WO2017145976A1 - Antibacterial and antiviral vinyl chloride-based resin composition - Google Patents

Antibacterial and antiviral vinyl chloride-based resin composition Download PDF

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Publication number
WO2017145976A1
WO2017145976A1 PCT/JP2017/006082 JP2017006082W WO2017145976A1 WO 2017145976 A1 WO2017145976 A1 WO 2017145976A1 JP 2017006082 W JP2017006082 W JP 2017006082W WO 2017145976 A1 WO2017145976 A1 WO 2017145976A1
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WIPO (PCT)
Prior art keywords
vinyl chloride
resin composition
copper
chloride resin
mass
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PCT/JP2017/006082
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French (fr)
Japanese (ja)
Inventor
嵩人 廣瀬
俊和 金田
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リケンテクノス株式会社
三井化学産資株式会社
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Priority to JP2018501663A priority Critical patent/JP6862412B2/en
Publication of WO2017145976A1 publication Critical patent/WO2017145976A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a vinyl chloride resin composition having antibacterial and antiviral properties.
  • a vinyl chloride resin composition in which a plasticizer is added to a vinyl chloride resin can be adjusted in a wide range of flexibility depending on the amount of the plasticizer, and has a moldability (extrusion moldability, injection moldability, etc.) Adhesiveness, flame retardancy, and heat resistance are also good, and since it is inexpensive, it is widely used as a material for handrails, drainage hoses, boots, gloves, and the like. These uses are required to have antibacterial and antiviral properties from the viewpoint of preventing nosocomial infections. Therefore, the vinyl chloride resin composition which is these materials is also required to have excellent antibacterial and antiviral properties.
  • the copper antibacterial agent has a problem that it is easily discolored in contact with moisture, acid, salt, and the like, and the appearance quality is lowered. Specifically, if moisture adheres to the surface of the copper-based antibacterial agent, there is a problem that patina is generated on the surface and the antibacterial performance deteriorates, and the color tone of the appearance changes greatly, so the usage environment is significantly restricted. There was a problem that it could not be used depending on the environment. In particular, vinyl chloride resin compositions are easily affected by various additives, and are affected by stabilizers in the process of melt mixing and molding, and the antibacterial properties are deactivated in a short time. Thus, no vinyl chloride resin composition has been found that exhibits a stable and sustained antibacterial property.
  • Antibacterial agents for imparting antibacterial properties to vinyl chloride resin compositions include those in which zeolite is substituted with silver ions (Patent Document 1), those composed of silver colloidal particles (Patent Document 2), and silver-containing materials. Proposals have been made of a compound containing a phosphoric acid-containing compound (Patent Document 3), an alloy powder of copper and tin (Patent Document 4), an organic antibacterial agent (Patent Document 5), and the like.
  • an object of the present invention is to provide a vinyl chloride resin composition that stably exhibits excellent antibacterial and antiviral properties despite containing a heat stabilizer.
  • the present invention (A) Vinyl chloride resin 100 parts by mass; A vinyl chloride resin composition comprising: (B) 1 to 150 parts by mass of a metal antibacterial agent; and (C) 0.1 to 10 parts by mass of an alkaline earth metal or a composite compound of an alkali metal and zinc.
  • the (B) metal antibacterial agent is copper-tin alloy particles, The copper-tin alloy particles in the copper-tin alloy particles have an atomic ratio of 50 to 99 at% copper and 50 to 1 at% tin, where the sum of copper and tin is 100 at%. This is a vinyl chloride resin composition.
  • the second invention is characterized in that the component (C) the alkaline earth metal or the composite compound of alkali metal and zinc is at least one selected from the group consisting of a barium / zinc composite compound and a calcium / zinc composite compound. It is a vinyl chloride-type resin composition as described in 1st invention containing a compound.
  • the third invention further includes (D) at least one plasticizer selected from the group consisting of a phthalate ester plasticizer and an epoxy plasticizer, and 1 component per 100 parts by mass of the component (A).
  • the vinyl chloride resin composition according to the first or second invention comprising ⁇ 120 parts by mass.
  • the fourth invention is an article comprising the vinyl chloride resin composition according to any one of the first to third inventions.
  • the vinyl chloride resin composition according to the present invention has excellent antibacterial and antiviral properties. Moreover, mechanical strength and moldability are also good, and it can be easily colored to a desired color. Therefore, articles that require antibacterial and antiviral properties, such as shoes used in food processing factories, pharmaceutical production factories, medical instrument production factories, and hospitals, shoes such as boots and sandals; yoga mats, etc. Mats; industrial hoses such as industrial blade hoses, food hoses, and industrial suction hoses; care products such as bedsore prevention products and hair washing products; hygiene products such as brushes and disposable gloves; used in medical machines, etc.
  • Medical equipment members such as electric wire covering materials; household electrical appliance members such as refrigerator packings; building materials such as handrails, door knobs, and grips; water supplies such as pools, floats, beach balls, boats, bath covers, floats; Indoor play equipment such as vehicles and slides; other materials, health goods, toys, furniture, and stationery supplies It is possible.
  • the term “resin” is used as a term including a resin mixture containing two or more resins and a resin composition containing components other than the resin.
  • the term “above” relating to a numerical range is used in the sense of a certain numerical value or a certain numerical value. For example, 20% or more means 20% or more than 20%.
  • the term “below” relating to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%.
  • the symbol “ ⁇ ” in a numerical range is used to mean a certain numerical value, a certain numerical value and less than a certain other numerical value, or another certain numerical value.
  • 10-90% means 10%, more than 10% and less than 90%, or 90%.
  • antibacterial not only means preventing the growth of bacteria such as bacteria and fungi but also includes the meaning of killing or reducing the bacteria. These bacteria are not particularly limited. Examples include bacteria such as MRSA, Bacillus cereus, Neisseria pneumoniae, and mold. The term “antiviral” means inactivating a part of the virus, specifically, suppressing the virus infectivity.
  • the virus is not particularly limited, and rhinovirus, poliovirus, rotavirus, foot-and-mouth disease virus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, type A, type B, type C influenza virus, Parainfluenza virus, mumps virus, measles virus, human metapneumovirus, RS virus, Nipah virus, Hendra virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, type B, hepatitis C virus, eastern part And Western equine encephalitis virus, Onyung Nyon virus, rubella virus, Lassa virus, Junin virus, Machupo virus, Guanarito virus, Sabia virus, Crimea congo hemorrhagic fever virus, Fever, hantavirus, sinombre virus, rabies virus, ebola virus, marburg virus, bat lyssa virus, human T cell leukemia virus, human immunodefici
  • the vinyl chloride resin composition according to the present invention includes (A) a vinyl chloride resin, (B) a metal antibacterial agent, and (C) an alkaline earth metal or a composite compound of an alkali metal and zinc.
  • the vinyl chloride resin composition of the present invention is preferably (A) a vinyl chloride resin, (B) a metal antibacterial agent, (C) an alkaline earth metal or a composite compound of an alkali metal and zinc, and (D) Contains plasticizer.
  • each component which comprises the vinyl chloride-type resin composition by this invention is demonstrated.
  • the vinyl chloride resin used as component (A) of the present invention refers to all polymers having a group represented by —CH 2 —CHCl—.
  • Examples of the vinyl chloride resin used as the component (A) of the present invention include vinyl chloride homopolymers; vinyl chloride / vinyl acetate copolymers, vinyl chloride / (meth) acrylic acid copolymers, vinyl chloride / ( (Meth) methyl acrylate copolymer, vinyl chloride / (meth) ethyl acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride ⁇ Styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride terpolymer,
  • a chlorinated polyolefin similar in structure to a vinyl chloride resin such as chlorinated polyethylene may be used.
  • the above component (A) is preferably a vinyl chloride homopolymer from the viewpoints of moldability, antibacterial properties and antiviral properties.
  • the average degree of polymerization calculated based on the specific viscosity from the specific viscosity measured in accordance with Appendix 4.1 specific viscosity of JIS K6720-2: 1999 of the above component (A) is a viewpoint of improving the mechanical strength. Therefore, it may be preferably 800 or more, more preferably 1000 or more. From the viewpoint of improving the moldability, it may be preferably 3000 or less, more preferably 2600 or less. From the viewpoint of the balance between mechanical strength and molding processability, it is preferably 800 to 3000, more preferably 1000 to 2600.
  • component (A) one or a mixture of two or more of these vinyl chloride resins can be used.
  • the component (B) is a metal antibacterial agent.
  • copper-tin alloy particles are used as the component (B).
  • the content ratio of copper and tin in the copper-tin alloy particles is such that a sufficient amount of copper ions is generated and good antibacterial and antiviral properties are expressed.
  • the copper percentage is 50 to 99 at% and the tin percentage is 50 to 1 at%, preferably 60 to 95 at% for copper and 40 to 5 at% for tin.
  • the copper tin-based alloy particles may further contain an element other than copper tin under the condition that the effects of the present invention are not impaired.
  • an element other than copper tin under the condition that the effects of the present invention are not impaired.
  • the other elements include aluminum, germanium, beryllium, nickel, and silicon.
  • other metals having antibacterial properties such as zinc, silver, and nickel may be contained as long as the corrosion resistance is not impaired.
  • oxygen atoms may be contained due to the fact that some of the copper-tin alloy particles are oxidized.
  • the copper-tin alloy particles may contain non-metallic elements such as oxygen, carbon, nitrogen, and chlorine.
  • the sum of the copper content and the tin content in the copper-tin alloy particles is an atomic ratio, and the total sum of all elements is 100 at%, usually 50 at% or more, preferably 90 at% or more, more preferably 95 at% or more, More preferably, it may be 99 at% or more and 100 at% or less.
  • the copper-tin alloy-based particles consist essentially of copper and tin, that is, the copper content in the copper-tin-based alloy particles
  • the sum of the tin contents is most preferably 100 at%, where the sum of all elements is 100 at%.
  • the component (B) is copper-tin alloy particles, and the particle size distribution may be such that the content of fine particles having a particle size of 45 ⁇ m or less is usually 80% by volume or more.
  • the particle size distribution was measured by a laser diffraction / scattering method in accordance with JIS R1629-1997.
  • the particle size distribution of the component (B) is such that the content of fine particles having a particle size of 45 ⁇ m or less is usually 80% by volume or more, preferably 90% by volume or more, good antibacterial properties, Viral properties are easily expressed.
  • the content of fine particles having a particle diameter of 45 ⁇ m or less is usually 99% by volume or less, preferably 95% by volume or less, the production cost can be easily reduced.
  • the component (B) is copper-tin alloy particles, and the apparent density thereof may be usually 0.5 to 3 g / cm 3 .
  • the apparent density refers to a density measured according to JIS Z 2504: 2012.
  • the apparent density of the component (B) is usually 3 g / cm 3 or less, preferably 2.8 g / cm 3 or less, from the viewpoint of antibacterial properties and antiviral properties.
