CN108384181B - Resin molded article and water-use site member - Google Patents
Resin molded article and water-use site member Download PDFInfo
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- CN108384181B CN108384181B CN201810029598.5A CN201810029598A CN108384181B CN 108384181 B CN108384181 B CN 108384181B CN 201810029598 A CN201810029598 A CN 201810029598A CN 108384181 B CN108384181 B CN 108384181B
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention aims to obtain a resin molded body and a water-use place member which can inhibit the proliferation of bacteria and mold for a long time. The present invention relates to a resin molded article comprising a resin, an organic antifungal/antibacterial agent supported on an inorganic compound, and an inorganic antibacterial agent, wherein the resin molded article contains the organic antifungal/antibacterial agent in an amount of 0.03 to 0.7 mass%, and contains 1.0 × 10‑43.6X 10 mass% or more‑3The inorganic antimicrobial agent is contained in an amount of not more than mass%. Thus, the proliferation of bacteria and mold can be inhibited for a long time. Further, a water-use site member comprising the resin molded article of the present invention can be obtained.
Description
Technical Field
The present invention relates to a resin molded article and a water-use site member.
Background
As a member used in a water-use place environment (hereinafter referred to as a water-use place member), a resin molded body made of a resin is known. The resin molded article is required to have antifouling property. In particular, when used in the presence of water, it is required that water and dirt are hard to adhere to.
It is known that when the resin molded body further contains an antibacterial agent and a fungicide, the propagation of bacteria such as bacteria and mold can be suppressed on the surface of the resin molded body.
For example, patent document 1 describes that a long-term antibacterial and antifungal effect can be obtained by adding a filler and an antibacterial and antifungal agent to a resin as a plate used for a drain pan used in an air conditioner.
Patent document 1: japanese laid-open patent publication No. 7-103500
Disclosure of Invention
For the resin molded body, it is required that an antibacterial agent or a fungicide is eluted from the resin molded body in order to continuously suppress the growth of bacteria and mold. Further, since the elution is required to be continued for a long period of time, a resin molded article capable of suppressing the growth of bacteria and mold for a long period of time is still required.
Accordingly, an object of the present invention is to provide a resin molded article which can suppress the growth of bacteria and mold for a long period of time.
Further, the resin molded article according to the present invention is a resin molded article comprising a thermoplastic resin, an organic antifungal/antibacterial agent supported on an inorganic compound, and an inorganic antibacterial agent, wherein the organic antifungal/antibacterial agent is 2-n-octyl-4-isothiazolin-3-one supported on an inorganic compound, and zinc pyrithione supported on an inorganic compoundThe inorganic antibacterial agent is a silver antibacterial agent in which silver ions are supported on an inorganic compound, and the resin molded body contains 0.1 to 0.38 mass% of the 2-n-octyl-4-isothiazolin-3-one and 0.06 to 0.25 mass% of the zinc pyrithione, and contains 8.6X 10-43.6X 10 mass% or more-3Less than or equal to mass% of silver ions of the silver-based antibacterial agent,
the elution rate of the zinc pyrithione from the resin molded article is 10-9g/cm2More than one hour of reaction time per hour,
the elution rate of the 2-n-octyl-4-isothiazolin-3-one from the resin molded body is 5 times or more as high as the elution rate of the zinc pyrithione,
the elution rate V of the zinc pyrithione and the 2-n-octyl-4-isothiazolin-3-one from the resin molded article is determined by placing the resin molded article having an area S and ultrapure water having a volume L in a vessel, and allowing the resin molded article to stand at 40 ℃ for a certain time T in a state where the whole resin molded article is immersed in water, according to the following equation:
dissolution velocity V (g/cm)2(ii)/h) concentration M (g/ml) of the antifungal/antibacterial agent eluted from the resin molded body x solvent amount L (ml)/(surface area S (cm) of the resin molded body2) Dissolution time T (h)).
The water-use site member of the present invention may be formed of the above-described resin molded article.
Drawings
FIG. 1 is a schematic view showing a mechanism of generation of bacteria and mold on the surface of a resin molded body.
Fig. 2 is a graph showing the results of the reference test.
Description of the symbols
1: a resin molded body; 2: fouling; 3: fungus; 4: a biofilm; 5: and (3) mold.
Detailed Description
Resin molded article
The resin molded body according to the present invention is a resin molded body containing a resin, an organic antifungal/antibacterial agent supported on an inorganic compound, and an inorganic antibacterial agent, wherein the resin molded body contains the organic antifungal/antibacterial agent in an amount of 1 to 10 mass%, and the inorganic antibacterial agent in an amount of 0.1 to 10 mass%. Thus, the proliferation of bacteria and mold can be inhibited for a long time.
Mechanism of growth of fungi and mold
The mechanism of growth of bacteria and mold (fungi) on the surface of the resin molded article is described with reference to fig. 1, and the following description is only a theory, and the present invention is not limited to the following description.
FIG. 1 is a schematic view showing a mechanism of generation of bacteria and mold on the surface of a resin molded body.
Fouling adhesion process
The fouling adhesion process is shown in fig. 1 (a). In general, when the resin molded article 1 is used in a water-use place environment, dirt components such as sebum and keratin (keratin) discharged from a human body by washing hands, faces, bathing, and the like are washed with water together with a surfactant contained in soap, bath lotion, and the like. Then, the fouling component adheres to the surface of the resin molded body 1. Most of the attached fouling components are washed out together with the running water. However, as shown in fig. 1(a), a part of the fouling component remains (residual water) on the surface of the resin molded body 1 as the sewage containing the fouling component, and the fouling 2 adheres to the surface of the resin molded body 1.
Growth process of bacteria
The growth process of the bacteria is shown in FIGS. 1(b) and (c). Fungi 3 grow on the surface of the resin molded body 1 using the dirt 2 and residual water adhering to the surface of the resin molded body 1 as a nutrient source (fig. 1 (b)). Fungi 3 present in the water-use environment may proliferate while discharging Exopolysaccharide (EPS). Such as mycrobacterium sp. The component mainly composed of the above-mentioned EPS is called a biofilm. Biofilm 4 is formed on the surface of the resin molded body 1 with the growth of fungi 3 (fig. 1 c). The biofilm 4 functions as a defense mechanism against external stimuli (e.g., running water, acid, alkali, heat, etc.) by the fungi 3. The biofilm 4 is also called slime, and increases the viscosity of the surface of the resin molded body 1. This is thought to promote adhesion of the soil 2 and growth of fungi 3 and 5.
Proliferation process of mold
The growth process of the mold 5 is shown in FIGS. 1(d) and (e). Since the mold 5 usually grows slower than the fungi 3, it is considered that the mold 5 further grows after the growth of the fungi 3 and the generation of the biofilm 4 accompanied therewith in a normal water use place environment. When mold spores adhere to the surface of the resin molded body 1 or the surface of the biofilm 4, the scale 2 adhering to the surface of the resin molded body 1 can be increased in nutrition. Some molds develop color with growth. Specific examples of the mold include Cladosporium sp.
