials in the compounding ratios of Examples 1 to 8 and Comparative Examples 1 to 14 shown in Tables 1 and 2 below were mixed in advance by dry blending, and the mixture was put into the hopper of an extruder ("Labo Plastomill" manufactured by Toyo Seiki Seisakusho, Ltd.). Thereafter, the mixture was melt-kneaded and extruded at a cylinder temperature of 170°C for 0.2 hours, and naturally cooled for 0.2 hours to obtain a 4 mm-thick plate-shaped (sheet-shaped) molded article of the vinyl chloride resin composition. Furthermore, the obtained plate-shaped molded article was cut out using a cutter to the size of the test piece of the molded article used in each test described below.

[0084] Details of the raw materials used are as follows: Vinyl chloride resin: Shin-Etsu Chemical Co., Ltd., "PVC resin", average degree of polymerization 1000 Antibacterial agent (zinc-based antibacterial agent): Toagosei Co., Ltd., "VZ100" Antibacterial agent (silver-based antibacterial agent): Toagosei Co., Ltd., "AG1100" Antiviral agent (organic-inorganic hybrid antiviral agent): "N-Clear AVPVC" manufactured by Nitto Corporation Antibacterial agent (Ca-Zn complex compound): ADEKA, "RX-218" Antibacterial agent (Pb-based compound): Mizusawa Chemicals, "OGF" Antibacterial agent (Sn-based compound): ADEKA, "OT-9"

[0085] Next, the performance of the test pieces of the molded articles of the vinyl chloride resin compositions of the respective Examples and Comparative Examples was evaluated. The detailed test methods for each performance evaluation are described below.

[0086] [Antiviral test] Among the test pieces of the molded vinyl chloride resin composition in each Example and Comparative Example, the antiviral test was performed on the test pieces of the molded product containing an antiviral agent. In the antiviral test, a test piece of the molded product having a size of 5 cm x 5 cm x 4 mm (thickness) was used, and the antiviral activity values ​​of influenza virus and feline calicivirus were measured in accordance with ISO 21702:2019 to evaluate the antiviral properties of the test piece of the molded product. The evaluation was performed on both the test piece that had been subjected to a water-resistant treatment as a pretreatment and the test piece that had been subjected to a light-resistant treatment. The evaluation criteria are shown below. 〇: Antiviral activity value is 2.0 or higher ×: Antiviral activity value is less than 2.0

[0087] [Antibacterial test] Among the test pieces of the molded vinyl chloride resin composition in each Example and Comparative Example, the test pieces of the molded product containing an antibacterial agent were subjected to this antibacterial test. In the antibacterial test, the test pieces of the molded product measuring 5 cm x 5 cm x 4 mm (thickness) were used, and the antibacterial activity values ​​of Staphylococcus aureus and Escherichia coli were measured in accordance with JIS Z 2801:2010 (ISO 22196:2007), and the antibacterial properties of the test pieces of the molded product were evaluated. The evaluation criteria are shown below. 〇: Antibacterial activity value is 2.0 or higher ×: Antibacterial activity value is less than 2.0

[0088] [Surface property test] In the surface property test, a molded test piece measuring 10 cm x 10 cm x 4 mm (thickness) was used, and the surface property (presence or absence of unevenness) was evaluated by observing the surface. The evaluation criteria are as follows. 〇: No irregularities are visible on the surface △: There are irregularities on some parts of the surface ×: Unevenness exists over the entire surface

[0089] [Charpy impact test] In the Charpy impact test, a molded test piece (Type 1 test piece specified in JIS K 7111-1:2012) measuring 80 cm x 10 cm x 4 mm (thickness) was used, and the Charpy impact strength (kJ / m 2 The evaluation criteria are as follows: Pass: Charpy impact strength is 7 (kJ / m 2 ) End Fail: Charpy impact strength is 7 (kJ / m 2 )less than

[0090] [Color change test] In the color change test, a molded test piece measuring 10 cm x 10 cm x 4 mm (thickness) was used, and the color change (presence or absence of dullness) was observed to evaluate the color. The evaluation criteria are as follows: 〇: No dullness is observed △: Some parts are dull ×: Dull throughout

[0091] The compounding ratios of various raw materials in the vinyl chloride resin compositions in each Example and Comparative Example, as well as the evaluation results of each test of the test pieces of the prepared molded bodies, are summarized in the following Tables 1 and 2. In the following Tables 1 and 2, "-" next to the compounding ratio indicates that it is not included in the composition.

[0092] [Table 1] The (※) in Table 1 above indicates that there is a risk of the surface discoloring after a certain period of time due to the generation of silver oxide.

[0093] [Table 2]

[0094] [Consideration] As can be seen from the results of Examples 1 to 5 and 8 in Table 1 above, when the Ca-Zn-based composite compound was contained in the range of 3.5 to 4.5 parts by mass as an antibacterial auxiliary, even if the amount of the antibacterial agent added was small (specifically, 0.1 to 0.7 parts by mass), the molded body exhibited excellent antibacterial performance, and at the same time, the results of the surface property test, Charpy impact test, and color change test were not ``X'' or failure.