  • the apparent density of the component (B) is usually 0.5 g / cm 3 or more, preferably 1 g / cm 3 or more, from the viewpoint of discoloration resistance.
  • the compounding amount of the component (B) is usually 1 part by mass or more, preferably 5 parts by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint of antibacterial and antiviral properties. From the viewpoint of antibacterial and antiviral properties, the larger the amount of the component (B), the better. On the other hand, from the viewpoints of mechanical strength, resin composition productivity, and molding processability, it may usually be 150 parts by mass or less, preferably 90 parts by mass or less.
  • the component (C) is an alkaline earth metal or a composite compound of an alkali metal and zinc.
  • the component (C) functions to impart thermal stability and processing stability to the vinyl chloride resin composition of the present invention without impairing its antibacterial and antiviral properties.
  • component (C) examples include alkaline earth metal / zinc composite compounds, alkali metal / zinc composite compounds, alkaline earth metal / alkali metal / zinc composite compounds, and mixtures of one or more thereof. Can do.
  • the component (C) preferably contains at least one compound selected from the group consisting of a barium / zinc composite compound and a calcium / zinc composite compound.
  • the component (C) is more preferably at least one compound selected from the group consisting of a barium / zinc composite compound and a calcium / zinc composite compound.
  • Examples of the barium / zinc composite compound include barium, zinc, and an organic acid barium / zinc composite salt containing an organic acid.
  • Examples of the calcium / zinc composite compound include calcium, zinc, and an organic acid calcium / zinc composite salt containing an organic acid.
  • organic acid examples include fatty acids such as stearic acid, palmitic acid, lauric acid, linoleic acid, ricinoleic acid, octylic acid, 2-ethylhexylic acid, and oleic acid; phosphites; and benzoic acid Aromatic carboxylic acids and the like can be mentioned. One or more of these can be used as the organic acid.
  • the component (C) may be made of “made of vinyl chloride” It is preferable to use what is described / registered in “Positive list ⁇ ⁇ ⁇ ⁇ : PL standard regarding food containers and packaging” in an amount within the range of the blending amount restriction described in the list. One or more of these can be used as the component (C).
  • a vinyl chloride resin composition having a good antibacterial property has not been obtained in the past is presumed to be because the heat stabilizer and the antibacterial agent caused an antagonistic action. It is specific that the component (C) and the component (B) are not antagonizing, and that a vinyl chloride resin composition having not only antibacterial properties but also good antiviral properties can be obtained. That is amazing. Stabilizers are essential for maintaining the thermal stability of vinyl chloride resin, and act to suppress the generation of corrosive gases such as hydrochloric acid gas due to thermal decomposition of vinyl chloride resin, but do not contain stabilizers.
  • a corrosive gas such as hydrochloric acid gas generated due to the thermal decomposition of the vinyl chloride resin causes corrosion of the surface of the antibacterial agent, thereby impairing the antibacterial property.
  • a means capable of achieving both the functions of not only preventing antibacterial properties but also preventing the antiviral effect and suppressing the thermal decomposition of vinyl chloride resin has been found. .
  • the compounding amount of the component (C) is usually 0.1 parts by mass or more, preferably 0.3 parts by mass or more with respect to 100 parts by mass of the component (A), from the viewpoint of thermal stability.
  • it may be usually 10 parts by mass or less, preferably 5 parts by mass or less.
  • the vinyl chloride resin composition according to the present invention preferably further contains one or more plasticizers.
  • the plasticizer functions to adjust the flexibility of the vinyl chloride resin composition of the present invention.
  • the component (D) can be appropriately selected and used depending on the purpose.
  • component (D) examples include phthalate ester plasticizers, trimellitic ester plasticizers, pyromellitic ester plasticizers, adipate ester plasticizers, itaconic ester plasticizers, and citrate esters.
  • examples thereof include a plasticizer, a cyclohexanedicarboxylate plasticizer, and an epoxy plasticizer.
  • component (D) examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butane.
  • polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butane.
  • polyester plasticizers that use pimelic acid, suberic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary, monohydric alcohol or monocarboxylic acid as a stopper. be able to.
  • phthalate ester plasticizer examples include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, And dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.
  • trimellitic acid ester plasticizer examples include tri (2-ethylhexyl) trimellitate, tri (n-octyl) trimellitate, and tri (isononyl) trimellitate.
  • adipate ester plasticizer examples include bis (2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.
  • epoxy plasticizer examples include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.
  • the component (D) is preferably a phthalate ester plasticizer and an epoxy plasticizer from the viewpoint of antibacterial properties, antiviral properties, and moldability.
  • the component (D) is selected from the group consisting of the phthalate ester plasticizer and the epoxy plasticizer from the viewpoints of thermal stability, antibacterial / antiviral properties, color stability, and moldability.
  • containing at least one kind of plasticizer more preferably containing the above phthalate ester plasticizer and the above epoxy plasticizer, and the total amount of the above component (D) as 100% by mass. It is more preferable to contain 90 to 99% by mass of an ester plasticizer and 10 to 1% by mass of the epoxy plasticizer.
  • ⁇ As the component (D), one or more of these can be used in combination.
  • the compounding amount of the component (D) is usually 1 part by mass or more, preferably 3 parts by mass or more, from the viewpoint of moldability with respect to 100 parts by mass of the component (A). On the other hand, from the viewpoint of productivity of the resin composition and mechanical strength, it may be usually 120 parts by mass or less, preferably 100 parts by mass or less.
  • various additives usually used in the vinyl chloride resin and its resin composition for example, other heat stabilizers, for example, as long as they do not contradict the purpose of the present invention.
  • Lubricants, pigments, UV absorbers, mold release agents, antistatic agents, metal deactivators, surfactants, foaming agents, etc. and various fillers (for example, calcium carbonate, clay, talc, etc.). Can be included.
  • the method for producing the vinyl chloride resin composition according to the present invention is not particularly limited, and can be produced by any method.
  • the vinyl chloride resin composition according to the present invention comprises the above-described components (A) to (C) and optional components used as desired in any melt kneader (eg, single screw extruder, twin screw extruder, roll). , A mixer, and various kneaders).
  • melt kneader eg, single screw extruder, twin screw extruder, roll.
  • a mixer e.g, single screw extruder, twin screw extruder, roll
  • various kneaders e.g, single screw extruder, twin screw extruder, roll.
  • it can be obtained by melt kneading at a resin temperature of 150 to 180 ° C. using a pressure kneader.
  • the vinyl chloride resin composition according to the present invention is preferably produced by a so-called master batch method.
  • a resin composition hereinafter abbreviated as “MB”
  • MB resin composition
  • the components (A) to (C), and optional components used as desired are melt-kneaded using any melt-kneader.
  • the dispersibility / uniformity of the component (B) in the composition can be improved, and as a result, antibacterial properties and antiviral properties can be improved.
  • the antibacterial activity of Staphylococcus aureus (Staphylococcus aureus) measured as described in the test (5) of the following example of the vinyl chloride resin composition according to the present invention is preferably a log reduction value of 2 or more, more preferably 2. It may be 5 or more, more preferably 3 or more, still more preferably 3.5 or more, and most preferably 4 or more.
  • the antiviral property against E. coli phage (Coliphage) measured by the test (6-1) of the following example of the vinyl chloride resin composition of the present invention has a log reduction value of preferably 2 or more, more preferably 2 .5 or more, more preferably 3 or more, even more preferably 3.5 or more, and most preferably 4 or more.
  • the antiviral property against feline calicivirus measured by the test (6-2) of the following example of the vinyl chloride resin composition of the present invention has a logarithmic decrease value of preferably 2 or more. More preferably, it may be 2.5 or more, more preferably 3 or more, still more preferably 3.5 or more, and most preferably 4 or more.
  • the molded body of the antibacterial vinyl chloride resin composition of the present invention can be formed into a desired shape by applying to various molding methods.
  • the molding method include known molding methods such as an extrusion molding method, an injection molding method, a blow molding method, a calender roll rolling film forming method, and an extrusion film forming method.
  • the molding conditions can be appropriately selected from known conditions according to the target article.
  • (A) Vinyl chloride resin (A-1) Polyvinyl chloride (manufactured by Shin Daiichi PVC Co., Ltd., “ZEST 1000Z (trade name)”, average degree of polymerization 1000) was used.
  • (B) Copper-tin alloy particles (B-1) Copper-tin alloy (copper content is 79.1 at% in atomic ratio, tin content is 20.9 at% in atomic ratio, content of fine particles having a particle diameter of 45 ⁇ m or less is 100 vol%, and apparent A density of 2.75 g / cm 3 ) was used.
  • C ′ Reference compound: (C′-1) Dimethyltin mercapto (“TM-181FSJ (trade name)” manufactured by Katsuta Chemical Co., Ltd.) was used. (C′-2) Lead stearate (“NSP-R (trade name)” manufactured by NI Chemtech Co., Ltd.) was used.
  • TM-181FSJ Dimethyltin mercapto
  • NSP-R Lead stearate
  • D Plasticizer
  • D-1 Diisononyl phthalate (“DINP (trade name)” manufactured by J-Plus Co., Ltd.) was used.
  • D-2) Epoxidized soybean oil (“O-130S (trade name)” manufactured by ADEKA Corporation) was used.
  • Examples 1 to 13 Examples 1S to 7S> A blend having a blending ratio (part by mass) shown in any one of Tables 1 to 3 is melt-kneaded at a resin temperature of 180 ° C. using a two-roll kneader manufactured by Kansai Roll Co., Ltd. A composition was obtained. Each of the obtained resin compositions was subjected to the following tests (1) to (6). The test results were as shown in any one of Tables 1 to 3 below.
  • Hardness The hardness (value for 15 seconds) of Shore A was measured according to JIS K7215: 1986. The sample used was a 6 mm thick press sheet obtained by hot pressing the dispensing sheet obtained above.
  • Antiviral 1 (E. coli phage): With reference to JIS Z 2801: 2010, antiviral properties were measured using Escherichia coli phages at the Kitasato Environmental Science Center. That is, a 50 mm ⁇ 50 mm test piece was cut out from a 1.0 mm-thick press sheet obtained by hot pressing the dispensing sheet obtained above, placed in a moisturizing petri dish, and 0.2 mL of coliphage was put on the test piece. The virus solution was covered with a 40 mm ⁇ 40 mm film. This was allowed to act at 25 ° C. for 24 hours (still), and then the virus solution was drawn from the test piece and the infectivity titer was measured.
  • the infectivity titer after acting for 24 hours at 25 ° C. was measured for the standard sample.
  • the result was shown as a logarithmic decrease value calculated using both values.
  • the log reduction value of 3 means that the infectious titer was 1/1000 of the standard sample.
  • the vinyl chloride resin composition according to the present invention has excellent antibacterial and antiviral properties.