The resin molded article of the present invention contains an organic antifungal/antibacterial agent and an inorganic antibacterial agent. Since the organic antifungal/antibacterial agent and the inorganic antibacterial agent are eluted from the surface of the resin molded body, bacteria are less likely to grow even if dirt adheres to the surface of the resin molded body. Thus, the generation of a biofilm and the generation of mold can be suppressed. The resin molded article of the present invention contains the organic antifungal/antibacterial agent in an amount of 1 to 10 mass%, preferably 0.03 to 0.7 mass%, and 0.1 to 10 mass%, preferably 1.0 × 10-43.6X 10 mass% or more-3An inorganic antimicrobial agent in an amount of not more than mass%. Accordingly, the organic antifungal antibacterial agent and the inorganic antibacterial agent can be continuously eluted from the surface of the resin molded body for a long period of time. Therefore, the proliferation of bacteria and mold can be inhibited for a long time.
Resin composition
In the present invention, the resin is contained as a main component in the resin molded body. The main component herein means that the resin molded product contains preferably 50 mass% or more, and more preferably 60 mass% or more. Thus, good moldability and appearance can be obtained.
In the present invention, any of thermosetting resins and thermoplastic resins can be used as the resin. When the resin molded article is large and high strength and heat resistance are required, a thermosetting resin is preferably used. On the other hand, when the resin molded body is small and has a complicated shape, a thermoplastic resin is preferably used.
In the present invention, as the thermosetting resin, one or more selected from urea resin, melamine resin, phenol resin, unsaturated polyester resin, epoxy resin, and silicone resin can be used.
In the present invention, as the thermoplastic resin, one or more selected from the group consisting of polypropylene resin (PP), polyethylene resin (PE), polyacetal resin (POM), polybutylene terephthalate resin (PBT), polyvinyl chloride resin (PVC), polystyrene resin (PS), acrylonitrile-butadiene-styrene copolymer resin (ABS), polyphenylene sulfide resin (PPs), polyethylene terephthalate resin (PET), polymethyl methacrylate resin (PMMA), polyamide resin (PA), polyether ether ketone resin (PEEK), polytrimethylene terephthalate resin (PTT), polycarbonate resin (PC), and polytetrafluoroethylene resin (PTFE) may be used.
In the present invention, a thermoplastic resin is preferably used as the resin. More preferably, as the resin, at least one selected from the group consisting of PP, PE, POM, PBT, PVC, ABS, PPs, PET, PMMA, PA, and PC is used. More preferably, the resin is one or more selected from the group consisting of PP, POM and PE.
Organic mildew-proof antibacterial agent
In the present invention, the organic antifungal/antibacterial agent is an organic drug having MIC (minimum inhibitory concentration) against bacteria and fungi as described in the dictionary for antifungal/antibacterial agents-code for protomer (Japan society for antifungal and antibacterial Properties, 1998, Vol.26).
In the present invention, as the organic type antifungal/antibacterial agent, for example, 1 or more selected from the group consisting of alcohol type antifungal/antibacterial agents, aldehyde type antifungal/antibacterial agents, thiazoline type antifungal/antibacterial agents, imidazole type antifungal/antibacterial agents, ester type antifungal/antibacterial agents, chlorine type antifungal/antibacterial agents, peroxide type antifungal/antibacterial agents, carboxylic acid type antifungal/antibacterial agents, carbamate type antifungal/antibacterial agents, sulfonamide type antifungal/antibacterial agents, quaternary ammonium salt type antifungal/antibacterial agents, biguanide type antifungal/antibacterial agents, pyridine type antifungal/antibacterial agents, phenol type antifungal/antibacterial agents, iodine type antifungal/antibacterial agents, and triazole type antifungal/antibacterial agents can be used.
In the present invention, as the organic antifungal/antibacterial agent, the following antifungal/antibacterial agents can be specifically used.
As the alcohol type antifungal/antibacterial agent, one or more selected from ethanol, isopropanol, propanol, trinitro (tris-hydroxymethyl-nitromethane), chlorobutanol (1, 1, 1-trichloro-2-methyl-2-propanol), and bronopol (2-bromo-2-nitropropane-1, 3-diol) can be used.
As the aldehyde-based antifungal antibacterial agent, one or more selected from glutaraldehyde, formaldehyde, BCA (α -bromocinnamaldehyde) can be used.
As the thiazoline-based antifungal/antibacterial agent, one or more selected from OIT (2-N-octyl-4-isothiazolin-3-one), MIT (2-methyl-4-isothiazolin-3-one), CMI (5-chloro-2-methyl-4-isothiazolin-3-one), BIT (1, 2-benzisothiazolone), and N-butyl BIT (N-butyl-1, 2-benzisothiazolin-3-one) can be used.
The structural formula of OIT is shown as formula 1.
The structural formula of MIT is shown in formula 2.
The structural formula of CMI is shown in formula 3.
The structural formula of BIT is shown in formula 4.
Formula 4
As the imidazole-based antifungal agent, at least one selected from TBZ (2- (4-thiazolyl) -benzimidazole) and BCM (methyl-2-benzimidazole formate) can be used.
As the ester type antifungal/antibacterial agent, dipropyl dodecanoate (glyceryl laurate) or the like can be used.
As the chlorine-based antifungal antibacterial agent, at least one of triclocarban (3, 4, 4' -trichlorocarbanilide), halocarbaban (4, 4-dichloro-3- (3-fluoromethyl) -carbanilide), 2, 4, 5, 6-tetrachloroisophthalonitrile, sodium hypochlorite, dichloroisocyanuric acid and trichloroisocyanuric acid can be used.
As the peroxide-based antifungal/antibacterial agent, one or more selected from hydrogen peroxide, chlorine dioxide and peracetic acid can be used.
As the carboxylic acid-based antifungal antibacterial agent, one or more selected from benzoic acid, ascorbic acid, octanoic acid, propionic acid, 10-undecenoic acid, potassium ascorbate, potassium propionate, calcium propionate, sodium benzoate, sodium propionate, magnesium dihydrobis (monoperoxyphthalate), and zinc undecylenate can be used.
As the carbamate-based antifungal/antibacterial agent, sodium N-methyldithiocarbamate and the like can be used.
As the sulfonamide antimycotic antibacterial agent, one or more selected from the group consisting of benfuramide and tolylfluanide can be used.
As the quaternary ammonium salt type antifungal/antibacterial agent, one or more selected from 4, 4 '- (tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide), benzalkonium chloride, benzethonium chloride, acetyl ammonium bromide, N' -hexamethylenebis (4-carbonyl-1-decylpyridinium bromide), and cetylpyridinium chloride may be used.
As the biguanide type antifungal/antibacterial agent, one or more selected from chlorhexidine gluconate, chlorhexidine hydrochloride, polybiguanide hydrochloride, and polyhexamethylene biguanide can be used.
As the pyridine-based antifungal/antibacterial agent, one or more selected from sodium pyrithione, zinc pyrithione (ZPT: zinc bis (2-thio-1-pyridineoxide)), Densil (2, 3, 5, 6-tetrachloro-4- (methylsulfonyl) pyridine), and copper pyrithione (copper bis (2-thio-1-pyridineoxide)).