[0095] On the other hand, as can be seen from the results of Comparative Examples 1 to 3 and 5 in Table 2 above, when an equivalent amount of a Pb-based compound or an Sd-based compound, which has traditionally been used as a stabilizer for polyvinyl chloride resin as a substitute for a Ca-Zn-based composite compound, was added (specifically, 4 parts by mass), and an equivalent amount of an antibacterial agent was also added (specifically, 0.1 to 0.7 parts by mass or 0.3 parts by mass, respectively), the molded body did not exhibit sufficient antibacterial properties.

[0096] As can be seen from the results of Comparative Examples 4, 6 and 7 in Table 2 above, when the material contained any of a Ca-Zn based composite compound, a Pb based compound and an Sd based compound but did not contain any antibacterial agent, the results of the surface property test, the Charpy impact test and the color change test were good, but no antibacterial properties were exhibited.

[0097] Furthermore, as can be seen from the results of Comparative Example 8 in Table 2 above, even when the same amount of Ca-Zn composite compound as the antibacterial auxiliary as in the Examples (specifically, 4 parts by mass) was included, when the amount of the antibacterial agent was too small (specifically, 0.07 parts by mass), sufficient antibacterial properties could not be exhibited. Also, as can be seen from the results of Comparative Example 9 in Table 2 above, even when the same amount of Ca-Zn composite compound as the Examples was included as the antibacterial auxiliary (specifically, 4 parts by mass), when the amount of the antibacterial agent was too large (specifically, 1 part by mass), the results were poor in the surface property test, Charpy impact test, and color change test.

[0098] In addition, the results of Example 8 show that even when a silver-based antibacterial agent is used as the antibacterial agent, the same effect as that of the zinc-based antibacterial agent in this embodiment can be achieved. However, since there is a risk that silver oxide will be generated over time after molding and the surface will discolor, it is preferable to use a zinc-based antibacterial agent as the antibacterial agent.

[0099] As can be seen from the results of Examples 6 and 7 in Table 1 above, when 4 parts by mass of a Ca-Zn-based composite compound was contained as an antibacterial auxiliary per 100 parts by mass of polyvinyl chloride resin, the molded article exhibited excellent antiviral performance even when the amount of antiviral agent added was small (specifically, 5 to 10 parts by mass), and at the same time, the results of the surface property test, Charpy impact test, and color change test were not "X" or did not correspond to failure.

[0100] On the other hand, as can be seen from the results of Comparative Example 10 in Table 2 above, even when the same amount of Ca-Zn-based composite compound was included as the antibacterial auxiliary, if the amount of antiviral agent was too small (specifically, 4 parts by mass), sufficient antiviral properties could not be exhibited. Also, as can be seen from the results of Comparative Example 11 in Table 2 above, even when the same amount of Ca-Zn-based composite compound was included as the antibacterial auxiliary, if the amount of antiviral agent was too large (specifically, 11 parts by mass), the results were inferior in the Charpy impact test and color change test.

[0101] As can be seen from the results of Comparative Examples 12 and 13 in Table 2 above, when the Ca-Zn based composite compound is contained in an amount outside the range of 3.5 parts by mass to 4.5 parts by mass (specifically, 5 parts by mass or 3 parts by mass), the resin composition becomes too fluid or burns or blooms during molding, making it impossible to mold.

[0102] Furthermore, as can be seen from the results of Comparative Example 14 in Table 2 above, when the polyvinyl chloride resin composition does not contain any of the Ca-Zn-based composite compound, the Pb-based compound, and the Sd-based compound, it is unstable and cannot be molded.

[0103] The embodiments and examples disclosed herein should be understood to be illustrative and not restrictive in all respects. The scope of the present invention is defined by the claims, not the above description, and is intended to include all modifications within the meaning and scope of the claims. [Explanation of symbols]

[0104] 1 Molded product 2 Base material 3 Surface layer

Claims

1. The composition comprises a vinyl chloride resin, 0.1 to 0.7 parts by mass of a zinc-based antibacterial agent relative to 100 parts by mass of the vinyl chloride resin, or 5 to 10 parts by mass of an organic-inorganic hybrid antiviral agent relative to 100 parts by mass of the vinyl chloride resin, and a Ca-Zn-based composite compound as an antibacterial auxiliary; The vinyl chloride resin composition contains 3.5 to 4.5 parts by mass of the Ca-Zn-based composite compound relative to 100 parts by mass of the vinyl chloride resin.

2. A molded article comprising the vinyl chloride resin composition according to claim 1.

3. A molded article comprising a substrate and a surface layer formed on the surface of the substrate, the surface layer being made of the vinyl chloride resin composition according to claim 1.

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