  • the preferred vinyl chloride resin composition of the present invention has excellent antibacterial and antiviral properties, and has good mechanical properties, heat aging characteristics, and extrusion processability. Therefore, it can be used widely and suitably as a material for articles requiring antibacterial and antiviral properties.

Abstract

Provided is a vinyl chloride-based resin composition having excellent antibacterial and antiviral performance. The vinyl chloride-based resin composition comprises (A) 100 parts by mass of a vinyl chloride-based resin; (B) 1 to 150 parts by mass of a metal-based antibacterial agent; and (C) 0.1 to 10 parts by mass of a conjugated compound of alkaline earth metal or alkali metal and zinc. The metal-based antibacterial agent (B) is copper-tin alloy particles, the content ratio of copper and tin in the copper-tin alloy is an atomic ratio of 50 to 99 at% of copper and 50 to 1 at% of tin when the total of copper and tin is 100 at%.

Description

抗菌・抗ウイルス性塩化ビニル系樹脂組成物Antibacterial and antiviral vinyl chloride resin composition
　本発明は、抗菌・抗ウイルス性を有する塩化ビニル系樹脂組成物に関する。 The present invention relates to a vinyl chloride resin composition having antibacterial and antiviral properties.
　近年、様々な菌やウイルスによる汚染の問題がクローズアップされており、例えば、院内感染などは社会問題化している。特に黄色ブドウ球菌、インフルエンザウイルス、およびノロウイルスなどの強力な菌やウイルス類による汚染が深刻な問題としてクローズアップされている。これらの菌やウイルス類は比較的短時間で増殖し、汚染力が強く、更に耐性もあり、感染が広範囲に急速に広まることから、抗菌・抗ウイルス機能としては、より短時間で増殖する菌やウイルスを抑制できることが求められている。 In recent years, the problem of contamination by various bacteria and viruses has been highlighted. For example, nosocomial infections have become social problems. In particular, contamination by powerful bacteria and viruses such as Staphylococcus aureus, influenza virus, and norovirus has been highlighted as a serious problem. These bacteria and viruses grow in a relatively short period of time, are highly contaminating, resistant, and spread rapidly over a wide area. And the ability to suppress viruses.
　塩化ビニル樹脂に可塑剤が添加された塩化ビニル樹脂組成物は、可塑剤の量の多少により、広範囲な柔軟性の調整が可能であり、成形加工性（押出成形性、射出成型性など）、接着性、難燃性、および耐熱性も良好であり、また低価格であることから、手摺り、排水用ホース、長靴、および手袋などの材料として広く使用されている。これらの用途では、院内感染を防止する観点から、抗菌・抗ウイルス性を有することが求められている。そのためこれらの材料である塩化ビニル系樹脂組成物にも、優れた抗菌・抗ウイルス性を有することが求められている。 A vinyl chloride resin composition in which a plasticizer is added to a vinyl chloride resin can be adjusted in a wide range of flexibility depending on the amount of the plasticizer, and has a moldability (extrusion moldability, injection moldability, etc.) Adhesiveness, flame retardancy, and heat resistance are also good, and since it is inexpensive, it is widely used as a material for handrails, drainage hoses, boots, gloves, and the like. These uses are required to have antibacterial and antiviral properties from the viewpoint of preventing nosocomial infections. Therefore, the vinyl chloride resin composition which is these materials is also required to have excellent antibacterial and antiviral properties.
　銅イオンや銀イオンが優れた抗菌性を有することは古くからよく知られている。しかし、銅系抗菌剤には水分や酸、塩分等との接触において変色を受けやすく、外観の品位が低下する問題があった。具体的には、銅系抗菌剤表面に水分が付着すると、表面に緑青が発生し、抗菌性能が低下する問題がある他、外観の色調も大きく変化することから、使用環境が著しく制約されたり、環境によっては使用できなくなったりする問題があった。特に塩化ビニル樹脂組成物においては、配合される様々な添加剤類の影響を受けやすく、溶融混合や成形加工の過程で特に安定剤類などによる作用を受けて、抗菌性が短時間で失活するなど、これまで安定して持続する抗菌性が発現する塩化ビニル樹脂組成物は見出されていない。 It has been well known for a long time that copper ions and silver ions have excellent antibacterial properties. However, the copper antibacterial agent has a problem that it is easily discolored in contact with moisture, acid, salt, and the like, and the appearance quality is lowered. Specifically, if moisture adheres to the surface of the copper-based antibacterial agent, there is a problem that patina is generated on the surface and the antibacterial performance deteriorates, and the color tone of the appearance changes greatly, so the usage environment is significantly restricted. There was a problem that it could not be used depending on the environment. In particular, vinyl chloride resin compositions are easily affected by various additives, and are affected by stabilizers in the process of melt mixing and molding, and the antibacterial properties are deactivated in a short time. Thus, no vinyl chloride resin composition has been found that exhibits a stable and sustained antibacterial property.
　塩化ビニル系樹脂組成物に抗菌性を付与するための抗菌剤としては、ゼオライトを銀イオンで置換したもの（特許文献１）、銀のコロイド粒子から成るもの（特許文献２）、銀含有物にリン酸含有化合物を共存させるもの（特許文献３）、銅と錫の合金粉（特許文献４）、および有機系抗菌剤（特許文献５）などが提案されている。 Antibacterial agents for imparting antibacterial properties to vinyl chloride resin compositions include those in which zeolite is substituted with silver ions (Patent Document 1), those composed of silver colloidal particles (Patent Document 2), and silver-containing materials. Proposals have been made of a compound containing a phosphoric acid-containing compound (Patent Document 3), an alloy powder of copper and tin (Patent Document 4), an organic antibacterial agent (Patent Document 5), and the like.
特開平３－１６１４０９号公報JP-A-3-161409 特開平４－３２１６２８号公報JP-A-4-321628 特開平３－３８５０４号公報JP-A-3-38504 特開平７－１１８１１４号公報JP 7-118114 A 特開平６－２８７４７７公報JP-A-6-287477
　しかしながら、上記特許文献等で提案されている抗菌剤を用いた塩化ビニル系樹脂組成物は、抗菌性が不十分であった。また、上記特許文献等には、抗ウイルス性については何の記載も示唆もない。したがって、本発明の課題は、熱安定剤を含有しているにもかかわらず、安定して優れた抗菌性、および抗ウイルス性を発揮する塩化ビニル系樹脂組成物を提供することである。 However, the vinyl chloride resin composition using the antibacterial agent proposed in the above-mentioned patent documents has insufficient antibacterial properties. In addition, the above-mentioned patent documents do not describe or suggest any antiviral properties. Accordingly, an object of the present invention is to provide a vinyl chloride resin composition that stably exhibits excellent antibacterial and antiviral properties despite containing a heat stabilizer.
　本発明者は、鋭意研究した結果、特定の塩化ビニル樹脂組成物により、上記課題を達成できることを見出した。 As a result of intensive studies, the present inventor has found that the above-mentioned problems can be achieved by a specific vinyl chloride resin composition.
　すなわち、本発明は、
　（Ａ）塩化ビニル系樹脂　１００質量部；
　（Ｂ）金属系抗菌剤　１～１５０質量部；および
　（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物　０．１～１０質量部；を含む塩化ビニル系樹脂組成物であって、
　前記（Ｂ）金属系抗菌剤が銅錫系合金粒子であり、
　前記銅錫系合金粒子における銅と錫の含有割合が、原子比で、銅と錫の和を１００ａｔ％として、銅　５０～９９ａｔ％、および錫 ５０～１ａｔ％である、
塩化ビニル系樹脂組成物である。 That is, the present invention
(A) Vinyl chloride resin 100 parts by mass;
A vinyl chloride resin composition comprising: (B) 1 to 150 parts by mass of a metal antibacterial agent; and (C) 0.1 to 10 parts by mass of an alkaline earth metal or a composite compound of an alkali metal and zinc.
The (B) metal antibacterial agent is copper-tin alloy particles,
The copper-tin alloy particles in the copper-tin alloy particles have an atomic ratio of 50 to 99 at% copper and 50 to 1 at% tin, where the sum of copper and tin is 100 at%.
This is a vinyl chloride resin composition.
　第２の発明は、前記成分（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物が、バリウム・亜鉛複合化合物、およびカルシウム・亜鉛複合化合物からなる群から選択される少なくとも１種以上の化合物を含む、第１の発明に記載の塩化ビニル系樹脂組成物である。 The second invention is characterized in that the component (C) the alkaline earth metal or the composite compound of alkali metal and zinc is at least one selected from the group consisting of a barium / zinc composite compound and a calcium / zinc composite compound. It is a vinyl chloride-type resin composition as described in 1st invention containing a compound.
　第３の発明は、更に（Ｄ）フタル酸エステル系可塑剤、およびエポキシ系可塑剤からなる群から選択される少なくとも１種以上の可塑剤、前記成分（Ａ）１００質量部に対して、１～１２０質量部を含む、第１の発明または第２の発明に記載の塩化ビニル系樹脂組成物である。 The third invention further includes (D) at least one plasticizer selected from the group consisting of a phthalate ester plasticizer and an epoxy plasticizer, and 1 component per 100 parts by mass of the component (A). The vinyl chloride resin composition according to the first or second invention, comprising ˜120 parts by mass.
　第４の発明は、第１～３の発明の何れか１に記載の塩化ビニル系樹脂組成物を含む物品である。 The fourth invention is an article comprising the vinyl chloride resin composition according to any one of the first to third inventions.
　本発明による塩化ビニル系樹脂組成物は優れた抗菌性、および抗ウイルス性を有する。また機械的強度、および成形加工性も良好であり、容易に所望の色に着色することができる。そのため抗菌性や抗ウイルス性が要求される物品、例えば、食品加工工場、医薬品生産工場、医療用器具生産工場、および病院などで使用される靴、長靴、およびサンダルなどの靴類；ヨガマットなどのマット類；工業用ブレードホース、食品用ホース、工業用サクションホースなどの工業用ホース類；床ずれ防止用品、洗髪用品などの介護用品；ブラシ、ディスポーザブル手袋などの衛生用品；医療機械等に使用される電線被覆材などの医療機器部材；冷蔵庫パッキン等の家電部材；手摺り、ドアノブ、およびグリップなどの建材；プール、浮輪、ビーチボール、ボート、風呂蓋、フロート類などの水物用品；ハウス類、乗物、滑り台などの室内遊具；その他雑貨類、健康グッズ、玩具、家具、および文具用品などの材料として好適に用いることができる。 The vinyl chloride resin composition according to the present invention has excellent antibacterial and antiviral properties. Moreover, mechanical strength and moldability are also good, and it can be easily colored to a desired color. Therefore, articles that require antibacterial and antiviral properties, such as shoes used in food processing factories, pharmaceutical production factories, medical instrument production factories, and hospitals, shoes such as boots and sandals; yoga mats, etc. Mats; industrial hoses such as industrial blade hoses, food hoses, and industrial suction hoses; care products such as bedsore prevention products and hair washing products; hygiene products such as brushes and disposable gloves; used in medical machines, etc. Medical equipment members such as electric wire covering materials; household electrical appliance members such as refrigerator packings; building materials such as handrails, door knobs, and grips; water supplies such as pools, floats, beach balls, boats, bath covers, floats; Indoor play equipment such as vehicles and slides; other materials, health goods, toys, furniture, and stationery supplies It is possible.