The structural formula of ZPT is shown in formula 5.
As the phenol type antifungal/antibacterial agent, one or more selected from thymol (2-isopropyl-5-methylphenol), BIOSOL (3-methyl-4-isopropylphenol), OPP (o-phenol), phenol, oxybenzone butyl ester (butyl-p-hydroxybenzoate), ethylparaben (ethyl-p-hydroxybenzoate), methylparaben (methyl-p-hydroxybenzoate), propylparaben (propyl-p-hydroxybenzoate), m-cresol, o-cresol, p-cresol, sodium o-phenol, chlorophenol (2-benzyl-4-chlorophenol), and chlorocresol (2-methyl-3-chlorophenol) can be used.
As the iodine type antifungal antibacterial agent, at least one selected from AMICAL 48 iodine (diiodomethyl-p-tris-sulfone), polyvinylpyrrolidone iodine, p-chlorophenyl-3-iodopropargyl dimethoxymethane, 3-bromo-2, 3-diiodo-propenyl ethyl carbonate, and 3-iodo-2-propynyl butyl carbonate can be used.
As the triazole antifungal/antibacterial agent, tebuconazole ((+ -) - α - [2- (4-chlorophenyl) ethyl ] - α - (1, 1-dimethylethyl) -1H-1, 2, 4-triazole-1-ethanol) and the like can be used.
In the present invention, as the organic antifungal antibacterial agent, one or more selected from thiazoline-based antifungal antibacterial agents and pyridine-based antifungal antibacterial agents are preferably used. Therefore, the proliferation of bacteria and mold can be further inhibited in the water-using place environment. As the organic antifungal antibacterial agent, thiazoline antifungal antibacterial agents and pyridine antifungal antibacterial agents are more preferably used.
Two or more organic antifungal/antibacterial agents may be used in the present invention. This can further inhibit the growth of bacteria and mold.
In the present invention, as the organic antifungal antibacterial agent, at least two or more organic antifungal antibacterial agents having different elution rates can be used. Thus, the growth of bacteria and mold can be further inhibited for a long period of time.
In the present invention, when two organic antifungal/antibacterial agents are used, the resin molded body contains a first organic antifungal/antibacterial agent and a second organic antifungal/antibacterial agentOrganic antifungal and antibacterial agents. The dissolution rate of the first organic antifungal/antibacterial agent is preferably 10-9g/cm2More than h, preferably 10-8g/cm2More than h. The elution rate of the second organic antifungal antibacterial agent is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more faster than the elution rate of the first organic antifungal antibacterial agent. Accordingly, since the second organic antifungal/antibacterial agent is quickly eluted from the surface of the resin molded body, the growth of bacteria and mold can be suppressed at the start of use of the resin molded body. Further, since the first organic antifungal/antibacterial agent is eluted at a slower rate than the second organic antifungal/antibacterial agent, the growth of bacteria and mold can be suppressed for a long period of time.
In the present invention, the elution rate of the organic antifungal/antibacterial agent can be determined by the following method.
A resin molded body having an area S and ultrapure water having a volume L were placed in a vessel, and the whole resin molded body was left standing at 40 ℃ for a certain period of time (T) while being immersed in water. Thereafter, the resin molded body is taken out from the container, and the concentration (M) of the organic antifungal/antibacterial agent eluted from the resin molded body within a predetermined time (T) is calculated using an analyzer. The analytical device can be selected according to the amount and type of the organic antifungal/antibacterial agent contained in the resin molded body, and for example, GC/MS, ICP-MS, or the like can be used. At this time, the concentration (M) of the organic antifungal/antibacterial agent is determined in consideration of the influence of contamination or the like. The elution rate (V) of the organic antifungal antibacterial agent is determined from the concentration (M) of the organic antifungal antibacterial agent eluted from the resin molded body, the area (S) of the resin molded body, and the elution time (T) as shown in the following formula.
Dissolution velocity V (g/cm) of organic antifungal/antibacterial agent2(ii)/h) concentration M (g/ml) of the antifungal/antibacterial agent eluted from the resin molded body x solvent amount L (ml)/(surface area S (cm) of the resin molded body2) Dissolution time T (h)
In the present invention, the elution rate means an elution rate calculated in an unused state after the production of a resin molded article. Here, the "unused state" refers to a state after production from a resin molded body, for example, before actual use as a water-use site member.
In the present invention, the above-mentioned elution rate is preferably satisfied even after the resin molded article is used. Therefore, the growth of bacteria and mould can be inhibited for a long time.
According to the ability of the resin molded article of the present invention to inhibit the growth of fungi and mold even after long-term use, it is preferable that the resin molded article is immersed in water at 90 ℃ for 19 hours as an accelerated test, for example, so that the dissolution rate of the first organic antifungal/antibacterial agent is maintained at 10-10g/cm2More than h, and the dissolution rate of the second antifungal antibacterial agent is more than 1.5 times of the dissolution rate of the first organic antifungal antibacterial agent. Preferably, the dissolution rate of the first organic antifungal/antibacterial agent is maintained at 10-9g/cm2And/h or more, and the dissolution rate of the second organic antifungal antibacterial agent is 3 times or more, more preferably 4 times or more, the dissolution rate of the first organic antifungal antibacterial agent.
In the present invention, as long as the first organic antifungal antibacterial agent and the second organic antifungal antibacterial agent are combinations satisfying the above-mentioned elution rates, organic antifungal antibacterial agents selected from the above-mentioned examples can be used. In the present invention, as the first organic antifungal/antibacterial agent, a pyridine antifungal/antibacterial agent is preferably used. Further, as the second organic type antifungal antibacterial agent, a thiazoline type antifungal antibacterial agent is preferably used. According to a preferred embodiment of the present invention, ZPT is preferably used as the pyridine antifungal agent of the first organic antifungal agent, and OIT is preferably used as the second organic antifungal agent.
In the present invention, the organic antifungal/antibacterial agent is preferably supported on the inorganic compound. The elution rate of the organic antifungal/antibacterial agent from the resin molded body can be controlled, and the growth of bacteria and mold can be suppressed for a long period of time.
As the inorganic compound, one or more selected from zeolite, glass, talc, silica gel, silicate, mica, sepiolite, and hydrotalcite can be used. Among the above, one or more selected from zeolite, talc and glass is preferably used.
In the present invention, the organic antifungal/antibacterial agent is contained in the resin molded body in an amount of 1 mass% or more and 10 mass% or less, preferably 1 mass% or more and 3 mass% or less, and more preferably 0.03 mass% or more and 0.7 mass% or less. This can impart a mold-proof and antibacterial property to the resin molded article. Thus, a long-term antifungal activity can be obtained.
The surface of the resin molded body according to the present invention preferably contains 0.1% by mass or more of an organic antifungal/antibacterial agent, and more preferably 0.3% by mass or more.
Inorganic antibacterial agent
In the present invention, the antibacterial agent is an inorganic agent having an MIC (minimum inhibitory concentration) at least with respect to bacteria, as described in the dictionary of antiseptics and mildewcides-code of proto- (journal of Japan society for antisepsis and mildewproofing, 1998, Vol.26).
In the present invention, the inorganic antibacterial agent may be one or more selected from the group consisting of a silver antibacterial agent, a zinc antibacterial agent, and a copper antibacterial agent. Accordingly, by imparting an antibacterial effect to a wide range of bacteria, the generation of a biofilm due to the growth of bacteria can be suppressed, and thus the growth of mold adhering to the biofilm as a scaffold can also be suppressed.
In the present invention, as the inorganic antibacterial agent, one or more inorganic antibacterial agents selected from silver ions, zinc ions, and copper ions supported on an inorganic compound can be used. As the inorganic compound, one or more selected from zeolite, glass, talc, silica gel, silicate, mica, sepiolite, and hydrotalcite can be used. When a plurality of ion species are used, each ion may be supported on the same inorganic compound. Specifically, an inorganic antimicrobial agent in which silver ions and zinc ions are supported on glass can be used. When a plurality of ion species are used, each ion may be supported on a different inorganic compound. Specifically, an inorganic antibacterial agent in which silver ions are supported on glass and an inorganic antibacterial agent in which zinc ions are supported on zeolite can be used.
In the present invention, as the silver-based antibacterial agent, a composite of silver and an inorganic oxide other than silver is preferably used. Specifically, silver-zirconium phosphate (Ag) selected from silver-zirconium phosphate (Ag) may be usedxHyNazZr2(PO)4)3) (x + y + z ═ 1), silver chloride-titanium oxide (a)gCl/TiO2) Silver-calcium zinc phosphate (Ag-Ca)xZnyAlz(PO)4)6(x + y + z 10), aluminum zinc silver silicate (mixture) M2/n·Na2O·2SiO2·xH2O(M：Ag，Zn，NH4) ) of the plurality of cells.
In the present invention, zinc oxide-silver/zirconium phosphate (ZnO, Ag) is used as the zinc-based antibacterial agentxHyNazZr2(PO)4)3) And the like.
In the present invention, as the copper-based antibacterial agent, N-stearoyl-L-glutamic acid AgCu salt or the like can be used.
In the present invention, a silver-based antibacterial agent is preferably used as the inorganic antibacterial agent. It is more preferable to use a composite of silver and an inorganic oxide other than silver. Accordingly, excessive elution of silver onto the surface of the resin molded body can be suppressed, and thus the growth of bacteria can be suppressed for a long period of time.
The resin molded article according to the present invention preferably contains 0.1 mass% or more and 5 mass% or less of the inorganic antimicrobial agent, more preferably 0.1 mass% or more and 1 mass% or less, and still more preferably 1.0 × 10-43.6X 10 mass% or more-3Mass% or less. Thus, the growth of bacteria can be inhibited for a long period of time, and the formation of a biofilm can be inhibited.
The surface of the resin molded body according to the present invention preferably contains 0.01 mass% or more of the inorganic antimicrobial agent, and more preferably 0.03 mass% or more. Thereby, an antibacterial effect against a wide variety of bacteria can be imparted.
In the resin molded body of the present invention, the dissolution rate of the inorganic antibacterial agent is preferably 5 to 1, more preferably 10 to 1, of the first organic antifungal antibacterial agent. That is, the elution rate of the first antifungal/antibacterial agent is preferably 5 times or more slower, and more preferably 10 times or more slower. Accordingly, since the elution speed of the first and second organic antifungal agents is slow, the elution of the inorganic antimicrobial agent can be continued even after the elution of the first and second organic antifungal agents is rapidly progressed on the surface of the resin molded body. Thus, the growth of bacteria and mold can be inhibited for a long period of time.
In the present invention, the elution rate of the inorganic antibacterial agent can be obtained in the same manner as the elution rate of the organic antifungal antibacterial agent.
The resin molded body and the amounts of the inorganic antibacterial agent and the organic antifungal antibacterial agent contained in the surface of the resin molded body can be obtained by the following methods.
The analysis method for obtaining the amount of the antifungal agent contained in the resin molded body includes a gas chromatography-mass spectrometry (GC/MS), a High Performance Liquid Chromatography (HPLC), a liquid chromatography-mass spectrometry (LC/MS), and the like, and can be appropriately selected depending on the kind of the antifungal agent.
Examples of the method for analyzing the amount of the antifungal agent contained in the surface of the obtained resin molded product include X-ray photoelectron spectroscopy (XPS), Auger Electron Spectroscopy (AES), Electron Probe Microanalyzer (EPMA), glow discharge spectroscopy (GD-OES), glow discharge mass spectroscopy (GD-MS), total reflection infrared spectroscopy (ATR-IR), and the like, and can be appropriately selected depending on the kind of the antifungal agent.
The amount of the antifungal agent contained in the surface of the resin molded body may also be obtained using the amount of the antifungal agent contained in the resin molded body obtained by the analysis method. The rate of elution of the antifungal agent from the resin molded body can be measured, and the amount of the antifungal agent contained in the surface of the resin molded body can be determined from the elution rate and elution time of the antifungal agent.
Surface concentration N (g/cm) of the antifungal and antibacterial agent2) Dissolution rate V (g/cm) of the antifungal/antibacterial agent2H) x dissolution time T (h))
In the present invention, it is preferable to select an organic antifungal/antibacterial agent and an inorganic antibacterial agent having different mechanisms of action. For example, according to a preferred embodiment of the present invention, as the organic-based antifungal/antibacterial agent, an antifungal/antibacterial agent that inhibits the metabolism of bacteria and molds is preferably used, and as the inorganic-based antibacterial agent, an antibacterial agent that inhibits cell membranes of bacteria is preferably used. By such a combination, the inorganic antibacterial agent destroys cell membranes of bacteria and molds, and the organic antifungal antibacterial agent easily invades into cells, so that there is an advantage that growth of bacteria and molds can be more effectively suppressed.
Further, according to a preferred embodiment of the present invention, an isothiazoline-based organic antifungal agent is used as the organic antifungal agent. The organic isothiazoline antifungal/antibacterial agents invade cell membranes of bacteria and molds, and inhibit the proliferation of bacteria and molds by inhibiting ATP synthesis by inhibiting dehydrogenase in TCA cycle.
In addition, according to another aspect, in the present invention, as the organic antifungal/antibacterial agent, a pyridine organic antifungal/antibacterial agent is preferably used. Further, an organic antifungal/antibacterial agent having a pyrithione skeleton is preferable. Accordingly, the membrane transport is restricted by invading the cell membrane of bacteria and molds and inhibiting the proton pump, so that ATP synthesis and the proliferation of bacteria and molds can be suppressed.
Further, according to another aspect of the present invention, it is preferable to use a silver-based antibacterial agent as the inorganic antibacterial agent. Accordingly, the membrane proteins are denatured by the combination of silver ions and-SH groups and disulfide bonds in the membrane proteins of bacteria, and thus, the cell membranes can be disrupted.