＜定義＞
　本明細書において「樹脂」の用語は、２以上の樹脂を含む樹脂混合物や、樹脂以外の成分を含む樹脂組成物をも含む用語として使用する。
　数値範囲に係る「以上」の用語は、ある数値またはある数値超の意味で使用する。例えば、２０％以上は、２０％または２０％超を意味する。
　数値範囲に係る「以下」の用語は、ある数値またはある数値未満の意味で使用する。例えば、２０％以下は、２０％または２０％未満を意味する。
　更に数値範囲に係る「～」の記号は、ある数値、ある数値超かつ他のある数値未満、または他のある数値の意味で使用する。ここで、他のある数値は、ある数値よりも大きい数値とする。例えば、１０～９０％は、１０％、１０％超かつ９０％未満、または９０％を意味する。 <Definition>
In this specification, the term “resin” is used as a term including a resin mixture containing two or more resins and a resin composition containing components other than the resin.
The term “above” relating to a numerical range is used in the sense of a certain numerical value or a certain numerical value. For example, 20% or more means 20% or more than 20%.
The term “below” relating to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%.
Further, the symbol “˜” in a numerical range is used to mean a certain numerical value, a certain numerical value and less than a certain other numerical value, or another certain numerical value. Here, it is assumed that some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, more than 10% and less than 90%, or 90%.
　また、本明細書において「抗菌性」の用語は、細菌やカビ菌等の菌の増殖を防ぐことを意味するだけでなく、菌を死滅ないし低減させる意味も包含するものとする。これらの菌は特に限定されるものではなく、大腸菌、黄色ぶどう球菌、表皮ぶどう球菌、連鎖球菌、肺炎球菌、インフルエンザ菌、百日咳菌、腸炎菌、肺炎桿菌、緑膿菌、ビブリオ、緑膿菌、ＭＲＳＡ、セレウス菌、肺炎桿菌などの細菌やカビなどがあげられる。
　また、「抗ウイルス性」の用語は、ウイルスの一部を不活性化することを意味し、具体的には、ウイルス感染価を抑制することを意味する。ウイルスは特に限定されるものではなく、ライノウイルス・ポリオウイルス・ロタウイルス・口蹄疫ウイルス・ノロウイルス・エンテロウイルス・ヘパトウイルス・アストロウイルス・サポウイルス・Ｅ型肝炎ウイルス・Ａ型、Ｂ型、Ｃ型インフルエンザウイルス、パラインフルエンザウイルス、ムンプスウイルス（おたふくかぜ）・麻疹ウイルス・ヒトメタニューモウイルス・ＲＳウイルス・ニパウイルス・ヘンドラウイルス・黄熱ウイルス・デングウイルス・日本脳炎ウイルス・ウエストナイルウイルス・Ｂ型、Ｃ型肝炎ウイルス・東部および西部馬脳炎ウイルス・オニョンニョンウイルス・風疹ウイルス・ラッサウイルス・フニンウイルス・マチュポウイルス・グアナリトウイルス・サビアウイルス・クリミアコンゴ出血熱ウイルス・スナバエ熱・ハンタウイルス・シンノンブレウイルス・狂犬病ウイルス・エボラウイルス・マーブルグウイルス・コウモリリッサウイルス・ヒトＴ細胞白血病ウイルス・ヒト免疫不全ウイルス・ヒトコロナウイルス・ＳＡＲＳコロナウイルス・ヒトポルボウイルス・ポリオーマウイルス、ヒトパピローマウイルス・アデノウイルス・ヘルペスウイルス・水痘・帯状発疹ウイルス・ＥＢウイルス・サイトメガロウイルス・天然痘ウイルス・サル痘ウイルス・牛痘ウイルス・モラシポックスウイルス・パラポックスウイルスなどがあげられる。 Further, in this specification, the term “antibacterial” not only means preventing the growth of bacteria such as bacteria and fungi but also includes the meaning of killing or reducing the bacteria. These bacteria are not particularly limited. Examples include bacteria such as MRSA, Bacillus cereus, Neisseria pneumoniae, and mold.
The term “antiviral” means inactivating a part of the virus, specifically, suppressing the virus infectivity. The virus is not particularly limited, and rhinovirus, poliovirus, rotavirus, foot-and-mouth disease virus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, type A, type B, type C influenza virus, Parainfluenza virus, mumps virus, measles virus, human metapneumovirus, RS virus, Nipah virus, Hendra virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, type B, hepatitis C virus, eastern part And Western equine encephalitis virus, Onyung Nyon virus, rubella virus, Lassa virus, Junin virus, Machupo virus, Guanarito virus, Sabia virus, Crimea congo hemorrhagic fever virus, Fever, hantavirus, sinombre virus, rabies virus, ebola virus, marburg virus, bat lyssa virus, human T cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS coronavirus, human porvovirus, polyoma Examples include viruses, human papillomavirus, adenovirus, herpes virus, varicella, zoster virus, EB virus, cytomegalovirus, smallpox virus, monkeypox virus, cowpox virus, molasipox virus, parapox virus, and the like.
＜塩化ビニル系樹脂組成物＞
　本発明による塩化ビニル系樹脂組成物は、（Ａ）塩化ビニル系樹脂、（Ｂ）金属系抗菌剤、および（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物を含む。本発明の塩化ビニル系樹脂組成物は、好ましくは（Ａ）塩化ビニル系樹脂、（Ｂ）金属系抗菌剤、（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物、および（Ｄ）可塑剤を含む。以下、本発明による塩化ビニル系樹脂組成物を構成する各成分について説明する。 <Vinyl chloride resin composition>
The vinyl chloride resin composition according to the present invention includes (A) a vinyl chloride resin, (B) a metal antibacterial agent, and (C) an alkaline earth metal or a composite compound of an alkali metal and zinc. The vinyl chloride resin composition of the present invention is preferably (A) a vinyl chloride resin, (B) a metal antibacterial agent, (C) an alkaline earth metal or a composite compound of an alkali metal and zinc, and (D) Contains plasticizer. Hereinafter, each component which comprises the vinyl chloride-type resin composition by this invention is demonstrated.
＜（Ａ）塩化ビニル系樹脂＞
　本発明の成分（Ａ）として用いる塩化ビニル系樹脂は、－ＣＨ２－ＣＨＣｌ－で表される基を有する全ての重合体を指す。本発明の成分（Ａ）として用いる塩化ビニル系樹脂としては、例えば、塩化ビニルの単独重合体；塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニルと塩化ビニルと共重合可能な他のモノマーとの共重合体；および、後塩素化ビニル共重合体等の塩化ビニル単独重合体や塩化ビニル系共重合体を改質したものなどをあげることができる。上記成分（Ａ）としては、さらには塩素化ポリエチレン等の構造上塩化ビニル樹脂と類似の塩素化ポリオレフィンを用いてもよい。上記成分（Ａ）としては、これらの中で、成形加工性、抗菌性・抗ウイルス性の観点から、塩化ビニルの単独重合体が好ましい。 <(A) Vinyl chloride resin>
The vinyl chloride resin used as component (A) of the present invention refers to all polymers having a group represented by —CH 2 —CHCl—. Examples of the vinyl chloride resin used as the component (A) of the present invention include vinyl chloride homopolymers; vinyl chloride / vinyl acetate copolymers, vinyl chloride / (meth) acrylic acid copolymers, vinyl chloride / ( (Meth) methyl acrylate copolymer, vinyl chloride / (meth) ethyl acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride・ Styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride terpolymer, vinyl chloride / styrene / acrylonitrile terpolymer, chloride Vinyl / butadiene copolymer, vinyl chloride / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride -Copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride, such as vinylidene chloride / vinyl acetate terpolymers, vinyl chloride / acrylonitrile copolymers, vinyl chloride / various vinyl ether copolymers; and Examples thereof include vinyl chloride homopolymers such as post-chlorinated vinyl copolymers and modified vinyl chloride copolymers. As the component (A), a chlorinated polyolefin similar in structure to a vinyl chloride resin such as chlorinated polyethylene may be used. Among these, the above component (A) is preferably a vinyl chloride homopolymer from the viewpoints of moldability, antibacterial properties and antiviral properties.
　上記成分（Ａ）のＪＩＳ　Ｋ６７２０－２：１９９９の付属書４．１比粘度に準拠して測定した比粘度から同規定に準拠して算出した平均重合度は、機械的強度を良好にする観点から、好ましくは８００以上、より好ましくは１０００以上であってよい。成形加工性を良好にする観点から、好ましくは３０００以下、より好ましくは２６００以下であってよい。機械的強度と成形加工性とのバランスの観点から、好ましくは８００～３０００、より好ましくは１０００～２６００であってよい。 The average degree of polymerization calculated based on the specific viscosity from the specific viscosity measured in accordance with Appendix 4.1 specific viscosity of JIS K6720-2: 1999 of the above component (A) is a viewpoint of improving the mechanical strength. Therefore, it may be preferably 800 or more, more preferably 1000 or more. From the viewpoint of improving the moldability, it may be preferably 3000 or less, more preferably 2600 or less. From the viewpoint of the balance between mechanical strength and molding processability, it is preferably 800 to 3000, more preferably 1000 to 2600.
　上記成分（Ａ）としては、これらの塩化ビニル系樹脂の１種または２種以上の混合物を用いることができる。 As the component (A), one or a mixture of two or more of these vinyl chloride resins can be used.
＜（Ｂ）金属系抗菌剤＞
　上記成分（Ｂ）は、金属系抗菌剤である。本発明では、上記成分（Ｂ）として銅錫系合金粒子を用いる。 <(B) Metal-based antibacterial agent>
The component (B) is a metal antibacterial agent. In the present invention, copper-tin alloy particles are used as the component (B).
　上記銅錫系合金粒子における銅と錫の含有割合は、十分な量の銅イオンを発生させ、良好な抗菌性、抗ウイルス性を発現させる観点から、原子比で、銅と錫の和を１００ａｔ％として、銅 ５０～９９ａｔ％、錫 ５０～１ａｔ％であり、好ましくは、銅６０～９５ａｔ％、錫４０～５ａｔ％である。 The content ratio of copper and tin in the copper-tin alloy particles is such that a sufficient amount of copper ions is generated and good antibacterial and antiviral properties are expressed. The copper percentage is 50 to 99 at% and the tin percentage is 50 to 1 at%, preferably 60 to 95 at% for copper and 40 to 5 at% for tin.