Polysiloxane compound
The resin molded article of the present invention may contain a polysiloxane compound. This improves the water repellency of the surface of the resin molded article and prevents adhesion of residual water and dirt.
In the present invention, the resin molded article preferably contains 0.1 mass% or more and 10 mass% or less of the polysiloxane compound, more preferably 0.1 mass% or more and 5 mass% or less, and still more preferably 2 mass% or more and 4 mass% or less. Accordingly, the organic antifungal/antibacterial agent and the inorganic antibacterial agent are likely to be accumulated on the surface of the resin molded body together with the polysiloxane, and therefore, the growth of bacteria and mold can be suppressed for a long period of time.
Reactive polysiloxanes
In the present invention, as the polysiloxane compound, a reactive polysiloxane can be used. As the reactive polysiloxane, a polysiloxane resin in which one-side end of a molecular chain is chain-closed with one selected from a dimethylvinylsiloxane group, an acryloyl group, and a methacryloyl group can be used. Specifically, one-side terminal-modified acrylic polysiloxane, one-side terminal-modified methacrylic polysiloxane, and the like can be mentioned.
In the present invention, the reactive polysiloxane is preferably used as a polysiloxane graft resin obtained by graft-polymerizing the reactive polysiloxane with a resin. Accordingly, the reactive polysiloxane can be immobilized on the resin, and thus the water repellency can be maintained for a long period of time.
In the present invention, the polysiloxane graft resin can be obtained by bonding, for example, a polysiloxane resin in which one end of a molecular chain is chain-closed with any one selected from the group consisting of a dimethylvinylsiloxane group, an acryloyl group, and a methacryloyl group to a main chain of the resin. Specific production methods and the like can be obtained by a known method described in, for example, Japanese patent application laid-open No. 8-127660.
For example, when silicone-grafted polypropylene is used as the silicone-grafted resin, commercially available silicone-grafted polypropylene is available, and such commercially available products can be used in the present invention. Examples of commercially available silicone-grafted polypropylene include X-22-2101 (shin-Etsu chemical Co., Ltd.), BY27-201(Toray Dow Corning Co., Ltd.), and the like.
In the present invention, the reactive polysiloxane is preferably contained in the resin molded product at 0 mass% or more and 10 mass% or less, more preferably at 0 mass% or more and 4 mass% or less, and still more preferably at 2 mass% or more and 4 mass% or less.
Non-reactive silicone oil
In the present invention, the resin molded body may contain a non-reactive silicone oil. The silicone oil is preferably represented by the general formula R3 SiO-(R2SiO)n-SiR3(Here, R represents an alkyl group which may be the same or different, preferably C1-6Alkyl) group.
As the non-reactive silicone oil, one or more selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil, polyether-modified silicone oil, and fatty acid ester-modified silicone oil can be used. The viscosity of the silicone oil is usually 0.5cSt to 1,000,000 cSt, and in the present invention, 10 to 1,000 cSt is preferable in view of bleeding of the non-reactive silicone oil. Accordingly, the non-reactive silicone oil is easily bleeds out on the surface of the resin molded body, and the surface of the resin molded body can be made water repellent.
In the present invention, the non-reactive silicone oil is preferably contained in the resin molded body in an amount of 0 mass% or more and 5 mass% or less, more preferably 0 mass% or more and 4 mass% or less, and still more preferably 0.2 mass% or more and 2 mass% or less.
In the present invention, as the silicone compound, a reactive silicone or a non-reactive silicone oil may be used, and both may be used.
Water spot component
The resin molded article of the present invention can be used as a water-use site member. The resin molded body can be processed into a desired shape and made into a water-use site member. The water use place member is a member used in a water use place environment, and examples of the water use place environment include a toilet, a bathroom, and a kitchen.
In the present invention, specific water-use site components include the following.
Examples of the member used in the toilet include a toilet stool, a toilet seat, a toilet lid, a casing of a private parts washing apparatus, a deodorizing apparatus, a remote controller, a washing nozzle, a hand washer, a paper roll, a face washer, a hand rail, a perforated plate for a urinal, a welfare equipment, and a hand dryer.
Examples of the components used in bathrooms include bathtubs, bathroom floors, bathroom walls, bathroom ceilings, armrests, bath chairs, drain pans, counters, shelves, traps, hair filters, drain flanges, water-sealed bottles, bathroom dryers, and the like.
Examples of the members used in the lavatory include washbasins, counters, traps, hair removers, drain flanges, water sealed bottles, drain covers, perforated plates, drain plugs, and racks.
Examples of the member used in the kitchen include a basket, a sink, a drain port, a trap, a drain flange, a water-sealed bottle, a drain port cover, a perforated plate, a drain plug, and a counter.
Manufacturing method
In the present invention, the following method can be used as a method for producing a resin molded article, but the present invention is not limited thereto.
First, raw materials necessary for forming a resin molded body are prepared. The resin raw material is weighed in a desired amount and mixed with an organic antifungal antibacterial agent and an inorganic antibacterial agent. As a method for mixing the resin material with the organic antifungal/antibacterial agent and the inorganic antibacterial agent, a composite method or a master batch method can be used.
The composite method is a method in which a predetermined amount of an organic antifungal antibacterial agent and an inorganic antibacterial agent are added and mixed in a state where a resin raw material is heated and melted, and the mixture is molded into pellets and used, for example.
The masterbatch method is a method in which a resin and an additive such as an organic antifungal/antibacterial agent or an inorganic antibacterial agent are concentrated and granulated, for example. An appropriate amount of the prepared master batch was mixed with the resin material and used in molding.
In the present invention, additives such as talc, glass fiber, carbon fiber, cellulose fiber, antioxidant, light stabilizer, ultraviolet absorber, colorant and the like may be contained in the raw material according to the purpose.
In consideration of design, inorganic pigments and organic pigments can be used as the colorant. As the inorganic pigment, titanium oxide, talc, silica, or the like can be used. As the organic pigment, pigment yellow 83, pigment red 48: 2. pigment red 48: 3. pigment violet 23, pigment blue 15: 1. pigment blue 15: 2. pigment blue 15: 3. pigment green 7, pigment green 36, and the like.
The mixed raw materials are formed into a desired shape. Examples of the molding method include injection molding, extrusion molding, compression molding, transfer molding, calender molding, vacuum molding, and blow molding. In the present invention, injection molding is preferably used.
The heating temperature in the injection molding may be selected according to the kind of the resin. For example, when a polypropylene resin or a polyacetal resin is used as the resin, it is preferably 160 ℃ or higher and 220 ℃ or lower, and more preferably 180 ℃ or higher and 210 ℃ or lower.
Examples
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.
As the raw materials, the following raw materials were used.