　本発明において、上記銅錫系合金粒子は、本発明の効果を損なわないという条件の下、銅錫以外の他の元素を更に含んでいてもよい。これにより、経済性、各種液体との親和性、基材樹脂との親和性、および最終成形品の色調などが調整される。上記他の元素としては、例えば、アルミニウム、ゲルマニウム、ベリリウム、ニッケル、およびシリコンなどをあげることができる。また耐食性を損なわない範囲で亜鉛、銀、およびニッケルなどの抗菌性を有する他の金属が含有されていてもよい。更に、上記銅錫系合金粒子の一部が酸化していることなどに起因して、酸素原子が含まれていてもよい。上記銅錫系合金粒子は、酸素、炭素、窒素、および塩素などの非金属元素を含むものであってもよい。上記銅錫系合金粒子中の銅含有量と錫含有量の和は、原子比で、全元素の総和を１００ａｔ％として、通常５０ａｔ％以上、好ましくは９０ａｔ％以上、より好ましくは９５ａｔ％以上、更に好ましくは９９ａｔ％以上、１００ａｔ％以下であってよい。抗菌・抗ウイルス性と耐食性を最大限に付与するという観点からは、上記銅錫合金系粒子が実質的に銅と錫のみからなること、即ち、上記銅錫系合金粒子中の銅含有量と錫含有量の和は、全元素の総和を１００ａｔ％として、１００ａｔ％であることが最も好ましい。 In the present invention, the copper tin-based alloy particles may further contain an element other than copper tin under the condition that the effects of the present invention are not impaired. Thereby, economic efficiency, affinity with various liquids, affinity with the base resin, and color tone of the final molded product are adjusted. Examples of the other elements include aluminum, germanium, beryllium, nickel, and silicon. In addition, other metals having antibacterial properties such as zinc, silver, and nickel may be contained as long as the corrosion resistance is not impaired. Furthermore, oxygen atoms may be contained due to the fact that some of the copper-tin alloy particles are oxidized. The copper-tin alloy particles may contain non-metallic elements such as oxygen, carbon, nitrogen, and chlorine. The sum of the copper content and the tin content in the copper-tin alloy particles is an atomic ratio, and the total sum of all elements is 100 at%, usually 50 at% or more, preferably 90 at% or more, more preferably 95 at% or more, More preferably, it may be 99 at% or more and 100 at% or less. From the viewpoint of providing antibacterial / antiviral properties and corrosion resistance to the maximum, the copper-tin alloy-based particles consist essentially of copper and tin, that is, the copper content in the copper-tin-based alloy particles The sum of the tin contents is most preferably 100 at%, where the sum of all elements is 100 at%.
　上記成分（Ｂ）は、銅錫系合金粒子であって、その粒子径分布は、粒子径４５μｍ以下の微細粒子の含有量が、通常８０体積％以上であってよい。上記粒度分布は、ＪＩＳ Ｒ１６２９－１９９７に準拠し、レーザ回折・散乱法により測定した。上記成分（Ｂ）の粒子径分布が、粒子径４５μｍ以下の微細粒子の含有量が通常８０体積％以上であることにより、好ましくは９０体積％以上であることにより、良好な抗菌性、および抗ウイルス性が発現し易くなる。また、粒子径４５μｍ以下の微細粒子の含有量が通常９９体積％以下、好ましくは９５体積％以下であることにより、製造コストをおさえることが容易になる。微細粒子の割合を多くして銅錫系合金粒子の表面積を最大限に広くすることにより、抗菌性・抗ウイルス性を効率よく発揮することができる。 The component (B) is copper-tin alloy particles, and the particle size distribution may be such that the content of fine particles having a particle size of 45 μm or less is usually 80% by volume or more. The particle size distribution was measured by a laser diffraction / scattering method in accordance with JIS R1629-1997. When the particle size distribution of the component (B) is such that the content of fine particles having a particle size of 45 μm or less is usually 80% by volume or more, preferably 90% by volume or more, good antibacterial properties, Viral properties are easily expressed. Further, since the content of fine particles having a particle diameter of 45 μm or less is usually 99% by volume or less, preferably 95% by volume or less, the production cost can be easily reduced. By increasing the proportion of fine particles and maximizing the surface area of the copper-tin alloy particles, antibacterial and antiviral properties can be efficiently exhibited.
　上記成分（Ｂ）は、銅錫系合金粒子であって、その見かけ密度は通常０．５～３ｇ／ｃｍ３であってよい。上記見かけ密度は、ＪＩＳ Ｚ　２５０４：２０１２に従い測定した密度をいうものとする。上記成分（Ｂ）の見かけ密度は、抗菌性、および抗ウイルス性の観点から、通常３ｇ／ｃｍ３以下、好ましくは２．８ｇ／ｃｍ３以下であってよい。一方、上記成分（Ｂ）の見かけ密度は、耐変色性の観点から、通常０．５ｇ／ｃｍ３以上、好ましくは１ｇ／ｃｍ３以上であってよい。 The component (B) is copper-tin alloy particles, and the apparent density thereof may be usually 0.5 to 3 g / cm 3 . The apparent density refers to a density measured according to JIS Z 2504: 2012. The apparent density of the component (B) is usually 3 g / cm 3 or less, preferably 2.8 g / cm 3 or less, from the viewpoint of antibacterial properties and antiviral properties. On the other hand, the apparent density of the component (B) is usually 0.5 g / cm 3 or more, preferably 1 g / cm 3 or more, from the viewpoint of discoloration resistance.
　上記成分（Ｂ）の配合量は、抗菌・抗ウイルス性の観点から、上記成分（Ａ）１００質量部に対して、通常１質量部以上、好ましくは５質量部以上である。上記成分（Ｂ）の配合量は、抗菌・抗ウイルス性の観点からは、多いほど好ましい。一方、機械的強度、樹脂組成物の生産性、および成形加工性の観点から、通常１５０質量部以下、好ましくは９０質量部以下であってよい。 The compounding amount of the component (B) is usually 1 part by mass or more, preferably 5 parts by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint of antibacterial and antiviral properties. From the viewpoint of antibacterial and antiviral properties, the larger the amount of the component (B), the better. On the other hand, from the viewpoints of mechanical strength, resin composition productivity, and molding processability, it may usually be 150 parts by mass or less, preferably 90 parts by mass or less.
＜（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物＞
　上記成分（Ｃ）は、アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物である。上記成分（Ｃ）は、本発明の塩化ビニル系樹脂組成物に、その抗菌・抗ウイルス性を損なうことなく、熱安定性や加工安定性を付与する働きをする。 <(C) Alkaline earth metal or composite compound of alkali metal and zinc>
The component (C) is an alkaline earth metal or a composite compound of an alkali metal and zinc. The component (C) functions to impart thermal stability and processing stability to the vinyl chloride resin composition of the present invention without impairing its antibacterial and antiviral properties.
　上記成分（Ｃ）としては、例えば、アルカリ土類金属・亜鉛複合化合物、アルカリ金属・亜鉛複合化合物、アルカリ土類金属・アルカリ金属・亜鉛複合化合物、およびこれらの１種以上の混合物などをあげることができる。 Examples of the component (C) include alkaline earth metal / zinc composite compounds, alkali metal / zinc composite compounds, alkaline earth metal / alkali metal / zinc composite compounds, and mixtures of one or more thereof. Can do.
　上記成分（Ｃ）は、好ましくはバリウム・亜鉛複合化合物、およびカルシウム・亜鉛複合化合物からなる群から選択される少なくとも１種以上の化合物を含む。上記成分（Ｃ）は、より好ましくはバリウム・亜鉛複合化合物、およびカルシウム・亜鉛複合化合物からなる群から選択される少なくとも１種以上の化合物である。 The component (C) preferably contains at least one compound selected from the group consisting of a barium / zinc composite compound and a calcium / zinc composite compound. The component (C) is more preferably at least one compound selected from the group consisting of a barium / zinc composite compound and a calcium / zinc composite compound.
　上記バリウム・亜鉛複合化合物としては、例えば、バリウム、亜鉛、および有機酸を含む有機酸バリウム・亜鉛複合塩などをあげることができる。 Examples of the barium / zinc composite compound include barium, zinc, and an organic acid barium / zinc composite salt containing an organic acid.
　上記カルシウム・亜鉛複合化合物としては、例えば、カルシウム、亜鉛、および有機酸を含む有機酸カルシウム・亜鉛複合塩などをあげることができる。 Examples of the calcium / zinc composite compound include calcium, zinc, and an organic acid calcium / zinc composite salt containing an organic acid.
　上記有機酸としては、例えば、ステアリン酸、パルミチン酸、ラウリン酸、リノール酸、リシノール酸、オクチル酸、２－エチルヘキシル酸、およびオレイン酸などの脂肪酸；亜リン酸エステル類；および、安息香酸などの芳香族系カルボン酸などをあげることができる。上記有機酸としては、これらの１種以上を用いることができる。 Examples of the organic acid include fatty acids such as stearic acid, palmitic acid, lauric acid, linoleic acid, ricinoleic acid, octylic acid, 2-ethylhexylic acid, and oleic acid; phosphites; and benzoic acid Aromatic carboxylic acids and the like can be mentioned. One or more of these can be used as the organic acid.
　本発明による塩化ビニル系樹脂組成物を、食品と直接接触する用途または直接接触する可能性のある用途に用いる場合には、上記成分（Ｃ）としては、塩ビ食品衛生協議会の「塩化ビニル製食品容器包装等に関するポジティブリスト : ＰＬ規格」に記載・登録されているものを、該リストに記載されている配合量制限の範囲内の量で用いることが好ましい。上記成分（Ｃ）としては、これらの１種以上を用いることができる。 When the vinyl chloride resin composition according to the present invention is used for an application that may be in direct contact with food or an application that may be in direct contact with the food, the component (C) may be made of “made of vinyl chloride” It is preferable to use what is described / registered in “Positive list に 関 す る: PL standard regarding food containers and packaging” in an amount within the range of the blending amount restriction described in the list. One or more of these can be used as the component (C).