The mildew-proof antibacterial agent A: OIT (2-n-octyl-4-isothiazolin-3-one) as a thiazoline type antifungal antibacterial agent was mixed in a ratio of 1: the ratio of 9 is supported on talc
And (3) mildew-proof antibacterial agent B: ZP (zinc pyrithione) as a pyridine antifungal antibacterial agent was mixed at a ratio of 1: 4 in a proportion to zeolite
An antibacterial agent A: silver-based antibacterial agent (containing 0.48 wt% of silver ions by supporting silver ions on glass)
An antibacterial agent B: zinc-based antibacterial agent (Zinc oxide)
Reactive polysiloxane: PP grafted polysiloxane
Non-reactive silicone oil: dimethyl silicone oil
Example 1
The polyacetal resins in the amounts shown in Table 1 were heated and melted at 200 ℃. The antifungal agent A, the antifungal agent B and the antibacterial agent A were compounded in the amounts shown in Table 1 and granulated. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Example 2
Talc in the amount shown in table 1 was melted with a polypropylene resin by heating at 180 ℃. The antifungal and antibacterial agent A, the antifungal and antibacterial agent B, the antibacterial agent A, the reactive polysiloxane and the non-reactive silicone oil were compounded in the amounts shown in Table 1 and pelletized. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Example 3
The polypropylene resins in the amounts shown in Table 1 were melted by heating at 180 ℃. The antifungal and antibacterial agent A, the antifungal and antibacterial agent B, the antibacterial agent A, the reactive polysiloxane and the non-reactive silicone oil were compounded in the amounts shown in Table 1 and pelletized. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Example 4
1000g of a polypropylene resin was melted by heating at 180 ℃. To this, the antifungal agent A600g, the antifungal agent B200g and the antimicrobial agent A120g were added and mixed. Thereafter, a granulated master batch was prepared. Next, the master batch, the polypropylene resin, the reactive polysiloxane, the non-reactive silicone oil, and the glass fiber as a filler were mixed in a tumbler mixer in the proportions shown in table 1, and then molded at 200 ℃ by a jet molding machine to prepare a sheet.
Example 5
The polyethylene resins in the amounts shown in Table 1 were heated and melted at 180 ℃. The antifungal agent A, the antifungal agent B and the antibacterial agent A were compounded in the amounts shown in Table 1 and granulated. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Example 6
Talc in the amount shown in table 1 was melted with a polypropylene resin by heating at 180 ℃. The antifungal and antibacterial agent A, the antifungal and antibacterial agent B, the antibacterial agent A, the reactive polysiloxane and the non-reactive silicone oil were compounded in the amounts shown in Table 1 and pelletized. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Example 7
Talc in the amount shown in table 1 was melted with a polypropylene resin by heating at 180 ℃. The antifungal agent A, the antifungal agent B and the antibacterial agent A were compounded in the amounts shown in Table 1 and granulated. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Examples 8 to 14
The polypropylene resins in the amounts shown in Table 1 or Table 2 were heated and melted at 180 ℃. The antifungal agent A, the antifungal agent B and the antibacterial agent A were compounded in the amounts shown in Table 1 or Table 2 and granulated. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Comparative example 1
The polypropylene resins in the amounts shown in Table 2 were heated and melted at 180 ℃ and the resulting pellets were injection molded at 200 ℃ to produce plates.
Comparative example 2
The polypropylene resins in the amounts shown in Table 2 were melted by heating at 180 ℃. The amount of the antifungal/antibacterial agent B shown in Table 1 was compounded therein and granulated. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Comparative example 3
The polypropylene resins in the amounts shown in Table 2 were melted by heating at 180 ℃. The amount of antibacterial agent a shown in table 1 was compounded therein and granulated. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Comparative example 4
Talc in the amount shown in table 2 was melted with a polypropylene resin by heating at 180 ℃. The antifungal and antibacterial agent A, the antifungal and antibacterial agent B, the reactive polysiloxane and the non-reactive silicone oil were compounded in the amounts shown in Table 1 and pelletized. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
Comparative example 5
The polypropylene resins in the amounts shown in Table 2 were melted by heating at 180 ℃. The antifungal and antibacterial agents A and B were compounded in the amounts shown in Table 1 and granulated. The prepared pellets were spray-molded at 200 ℃ to prepare a plate.
TABLE 1
TABLE 2
The obtained plate was evaluated by the following method.
Preparation before testing
The plates, equipment, reagents used in the test were all used after sterilization was completed.
Production of deteriorated plate
To evaluate the durability, a deteriorated plate (plate B) was produced by immersing the produced plate in ultrapure water at 90 ℃ for 19 hours. The following tests were carried out on this panel B and on an initial panel (panel A) which had not been subjected to any treatment. In the following description of the test method, "plate" means "plate a" and "plate B".
Reference test: mildew resistance test
The relationship between the thickness of the biofilm and the number of cells attached to the biofilm was examined using the plate a of comparative example 1.
Conditioning of suspensions of spores
Cladosporium sp. parent strain collected from a drain port of a general household toilet was inoculated to a slant culture medium of a potato dextrose agar medium using an inoculating loop and cultured for 7 days. 10ml of a nonionic surfactant (0.005%) was added to the cultured slant bacteria. Further, the cells were suspended by blowing air into the slant bacteria using a syringe to adjust the suspension to 1 × 106cell suspension at cfu/mL concentration. At this time, a blood cell count plate was used to confirm that the cell concentration was a predetermined concentration.
Test bacterial liquid
The conditioned suspension of spores was mixed with 1-part Czapek Dox liquid medium diluted in 5 parts with purified water according to 1: 1, mixing and preparing a test bacterium solution.
Imitation biological film
Assuming a biofilm formed in an aqueous field environment, a 3% aqueous xanthan gum solution having a viscosity close to that of the biofilm formed in the aqueous field environment was used.
Test method
A simulated biofilm of a specific thickness was placed on a plate cut into a 50mm square and spread evenly using a spatula. Thereafter, 200. mu.L of the test bacterial suspension was dropped onto the entire surface of the plate for 16 drops in total. And the thicknesses of the simulated biofilm used were 0.2mm, 0.4mm, 0.8mm, and 1.0 mm.
Subsequently, the entire surface of the plate was washed with 10ml of purified water using an electric pipette. Will be placed at
The washed plate in the petri dish was put into a bucket adjusted to a humidity of 99% and incubated at 28 ℃ for 1 week with an incubator.
The cultured sample was placed in a homogenization bag, and 5mL of 0.005% nonionic surfactant was further added by a pipette. The test bacteria were washed by rubbing them thoroughly with hands. The liquid was used as a rinse. All the washing solution was put into the test tube.
0.5mL of the washing solution put into the test tube was collected by a pipette, added to a test tube containing 4.5mL of 0.005% nonionic surfactant, and mixed by using a vortex machine. Further, 0.5ml of the mixture was taken out of the tube by a pipette and put into another tube containing 4.5ml of 0.005% nonionic surfactant, and mixed by a vortex machine. This procedure was repeated in order to prepare 10-fold dilution series.
1ml was collected from the rinse and each dilution by pipette. Adding the collected liquid into the liquid container via a liquid transfer device
In the culture dish of (1). 20ml of standard agar medium incubated at 48 ℃ were added to each dish and mixed. Thereafter, each dish was covered with a lid and left at room temperature. After the medium solidified, each dish was inverted and incubated at a temperature of 28. + -. 1 ℃ for 1 week.
Evaluation of
After the culture, the number of colonies was measured in the dilution series of the petri dishes in which 30 to 300 colonies appeared. And the number of colonies in the culture dish was determined by visual counting. From the measurement results, the number of fungi propagated on the plate was calculated by the following formula. The results are shown in FIG. 2.
Number of fungi (cfu/cm)2) Number of colonies on the culture dish × 5ml/16cm2
In fig. 2, the horizontal axis represents the thickness of the attached pseudo biofilm, and the vertical axis represents the number of fungi in each pseudo biofilm. As shown in fig. 2, it is understood that the number of adhered mold spores increases when the thickness of a pseudo biofilm simulating a biofilm formed by bacteria increases. From this, it is found that it is important to suppress the thickness of the biofilm as an element for suppressing the growth of mold.
Test 1: bacterial growth inhibition assay
Adjustment of bacterial liquid
Microbacterium sp. cultured at 35 ℃ for about 16 hours was mixed with 1/500NB (NB: common broth medium) to give a bacterial concentration of 1.25X 108cfu/mL to prepare a bacterial solution.
Test method
Antibacterial processed product-antibacterial according to JIS Z2801 (2010)Methods of testing for Properties and antibacterial Effect. Cleaning with 90% ethanol at 2.5 × 2.5cm250. mu.L of the culture broth was added dropwise to the plate. Covering it with polyethylene film 1.5X 1.5cm2And placing into a culture dish, and culturing at a temperature of 35 +/-1 ℃ and a relative humidity of more than 90% for 24 hours. After the culture, the culture medium is placed into a homogenizing bag, 10mL of SCDLP culture medium is added, and the test bacteria are washed by fully rubbing. The rinse solution was diluted with physiological saline as appropriate. 1mL of the dilution was cultured with SMA (Standard agar Medium) and the number of viable cells on the plate (N) was determinedA)。
For 2.5X 2.5cm2The same test as above was carried out to determine the number of viable cells (N) on the polyethylene film of (1)B)。
The obtained NAAnd NBSubstituting the formula and obtaining the antibacterial activity value (R). The antibacterial activity value (R) was evaluated by the following evaluation criteria. The results are shown in Table 3.
R＝log(NB/NA)
Evaluation criteria
The evaluation was carried out using the following evaluation criteria.
2, above: a. the
1 or more: b is
Less than 1: c
Test 2: biofilm formation assay
Preparation of the culture solution
Czapek Dox medium diluted to 1 in 10 parts with purified water was mixed with Microbacterium sp, Methylobacterium sp and Pseudomonas sp, which were collected from a washroom, isolated and cultured for 16 hours, to give a bacterial solution concentration of about 1.0X 104cfu/mL to prepare a culture solution.
Test method
Attaching 2.3X 2.3cm to the inner wall of the flow cell2The plate of (1). The culture solution was pumped into the flow cell at a flow rate of 0.9ml/L using a pump, and left at 30 ℃ for 2 days or 3 days to form a biofilm on the plate.
Evaluation of
The thickness of the biofilm formed on the plate was measured with a laser microscope. The obtained thickness was evaluated using the following evaluation criteria. The results are shown in Table 3.
Evaluation criteria
Less than 35 μm: a. the
Less than 45 μm: b is
45 μm or more: c
Test 3: mildew resistance test (Z2911)
Conditioning of suspensions of spores
The cell suspension was adjusted in the same manner as described above using Aspergillus niger (NBRC105649), Penicillium pinophilum (NBRC33285), Paecilomyces variotii (NBRC33284), Trichoderma virens (NBRC6355) and Chaetomium globosum (NBRC 6347).
Test method
The test was carried out according to test method B of JIS 2911 plastic products. By being at
Glucose/inorganic salt agar medium was added to the petri dish and allowed to stand at room temperature to solidify the medium. Plates were attached to the medium and the cell suspension was sprayed. The dishes were placed in a bucket humidity adjusted to 99% and incubated at 28 ℃ for 4 weeks in an incubator at 29. + -. 1 ℃.
Evaluation of
The growth state of mold on the plate was visually evaluated every week with a microscope, and the evaluation result after 4 weeks was used as the final evaluation result. The results are shown in Table 3.
Evaluation criteria
Let A be the following
0: no mold growth was observed under the naked eye and microscope
1: the growth of mold was not observed with the naked eye, but was observed under a microscope
Let B be the following
2: the growth of the mold occupies less than 25% of the area of the plate
Let the following be C
3: the growth of the mould occupies 25 to 50 percent of the area of the plate
Let D be the following
4: the growth of the mould occupies 50-100% of the area of the plate
5: hypha develops vigorously and covers the whole sample
Test 4: biofilm formation test (oscillation test)
Preparation of the culture solution
Czapek Dox medium was mixed with Microbacterium.sp., Methylobacterium.sp., and Pseudomonas sp., collected from a washroom, isolated, and cultured for 16 hours, to give a bacterial solution concentration of about 3.0X 104cfu/mL to prepare a culture solution.
Test method
Placing 1.1 × 2.3cm in plastic pipe2The plate of (1). A culture medium was placed in the tube so that the entire plate was immersed in the culture medium, and the plate was shaken at a shaking speed of 120r/min at 30 ℃ for 3 weeks to form a biofilm on the plate.
Evaluation of
The plate was washed with purified water and left to dry at room temperature. The biofilm formed on the plate was stained by immersing it in a 0.2% crystal violet solution for 30 minutes. The plate was washed with purified water and left to dry at room temperature. The supernatant was separated from the precipitate by washing with 1mL of 99% ethanol and centrifuging at 5000rpm for 1 minute. The absorbance of ethanol as the supernatant at a wavelength of 590nm was measured using a spectrophotometer. The obtained values were evaluated using the following evaluation criteria. The results are shown in Table 3.
Evaluation criteria
0.09 following: a. the
Greater than 0.09, less than 0.1: b is
0.1 or more: c
Test 5: dissolution Rate test
Dissolution rate of OIT
A glass bottle was charged with a solution having a surface area S of 11.4 (2.3X 2+ 2.3X 0.1X 4) cm2The plate of (2) was mixed with 30ml of ultrapure water. The plate was left standing at 40 ℃ for 24 hours in a state where the whole plate was immersed in water. After which the plate was removed from the vial. Subsequently, 6ml of hexane (lh) was added to the glass bottle and sufficiently stirred, and OIT dissolved out from water was extracted into hexane. Calculation by GC/MSOIT concentration (MA) of the hexane solution.
Next, the molded article was filled with 11.4 (2.3X 2+ 2.3X 0.1X 4) cm of a polypropylene resin containing no antifungal agent2The plate glass bottle of (1) was measured by GC/MS under the same conditions as described above, and the OIT concentration (MB) of the operation blank was calculated.