　理論に拘束される意図はないが、従来、抗菌性の良好な塩化ビニル系樹脂組成物が得られなかったのは、熱安定剤と抗菌剤とが拮抗作用を起こしていたためと推測される。上記成分（Ｃ）と上記成分（Ｂ）とが、拮抗作用を起こすことなく、更には抗菌性だけでなく、抗ウイルス性も良好な塩化ビニル系樹脂組成物が得られることは、特異的なことであり、驚くべきことである。安定剤は塩化ビニル樹脂の熱安定性を保持する上では必須であり、塩化ビニル樹脂が熱分解することによる塩酸ガス等の腐食性ガス発生を抑制する働きをするが、安定剤が含まれない場合は、塩化ビニル樹脂の熱分解に伴って発生する塩酸ガス等の腐食性ガスが、抗菌剤表面の腐食を招き、抗菌性を損なう課題があった。本発明のように、抗菌性だけでなく抗ウイルス効果をも損なわず、かつ塩化ビニル樹脂の熱分解を抑制する、という機能が両立できる手段が見出されたことは画期的なことである。 Although it is not intended to be bound by theory, the reason why a vinyl chloride resin composition having a good antibacterial property has not been obtained in the past is presumed to be because the heat stabilizer and the antibacterial agent caused an antagonistic action. It is specific that the component (C) and the component (B) are not antagonizing, and that a vinyl chloride resin composition having not only antibacterial properties but also good antiviral properties can be obtained. That is amazing. Stabilizers are essential for maintaining the thermal stability of vinyl chloride resin, and act to suppress the generation of corrosive gases such as hydrochloric acid gas due to thermal decomposition of vinyl chloride resin, but do not contain stabilizers. In such a case, a corrosive gas such as hydrochloric acid gas generated due to the thermal decomposition of the vinyl chloride resin causes corrosion of the surface of the antibacterial agent, thereby impairing the antibacterial property. As in the present invention, it is epoch-making that a means capable of achieving both the functions of not only preventing antibacterial properties but also preventing the antiviral effect and suppressing the thermal decomposition of vinyl chloride resin has been found. .
　上記成分（Ｃ）の配合量は、上記成分（Ａ）１００質量部に対して、熱安定性の観点から、通常０．１質量部以上、好ましくは０．３質量部以上である。一方、耐ブルーム性、成形加工性、抗菌性、および抗ウイルス性の観点から、通常１０質量部以下、好ましくは５質量部以下であってよい。 The compounding amount of the component (C) is usually 0.1 parts by mass or more, preferably 0.3 parts by mass or more with respect to 100 parts by mass of the component (A), from the viewpoint of thermal stability. On the other hand, from the viewpoint of bloom resistance, molding processability, antibacterial properties, and antiviral properties, it may be usually 10 parts by mass or less, preferably 5 parts by mass or less.
＜（Ｄ）可塑剤＞
　本発明による塩化ビニル系樹脂組成物は、更に、１種以上の可塑剤を含むことが好ましい。（Ｄ）可塑剤は本発明の塩化ビニル系樹脂組成物の柔軟性を調整する働きをする。上記成分（Ｄ）は、目的に応じて適宜選択して使用することができる。 <(D) Plasticizer>
The vinyl chloride resin composition according to the present invention preferably further contains one or more plasticizers. (D) The plasticizer functions to adjust the flexibility of the vinyl chloride resin composition of the present invention. The component (D) can be appropriately selected and used depending on the purpose.
　上記成分（Ｄ）としては、例えば、フタル酸エステル系可塑剤、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤、アジピン酸エステル系可塑剤、イタコン酸エステル系可塑剤、クエン酸エステル系可塑剤、シクロヘキサンジカルボキシレート系可塑剤、およびエポキシ系可塑剤などをあげることができる。 Examples of the component (D) include phthalate ester plasticizers, trimellitic ester plasticizers, pyromellitic ester plasticizers, adipate ester plasticizers, itaconic ester plasticizers, and citrate esters. Examples thereof include a plasticizer, a cyclohexanedicarboxylate plasticizer, and an epoxy plasticizer.
　上記成分（Ｄ）としては、例えば、多価アルコールとして、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－へキサンジオール、１，６－へキサンジオール、ネオペンチルグリコールなどを用い、多価カルボン酸として、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、トリメリット酸、ピメリン酸、スベリン酸、マレイン酸、アゼライン酸、セバチン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸などを用い、必要により一価アルコール、モノカルボン酸をストッパーに使用したポリエステル系可塑剤をあげることができる。 Examples of the component (D) include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc., and polyvalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, trimellitic acid, Examples include polyester plasticizers that use pimelic acid, suberic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary, monohydric alcohol or monocarboxylic acid as a stopper. be able to.
　上記フタル酸エステル系可塑剤としては、例えば、フタル酸ジブチル、フタル酸ブチルヘキシル、フタル酸ジヘプチル、フタル酸ジ（２－エチルヘキシル）、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジウンデシル、フタル酸ジトリデシル、フタル酸ジラウリル、フタル酸ジシクロヘキシル、およびテレフタル酸ジオクチルなどをあげることができる。 Examples of the phthalate ester plasticizer include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, And dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.
　上記トリメリット酸エステル系可塑剤としては、例えば、トリ（２－エチルヘキシル）トリメリテート、トリ（ｎ－オクチル）トリメリテート、およびトリ（イソノニル）トリメリテートなどをあげることができる。 Examples of the trimellitic acid ester plasticizer include tri (2-ethylhexyl) trimellitate, tri (n-octyl) trimellitate, and tri (isononyl) trimellitate.
　上記アジピン酸エステル系可塑剤としては、例えば、アジピン酸ビス（２－エチルヘキシル）、アジピン酸ジオクチル、アジピン酸ジイソノニル、およびアジピン酸ジイソデシルなどをあげることができる。 Examples of the adipate ester plasticizer include bis (2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.
　上記エポキシ系可塑剤としては、エポキシ化大豆油、エポキシ化アマニ油、エポキシ化脂肪酸オクチルエステル、およびエポキシ化脂肪酸アルキルエステルなどをあげることができる。 Examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.
　上記成分（Ｄ）としては、抗菌性、抗ウイルス性、および成形加工性の観点から、フタル酸エステル系可塑剤、およびエポキシ系可塑剤が好ましい。 The component (D) is preferably a phthalate ester plasticizer and an epoxy plasticizer from the viewpoint of antibacterial properties, antiviral properties, and moldability.
　上記成分（Ｄ）としては、熱安定性、抗菌・抗ウイルス性、色調安定性、および成形加工性の観点から、上記フタル酸エステル系可塑剤、および上記エポキシ系可塑剤からなる群から選択される少なくとも１種以上の可塑剤を含むものが好ましく、上記フタル酸エステル系可塑剤と上記エポキシ系可塑剤を含むものがより好ましく、上記成分（Ｄ）の総量を１００質量％として、上記フタル酸エステル系可塑剤９０～９９質量％と上記エポキシ系可塑剤を１０～１質量％とを含むものが更に好ましい。 The component (D) is selected from the group consisting of the phthalate ester plasticizer and the epoxy plasticizer from the viewpoints of thermal stability, antibacterial / antiviral properties, color stability, and moldability. Preferably containing at least one kind of plasticizer, more preferably containing the above phthalate ester plasticizer and the above epoxy plasticizer, and the total amount of the above component (D) as 100% by mass. It is more preferable to contain 90 to 99% by mass of an ester plasticizer and 10 to 1% by mass of the epoxy plasticizer.
　上記成分（Ｄ）としては、これらの１種または２種以上を組みあわせて用いることができる。 ¡As the component (D), one or more of these can be used in combination.
　上記成分（Ｄ）の配合量は、上記成分（Ａ）１００質量部に対して、成形加工性の観点から、通常１質量部以上、好ましくは３質量部以上であってよい。一方、樹脂組成物の生産性、および機械的強度の観点から通常１２０質量部以下、好ましくは１００質量部以下であってよい。 The compounding amount of the component (D) is usually 1 part by mass or more, preferably 3 parts by mass or more, from the viewpoint of moldability with respect to 100 parts by mass of the component (A). On the other hand, from the viewpoint of productivity of the resin composition and mechanical strength, it may be usually 120 parts by mass or less, preferably 100 parts by mass or less.
　本発明の塩化ビニル系樹脂組成物には、本発明の目的に反しない限度において、所望により、塩化ビニル系樹脂およびその樹脂組成物に通常用いられる各種添加剤（例えば、他の熱安定剤類、滑剤、顔料、紫外線吸収剤、離型剤、帯電防止剤、金属不活性剤、界面活性剤、および発泡剤など。）や各種充填材（例えば、炭酸カルシウム、クレー、タルクなど。）を更に含ませることができる。 In the vinyl chloride resin composition of the present invention, various additives usually used in the vinyl chloride resin and its resin composition (for example, other heat stabilizers, for example), as long as they do not contradict the purpose of the present invention. , Lubricants, pigments, UV absorbers, mold release agents, antistatic agents, metal deactivators, surfactants, foaming agents, etc.) and various fillers (for example, calcium carbonate, clay, talc, etc.). Can be included.
＜塩化ビニル系樹脂組成物の製造方法＞
　本発明による塩化ビニル系樹脂組成物を製造する方法は、特に制限されず、任意の方法で製造することができる。本発明による塩化ビニル系樹脂組成物は、上記成分（Ａ）～（Ｃ）、および所望に応じて用いる任意成分を、任意の溶融混練機（例えば、単軸押出機、二軸押出機、ロール、ミキサー、および各種のニーダーなど）を使用して溶融混練することにより得ることができる。好ましくは加圧ニーダーを用い、樹脂温度１５０～１８０℃で溶融混練することにより得ることができる。 <Method for producing vinyl chloride resin composition>
The method for producing the vinyl chloride resin composition according to the present invention is not particularly limited, and can be produced by any method. The vinyl chloride resin composition according to the present invention comprises the above-described components (A) to (C) and optional components used as desired in any melt kneader (eg, single screw extruder, twin screw extruder, roll). , A mixer, and various kneaders). Preferably, it can be obtained by melt kneading at a resin temperature of 150 to 180 ° C. using a pressure kneader.
　本発明による塩化ビニル系樹脂組成物を、所謂マスターバッチ法により生産することが好ましい。上記マスターバッチ法としては、例えば、上記成分（Ａ）１００質量部に対して、上記成分（Ｂ）３０～３００質量部を含む樹脂組成物（以下、「ＭＢ」と略す。）を任意の溶融混練機を使用して溶融混練して得た後、上記ＭＢと上記成分（Ａ）～（Ｃ）、および所望に応じて用いる任意成分とを任意の溶融混練機を使用して溶融混練することにより得る方法をあげることができる。このような方法を採用することにより、上記成分（Ｂ）の組成物中における分散性／均一性を向上させ、ひいては抗菌性、および抗ウイルス性を良好にすることができる。 The vinyl chloride resin composition according to the present invention is preferably produced by a so-called master batch method. As the master batch method, for example, a resin composition (hereinafter abbreviated as “MB”) containing 30 to 300 parts by mass of the component (B) is arbitrarily melted with respect to 100 parts by mass of the component (A). After being obtained by melt-kneading using a kneader, the MB, the components (A) to (C), and optional components used as desired are melt-kneaded using any melt-kneader. Can be mentioned. By adopting such a method, the dispersibility / uniformity of the component (B) in the composition can be improved, and as a result, antibacterial properties and antiviral properties can be improved.