The dissolution rate (V) of OIT from the plate was determined from the following equationOIT)。
VOIT＝OS×LH/(S×T)＝(OA-OB)×LH/(S×T)
VOIT: dissolution Rate (g/cm) of OIT from plates2/h)
OS: OIT concentration (g/ml) ═ O eluted from the platesA-OB
OA: OIT concentration (g/ml) of hexane solution
OB: OIT concentration (g/ml) for run blank
LH: amount of hexane (6ml)
S: plate surface area (11.4 cm)2)
T: dissolution time (24 hours)
Dissolution rate of ZPT and Ag ion
A bottle made of polypropylene was charged with a surface area S of 11.4 (2.3X 2+ 2.3X 0.1X 4) cm2With 44ml (L)W) The ultrapure water of (1). The whole test piece was left standing at 40 ℃ for 24 hours in a state of being immersed in water. Thereafter, the plate was taken out of the bottle and ultra-high purity nitric acid was added so that the nitric acid concentration became 5 vol%. The zinc ion concentration (Zn) of the nitric acid solution was calculated by ICP-MSA) And silver ion concentration (Ag)A)。
About 11.4 (2.3X 2+ 2.3X 0.1X 4) cm filled with a polypropylene resin containing no antifungal agent2The plate of glass bottle (1) was measured by ICP-MS under the same conditions as described above, and the zinc ion concentration (Zn) of the operation blank was calculatedB) Or silver ion concentration (Ag)B)。
Then, the elution rates of zinc ions eluted from the plates were determined by the following equations, respectively(VZn) And the dissolution rate (V) of silver ionsAg)。
VZn＝ZnS×LW/(S×T)＝(ZnA-ZnB)×LW/(S×T)
VZn: elution rate (g/cm) of zinc ions eluted from the plate2/h)
ZnS: concentration (g/ml) of zinc ion eluted from the plate as ZnA-ZnB
ZnA: zinc ion concentration (g/ml) of nitric acid solution
ZnB: zinc ion concentration (g/ml) of run blank
LW: amount of ultrapure water (44ml)
S: plate surface area (11.4 cm)2)
T: dissolution time (24 hours)
VAg＝AgS×LW/(S×T)＝(AgA-AgB)×LW/(S×T)
VAg: dissolution rate (g/cm) of silver ions from the plate2/h)
AgSConcentration (g/ml) of silver ion eluted from the plate as AgA-AgB
AgA: concentration of silver ions (g/ml) of nitric acid solution
AgB: silver ion concentration (g/ml) of the operation blank
LW: ultrapure water quantity (44ml)
S: plate surface area (11.4 cm)2)
T: dissolution time (24 hours)
The ZPT dissolution rate (V) was determined from the following equationZPT)。
VZPT＝VZnZn atomic weight XZPT molecular weight
TABLE 3
Claims (4)
1. A resin molded body comprising a resin, an organic antifungal antibacterial agent and an inorganic antibacterial agent, wherein the resin is a thermoplastic resin, the organic antifungal antibacterial agent is 2-n-octyl-4-isothiazolin-3-one supported on an inorganic compound and zinc pyrithione supported on the inorganic compound, the inorganic antibacterial agent is a silver antibacterial agent in which silver ions are supported on the inorganic compound,
the resin molded body is characterized in that,
the resin molded body contains 0.1 to 0.38 mass% of the 2-n-octyl-4-isothiazolin-3-one and 0.06 to 0.25 mass% of the zinc pyrithione, and contains 8.6X 10-43.6X 10 mass% or more-3Less than or equal to mass% of silver ions of the silver-based antibacterial agent,
the elution rate of the zinc pyrithione from the resin molded article is 10-9g/cm2More than one hour of reaction time per hour,
the elution rate of the 2-n-octyl-4-isothiazolin-3-one from the resin molded body is 5 times or more as high as the elution rate of the zinc pyrithione,
the elution rate V of the zinc pyrithione and the 2-n-octyl-4-isothiazolin-3-one from the resin molded article is determined by placing the resin molded article having an area S and ultrapure water having a volume L in a vessel, and allowing the resin molded article to stand at 40 ℃ for a certain time T in a state where the whole resin molded article is immersed in water, according to the following equation:
dissolution velocity V (g/cm)2(ii)/h) concentration M (g/ml) of the antifungal/antibacterial agent eluted from the resin molded body x solvent amount L (ml)/(surface area S (cm) of the resin molded body2) Dissolution time T (h)).
2. The resin molded body according to claim 1, wherein after the resin molded body is immersed in water at 90 ℃ for 19 hours,
the dissolution rate of the zinc pyrithione is 10-10g/cm2More than one hour of reaction time per hour,
the dissolution rate of the 2-n-octyl-4-isothiazolin-3-one is 1.5 times or more of the dissolution rate of the zinc pyrithione.
3. The resin molded body according to claim 2, wherein an elution rate of the silver ions from the resin molded body is 5 to 1 inclusive with respect to an elution rate of the zinc pyrithione.
4. A water-use site member comprising the resin molded article according to claim 1.
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| JP2017003374 | 2017-01-12 | ||
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| JP2017003375 | 2017-01-12 | ||
| JP2017108488 | 2017-05-31 | ||
| JP2017-108488 | 2017-05-31 | ||
| JP2017108489A JP6784230B2 (en) | 2017-01-12 | 2017-05-31 | Resin molded body and water supply member |
| JP2017-108489 | 2017-05-31 | ||
| JP2018001683A JP6638742B2 (en) | 2017-01-12 | 2018-01-10 | Resin molded body and water surrounding member |
| JP2018-001683 | 2018-01-10 |
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| JPH10237716A (en) * | 1997-02-20 | 1998-09-08 | Kanebo Ltd | Anti-bacterial and anti-fungal monofilament |
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2018
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| US4775585A (en) * | 1983-01-21 | 1988-10-04 | Kanebo Ltd./Kanto Chemical Co. | Polymer article having an antibacterial property containing zeolite particles therein and the processes for producing same |
| JPH10237716A (en) * | 1997-02-20 | 1998-09-08 | Kanebo Ltd | Anti-bacterial and anti-fungal monofilament |
| JPH11279417A (en) * | 1998-03-30 | 1999-10-12 | Sanyo Electric Co Ltd | Antibacterial and antifungal resin composition |
| JPH11279350A (en) * | 1998-03-30 | 1999-10-12 | Sanyo Electric Co Ltd | Antimicrobial antifungal resin composition |
| CN101005762A (en) * | 2004-07-13 | 2007-07-25 | 出光技优股份有限公司 | Antibacterial composition, antibacterial molding, solution containing antibacterial composition, detergent, surface of tatami mat and tatami mat |
| CN102258064A (en) * | 2011-05-12 | 2011-11-30 | 赵正坤 | Antibacterial composition and application thereof |
| CN103073784A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial polypropylene composition and preparation method thereof |
| CN103073907A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial thermoplastic plastic composition and preparation method thereof |
| CN103627239A (en) * | 2013-12-12 | 2014-03-12 | 李泽国 | Antibacterial, mildew-proof and algae-proof auxiliary of aqueous paint and preparation method thereof |
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