　本発明による塩化ビニル系樹脂組成物の下記実施例の試験（５）のようにして測定したＳｔａｐｈｙｌｏｃｏｃｃｕｓ　ａｕｒｅｕｓ（黄色ブドウ球菌）に対する抗菌性は、対数減少値が好ましくは２以上、より好ましくは２．５以上、更に好ましくは３以上、より更に好ましくは３．５以上、最も好ましくは４以上であってよい。 The antibacterial activity of Staphylococcus aureus (Staphylococcus aureus) measured as described in the test (5) of the following example of the vinyl chloride resin composition according to the present invention is preferably a log reduction value of 2 or more, more preferably 2. It may be 5 or more, more preferably 3 or more, still more preferably 3.5 or more, and most preferably 4 or more.
　本発明の塩化ビニル系樹脂組成物の下記実施例の試験（６－１）のようにして測定した大腸菌ファージ（Ｃｏｌｉｐｈａｇｅ）に対する抗ウイルス性は、対数減少値が好ましくは２以上、より好ましくは２．５以上、更に好ましくは３以上、より更に好ましくは３．５以上、最も好ましくは４以上であってよい。 The antiviral property against E. coli phage (Coliphage) measured by the test (6-1) of the following example of the vinyl chloride resin composition of the present invention has a log reduction value of preferably 2 or more, more preferably 2 .5 or more, more preferably 3 or more, even more preferably 3.5 or more, and most preferably 4 or more.
　本発明の塩化ビニル系樹脂組成物の下記実施例の試験（６－２）のようにして測定したネコカリシウイルス（Ｆｅｌｉｎｅ　ｃａｌｉｃｉｖｉｒｕｓ　Ｆ－９）に対する抗ウイルス性は、対数減少値が好ましくは２以上、より好ましくは２．５以上、更に好ましくは３以上、より更に好ましくは３．５以上、最も好ましくは４以上であってよい。 The antiviral property against feline calicivirus (Feline calicivirus F-9) measured by the test (6-2) of the following example of the vinyl chloride resin composition of the present invention has a logarithmic decrease value of preferably 2 or more. More preferably, it may be 2.5 or more, more preferably 3 or more, still more preferably 3.5 or more, and most preferably 4 or more.
　本発明の抗菌性塩化ビニル系樹脂組成物による成形体は、各種成形法に適用することにより、所望の形状とすることができる。上記成形法としては、公知の成形法、例えば、押出成形法、射出成形法、ブロー成形法、カレンダーロール圧延製膜法、および押出製膜法などをあげることができる。成形条件は、目的とする物品に応じて公知の条件の中から適宜選択することができる。 The molded body of the antibacterial vinyl chloride resin composition of the present invention can be formed into a desired shape by applying to various molding methods. Examples of the molding method include known molding methods such as an extrusion molding method, an injection molding method, a blow molding method, a calender roll rolling film forming method, and an extrusion film forming method. The molding conditions can be appropriately selected from known conditions according to the target article.
　以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example explains the present invention, the present invention is not limited to these.
＜使用した原材料＞
（Ａ）塩化ビニル系樹脂：
　（Ａ－１）ポリ塩化ビニル（新第一塩ビ株式会社製、「ＺＥＳＴ　１０００Ｚ（商品名）」、平均重合度１０００）を用いた。 <Raw materials used>
(A) Vinyl chloride resin:
(A-1) Polyvinyl chloride (manufactured by Shin Daiichi PVC Co., Ltd., “ZEST 1000Z (trade name)”, average degree of polymerization 1000) was used.
（Ｂ）銅錫系合金粒子：
　（Ｂ－１）銅錫合金（銅含有量は原子比で７９．１ａｔ％、錫含有量は原子比で２０．９ａｔ％、粒子径４５μｍ以下の微細粒子の含有量は１００体積％、および見かけ密度２．７５ｇ／ｃｍ３）を用いた。 (B) Copper-tin alloy particles:
(B-1) Copper-tin alloy (copper content is 79.1 at% in atomic ratio, tin content is 20.9 at% in atomic ratio, content of fine particles having a particle diameter of 45 μm or less is 100 vol%, and apparent A density of 2.75 g / cm 3 ) was used.
（Ｂ’）参考金属系抗菌剤：
　（Ｂ’－１）銅（銅含有量は原子比で１００ａｔ％、粒子径４５μｍ以下の微細粒子の含有量は４５体積％、および見かけ密度３．０ｇ／ｃｍ３）を用いた。
　（Ｂ’－２）錫（錫含有量は原子比で１００ａｔ％、粒子径４５μｍ以下の微細粒子の含有量は７０体積％、および見かけ密度２．１ｇ／ｃｍ３）を用いた。 (B ′) Reference metal antibacterial agent:
(B′-1) Copper (copper content was 100 atomic% in atomic ratio, content of fine particles having a particle diameter of 45 μm or less was 45 volume%, and apparent density was 3.0 g / cm 3 ).
(B′-2) Tin (the tin content was 100 atomic% in atomic ratio, the content of fine particles having a particle diameter of 45 μm or less was 70 volume%, and the apparent density was 2.1 g / cm 3 ) was used.
（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物：
　（Ｃ－１）バリウム・亜鉛複合化合物（株式会社ＡＤＥＫＡ製、「ＡＣ２９０（商品名）」）を用いた。
　（Ｃ－２）上記「塩化ビニル製食品容器包装等に関するポジティブリスト : ＰＬ規格」に記載・登録されているカルシウム・亜鉛複合化合物（株式会社ＡＤＥＫＡ製、「ＳＰ－２０１５（商品名）」）を用いた。 (C) Alkaline earth metal or composite compound of alkali metal and zinc:
(C-1) A barium / zinc composite compound (manufactured by ADEKA Corporation, “AC290 (trade name)”) was used.
(C-2) Calcium / zinc complex compound (“SP-2015 (trade name)” manufactured by ADEKA Co., Ltd.) described and registered in the above “Positive list of food containers and packaging made of vinyl chloride: PL standard” Using.
（Ｃ’）参考化合物：
　（Ｃ’－１）ジメチル錫メルカプト（勝田化工株式会社製、「ＴＭ－１８１ＦＳＪ（商品名）」）を用いた。
　（Ｃ’－２）ステアリン酸鉛（ＮＩケミテック株式会社製、「ＮＳＰ－Ｒ（商品名）」）を用いた。 (C ′) Reference compound:
(C′-1) Dimethyltin mercapto (“TM-181FSJ (trade name)” manufactured by Katsuta Chemical Co., Ltd.) was used.
(C′-2) Lead stearate (“NSP-R (trade name)” manufactured by NI Chemtech Co., Ltd.) was used.
（Ｄ）可塑剤
　（Ｄ－１）フタル酸ジイソノニル（株式会社ジェイプラス製、「ＤＩＮＰ（商品名）」を用いた。
　（Ｄ－２）エポキシ化大豆油（株式会社ＡＤＥＫＡ製、「Ｏ-１３０Ｓ（商品名）」）を用いた。 (D) Plasticizer (D-1) Diisononyl phthalate (“DINP (trade name)” manufactured by J-Plus Co., Ltd.) was used.
(D-2) Epoxidized soybean oil (“O-130S (trade name)” manufactured by ADEKA Corporation) was used.
＜例１～１３、例１Ｓ～７Ｓ＞
　表１～３の何れか１に示した配合比（質量部）の配合物を、関西ロール株式会社の２本ロール混練機を使用し、樹脂温度１８０℃で溶融混練し、分出しシートとして樹脂組成物を得た。得られた各樹脂組成物について、下記の試験（１）～（６）を行った。試験結果は下記の表１～３の何れか１に示されるとおりであった。 <Examples 1 to 13, Examples 1S to 7S>
A blend having a blending ratio (part by mass) shown in any one of Tables 1 to 3 is melt-kneaded at a resin temperature of 180 ° C. using a two-roll kneader manufactured by Kansai Roll Co., Ltd. A composition was obtained. Each of the obtained resin compositions was subjected to the following tests (1) to (6). The test results were as shown in any one of Tables 1 to 3 below.
（１）硬さ：
　ＪＩＳ　Ｋ７２１５：１９８６　に準拠してショアＡの硬さ（１５秒値）を測定した。サンプルには、上記で得た分出しシートを熱プレスして得た６ｍｍ厚のプレスシートを用いた。 (1) Hardness:
The hardness (value for 15 seconds) of Shore A was measured according to JIS K7215: 1986. The sample used was a 6 mm thick press sheet obtained by hot pressing the dispensing sheet obtained above.
（２）引張強度、引張伸び：
　ＪＩＳ　Ｋ６７２３：１９９５に準拠し、上記で得た分出しシートを熱プレスして得た１．０ｍｍ厚みのプレスシートをダンベル２号形で打ち抜き、２５ｍｍの標線を記入して試験片とした。試験温度２３℃、相対湿度５０％の恒温室にて試料調整をした後、引張試験機を用いて、引張速度２００ｍｍ／分で測定した。 (2) Tensile strength, tensile elongation:
In accordance with JIS K6723: 1995, a 1.0 mm-thick press sheet obtained by hot pressing the dispensing sheet obtained above was punched out with a dumbbell No. 2 shape, and a 25 mm mark was entered to give a test piece. The sample was adjusted in a constant temperature room at a test temperature of 23 ° C. and a relative humidity of 50%, and then measured using a tensile tester at a tensile rate of 200 mm / min.
（３）耐熱老化特性：
　引張試験を行う前に、試験片を所定の時間（１２０時間、２４０時間、および５００時間の何れか１）、１００℃のギアオーブン内で処理したこと以外は、上記試験（２）と同様に引張強度残率、および引張伸び残率を測定した。上記試験（２）の値を１００％とする残率「試験（３）の値／試験（２）の値×１００（％）」として表記した。　 (3) Heat aging characteristics:
Similar to test (2) above, except that the specimen was treated in a gear oven at 100 ° C. for a predetermined time (one of 120 hours, 240 hours, and 500 hours) before performing the tensile test. Tensile strength residual ratio and tensile elongation residual ratio were measured. The residual rate with the value of the test (2) as 100% was expressed as “value of test (3) / value of test (2) × 100 (%)”.
（４）押出加工性：
　単軸押出機（Ｌ／Ｄ＝２８）とＴダイとを備える装置を使用し、ダイ出口樹脂温度１８０℃の条件で、幅２５ｍｍ、厚み１．０ｍｍのテープを押出成形した。ドローダウン性、シートの表面外観、シートの形状、およびシートの色調の目視観察結果、および押出負荷の観点から以下の基準で評価した。
　◎：全く不具合がない。
　○：テープ表面に僅かな荒れ、微小な溶融不良物を認めるが、その他は特に問題はない。
　△：テープ表面に荒れを認め、また視認できる程度の溶融不良が存在するが、使用上は特に問題がない。
　×：テープ表面に荒れ、溶融不良を多数認める他、シートの形状、加工時の負荷、変色が大きく、ブルーム、ブリード等外観の悪化が発生する等の不具合が多く使用できない。　 (4) Extrudability:
A tape having a width of 25 mm and a thickness of 1.0 mm was extrusion-molded using a single-screw extruder (L / D = 28) and a device having a T die under the conditions of a die outlet resin temperature of 180 ° C. From the viewpoints of drawdown property, sheet surface appearance, sheet shape and sheet color tone, and extrusion load, the following criteria were used for evaluation.
A: There is no defect at all.
◯: Slight roughness on the surface of the tape and minute melt defects are recognized, but there is no particular problem in other cases.
(Triangle | delta): Although the roughening is recognized to the tape surface and there exists a melting defect of the level which can be visually recognized, there is no problem in use especially.
X: The surface of the tape is rough and many melting defects are observed. In addition, the sheet shape, processing load and discoloration are large, and there are many problems such as bloom, bleed and other appearance deterioration.
（５）抗菌性（黄色ブドウ球菌）：
　ＪＩＳ Ｚ ２８０１：２０１０に準拠し、一般社団法人京都微生物研究所において測定した。即ち、上記で得た分出しシートを熱プレスして得た１．０ｍｍ厚みのプレスシートの表面に、１／５００普通ブイヨンで調整したＳｔａｐｈｙｌｏｃｏｃｃｕｓ　ａｕｒｅｕｓ（黄色ブドウ球菌）の菌液を滴下し、フィルムで密着させて３５℃で２４時間保存し、上記シート表面上の菌液について生菌数を測定した。同様にして、下記標準サンプルについて、３５℃で２４時間保存後の生菌数を測定した。結果は、両者の値を使用して算出した対数減少値として示した。なお対数減少値が３であったとは、生菌数が標準サンプルの１／１０００であったことを意味する。 (5) Antibacterial (Staphylococcus aureus):
In accordance with JIS Z 2801: 2010, measurements were taken at the Kyoto Microbiology Research Institute. That is, a bacterial solution of Staphylococcus aureus (staphylococcus aureus) adjusted with 1/500 ordinary bouillon is dropped on the surface of a 1.0 mm thick press sheet obtained by hot pressing the dispensing sheet obtained above, and a film And kept at 35 ° C. for 24 hours, and the viable cell count was measured for the bacterial solution on the surface of the sheet. Similarly, for the following standard samples, the viable cell count after storage at 35 ° C. for 24 hours was measured. The result was shown as a logarithmic decrease value calculated using both values. The log reduction value of 3 means that the viable cell count was 1/1000 of the standard sample.
＜標準サンプル（上記成分（Ｂ）を含まない。）の準備＞
　上記（Ａ－１）１００質量部、上記（Ｃ－１）２質量部、上記（Ｄ－１）３５質量部、および上記（Ｄ－２）３質量部の配合物を、関西ロール株式会社の２本ロール混練機を使用し、樹脂温度１８０℃で５分間溶融混練して得られた樹脂組成物の分出しシートを、熱プレスして得た１．０ｍｍ厚みのプレスシートを標準サンプルとした。　 <Preparation of standard sample (not including above component (B))>
A blend of 100 parts by mass of (A-1), 2 parts by mass of (C-1), 35 parts by mass of (D-1), and 3 parts by mass of (D-2) was obtained from Kansai Roll Co., Ltd. Using a two-roll kneader and melt-kneading the resin composition at a resin temperature of 180 ° C. for 5 minutes, a 1.0 mm-thick press sheet obtained by hot pressing the dispensing sheet of the resin composition was used as a standard sample. .
（６－１）抗ウイルス性１（大腸菌ファージ）：
　ＪＩＳ Ｚ　２８０１：２０１０を参考として、一般財団法人北里環境科学センターにおいて大腸菌ファージを用いて抗ウイルス性を測定した。即ち、上記で得た分出しシートを熱プレスして得た１．０ｍｍ厚みのプレスシートから５０ｍｍ×５０ｍｍの試験片を切り出し、保湿シャーレに入れ、大腸菌ファージ（Ｃｏｌｉｐｈａｇｅ）０．２ｍＬを試験片上に添加し、４０ｍｍ×４０ｍｍのフィルムでウイルス液をカバーした。これを２５℃で２４時間作用（静置）させた後、ウイルス液を試験片から誘出させて感染価を測定した。同様にして、上記標準サンプルについて、２５℃で２４時間作用後の感染価を測定した。結果は、両者の値を使用して算出した対数減少値として示した。なお対数減少値が３であったとは、感染価が標準サンプルの１／１０００であったことを意味する。　 (6-1) Antiviral 1 (E. coli phage):
With reference to JIS Z 2801: 2010, antiviral properties were measured using Escherichia coli phages at the Kitasato Environmental Science Center. That is, a 50 mm × 50 mm test piece was cut out from a 1.0 mm-thick press sheet obtained by hot pressing the dispensing sheet obtained above, placed in a moisturizing petri dish, and 0.2 mL of coliphage was put on the test piece. The virus solution was covered with a 40 mm × 40 mm film. This was allowed to act at 25 ° C. for 24 hours (still), and then the virus solution was drawn from the test piece and the infectivity titer was measured. Similarly, the infectivity titer after acting for 24 hours at 25 ° C. was measured for the standard sample. The result was shown as a logarithmic decrease value calculated using both values. The log reduction value of 3 means that the infectious titer was 1/1000 of the standard sample. 　
（６－２）抗ウイルス性２（ネコカリシウイルス）：
　例１と例５を選定し、更に、ネコカリシウイルス（ノロウイルスの代替ウイルス）を用いた抗ウイルス性試験を行った。ＪＩＳ Ｚ　２８０１：２０１０を参考として、一般財団法人北里環境科学センターにおいて、ネコカリシウイルスを用いて抗ウイルス性を測定した。上記で得た分出しシートを熱プレスして得た１．０ｍｍ厚みのプレスシートから５０ｍｍ×５０ｍｍの試験片を切り出し、保湿シャーレに入れ、ネコカリシウイルス（Ｆｅｌｉｎｅ　ｃａｌｉｃｉｖｉｒｕｓ　Ｆ－９）０．２ｍＬを試験片上に添加し、４０ｍｍ×４０ｍｍのフィルムでウイルス液をカバーした。これを２５℃で２４時間作用（静置）させた後、ウイルス液を試験片から誘出させて感染価を測定した。同様にして、上記標準サンプルについて、２５℃で２４時間作用後の感染価を測定した。結果は、両者の値を使用して算出した対数減少値として示した。　 (6-2) Antiviral 2 (feline calicivirus):
Examples 1 and 5 were selected, and an antiviral test using feline calicivirus (a substitute virus for Norovirus) was further conducted. With reference to JIS Z 2801: 2010, the antiviral property was measured using feline calicivirus at Kitasato Environmental Science Center. A 50 mm × 50 mm test piece was cut out from a 1.0 mm-thick press sheet obtained by hot pressing the dispensing sheet obtained above, placed in a moisturizing petri dish, and 0.2 mL of feline calicivirus F-9 (Feline calicivirus F-9) was added. It added on the test piece and the virus liquid was covered with the film of 40 mm x 40 mm. This was allowed to act at 25 ° C. for 24 hours (still), and then the virus solution was drawn from the test piece and the infectivity titer was measured. Similarly, the infectivity titer after acting for 24 hours at 25 ° C. was measured for the standard sample. The result was shown as a logarithmic decrease value calculated using both values.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明による塩化ビニル系樹脂組成物は、優れた抗菌性・抗ウイルス性を有する。また本発明の好ましい塩化ビニル系樹脂組成物は、優れた抗菌性・抗ウイルス性を有し、機械的物性、耐熱老化特性、および押出加工性も良好である。そのため抗菌・抗ウイルス性が求められる物品用の材料として広く、好適に用いることができる。 The vinyl chloride resin composition according to the present invention has excellent antibacterial and antiviral properties. The preferred vinyl chloride resin composition of the present invention has excellent antibacterial and antiviral properties, and has good mechanical properties, heat aging characteristics, and extrusion processability. Therefore, it can be used widely and suitably as a material for articles requiring antibacterial and antiviral properties.

Claims (4)

  1. 　（Ａ）塩化ビニル系樹脂　１００質量部；
    　（Ｂ）金属系抗菌剤　１～１５０質量部；および
    　（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物 ０．１～１０質量部；
    を含む塩化ビニル系樹脂組成物であって、
    　前記（Ｂ）金属系抗菌剤が銅錫系合金粒子であり、
    　前記銅錫系合金粒子における銅と錫の含有割合が、原子比で、銅と錫の和を１００ａｔ％として、銅　５０～９９ａｔ％、および錫 ５０～１ａｔ％である、
    塩化ビニル系樹脂組成物。     (A) Vinyl chloride resin 100 parts by mass;
    (B) 1 to 150 parts by mass of a metal-based antibacterial agent; and (C) 0.1 to 10 parts by mass of an alkaline earth metal or a composite compound of an alkali metal and zinc;
    A vinyl chloride resin composition comprising
    The (B) metal antibacterial agent is copper-tin alloy particles,
    The copper-tin alloy particles in the copper-tin alloy particles have an atomic ratio of 50 to 99 at% copper and 50 to 1 at% tin, where the sum of copper and tin is 100 at%.
    Vinyl chloride resin composition.
  2. 　前記成分（Ｃ）アルカリ土類金属またはアルカリ金属と亜鉛との複合化合物が、バリウム・亜鉛複合化合物、およびカルシウム・亜鉛複合化合物からなる群から選択される少なくとも１種以上の化合物を含む、請求項１に記載の塩化ビニル系樹脂組成物。 The component (C), an alkaline earth metal or a composite compound of alkali metal and zinc, contains at least one compound selected from the group consisting of a barium / zinc composite compound and a calcium / zinc composite compound. 2. The vinyl chloride resin composition according to 1.
  3. 　更に（Ｄ）フタル酸エステル系可塑剤、およびエポキシ系可塑剤からなる群から選択される少なくとも１種以上の可塑剤を、前記成分（Ａ）１００質量部に対して、１～１２０質量部含む、請求項１または２に記載の塩化ビニル系樹脂組成物。 Further, (D) 1 to 120 parts by mass of at least one plasticizer selected from the group consisting of a phthalate ester plasticizer and an epoxy plasticizer is contained with respect to 100 parts by mass of the component (A). The vinyl chloride resin composition according to claim 1 or 2.
  4. 　請求項１～３の何れか１項に記載の塩化ビニル系樹脂組成物を含む物品。 An article comprising the vinyl chloride resin composition according to any one of claims 1 to 3.
PCT/JP2017/006082 2016-02-24 2017-02-20 Antibacterial and antiviral vinyl chloride-based resin composition WO2017145976A1 (en)

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