JP6784230B2 - Resin molded body and water supply member - Google Patents

Description

The present invention relates to a resin molded product and a water peripheral member.

It is known that a resin molded body made of resin is used as a member used around water (hereinafter referred to as a water-related member). The resin molded product is required to have antifouling properties. In particular, when used in the presence of water, it is required that water and dirt are less likely to adhere.

It is known that the resin molded product further contains an antibacterial agent and an antifungal agent to suppress the growth of fungi such as bacteria and mold on the surface of the resin molded product.

For example, Patent Document 1 states that a long-term antibacterial and antifungal effect can be obtained by containing a filler and an antibacterial and antifungal agent in a resin as a plate used for a drain dish used in an air conditioner. Is described.

Japanese Unexamined Patent Publication No. 7-103500

In order to continue to suppress the growth of bacteria and mold as a resin molded product, it is required that an antibacterial agent and an antifungal agent are eluted from the resin molded product. Further, this elution is required for a long period of time, and therefore, a resin molded product capable of suppressing the growth of bacteria and mold in the long term is still required.

Therefore, an object of the present invention is to obtain a resin molded product capable of suppressing the growth of bacteria and mold in the long term.

The resin molded body according to the present invention is a resin molded body containing a resin, an organic antibacterial antifungal agent supported on an inorganic compound, and an inorganic antibacterial agent, and the organic antibacterial body is contained in the resin molded body. It contains 0.1% by mass or more and 0.6% by mass or less of the fungicide, and 1.0 × 10 ^-4 % by mass or more and 3.6 × 10 ^-3 % by mass or less of the inorganic antibacterial agent.

Further, the water-related member of the present invention can be made of the above-mentioned resin molded product.

It is a schematic diagram which shows the mechanism which fungus and mold grow on the surface of a resin molded article. It is a figure which shows the result of the reference test.

Resin molded body The resin molded body according to the present invention is a resin molded body containing a resin, an organic antibacterial antifungal agent supported on an inorganic compound, and an inorganic antibacterial agent, and the resin molded body is organic. It contains 1% by mass or more and 10% by mass or less of an antibacterial antifungal agent, and 0.1% by mass or more and 10% by mass or less of an inorganic antibacterial agent. This makes it possible to suppress the growth of fungi and molds in the long term.

Growth Mechanism of Bacteria and Molds The growth mechanism of fungi and molds (fungi) on the surface of the resin molded product will be described with reference to FIG. 1, but the following description is merely one theory, and the present invention is described below. It is not bound.

FIG. 1 is a schematic view showing a mechanism by which bacteria and mold are generated on the surface of a resin molded product.

Dirt adhesion process The dirt adhesion process is shown in FIG. 1 (a). Generally, when the resin molded body 1 is used around water, an interface in which dirt components such as sebum and keratin (keratin protein) discharged from the human body due to actions such as hand washing, face washing, and bathing are contained in soap and body soap. Rinse with water with activator. Then, this dirt component adheres to the surface of the resin molded product 1. Most of the attached dirt components are washed away with running water. However, as shown in FIG. 1A, a part of the dirt component remains (residual water) on the surface of the resin molded body 1 as sewage containing the dirt component, and the dirt 2 is left on the surface of the resin molded body 1. Adhere to.

Bacterial growth process The bacterial growth process is shown in FIGS. 1 (b) and 1 (c). Fungi 3 grow on the surface of the resin molded product 1 using the dirt 2 and residual water adhering to the surface of the resin molded product 1 as a nutrient source (FIG. 1 (b)). Some fungi 3 that exist around water grow while excreting extracellular polysaccharides (EPS) as they grow. For example, Mycrobacterium.sp ,, Methylobacterium.sp., Pseudomonas.sp., Etc. The component mainly composed of EPS is called a biofilm. A biofilm 4 is formed on the surface of the resin molded product 1 with the growth of the fungi 3 (FIG. 1 (c)). The biofilm 4 acts as a defense mechanism against external stimuli (running water, acid, alkali, heat, etc.) of the fungus 3. The biofilm 4 is also called slime, and the viscosity of the surface of the resin molded product 1 is increased. It is considered that this promotes the adhesion of dirt 2 and the growth of fungi 3 and mold 5.

Mold Growth Process The mold growth process is shown in FIGS. 1 (d) and 1 (e). Since the growth of mold 5 is generally slower than that of fungus 3, it is considered that the growth of mold 5 proceeds after the growth of fungus 3 and the accompanying formation of biofilm 4 under a normal water environment. The mold spores adhere to the surface of the resin molded product 1 and the surface of the biofilm 4, and then grow nourishingly on the dirt 2 attached to the surface of the resin molded product 1. Some molds develop color as they grow. Specific molds include, for example, Cladosporium sp.

The resin molded product of the present invention contains an organic antibacterial and antifungal agent and an inorganic antibacterial agent. Since the organic antibacterial fungicide and the inorganic antibacterial agent are eluted on the surface of the resin molded product, even if the surface of the resin molded product is dirty, it is possible to prevent the growth of bacteria. Therefore, it is possible to suppress the formation of biofilm and the generation of mold. Further, the organic antibacterial and antifungal agents include those in which 2-n-octyl-4-isothiazolin-3-one (OIT) is supported on an inorganic compound and those in which zinc pyrithione (ZPT) is supported on an inorganic compound. The inorganic antibacterial agent is a silver-based antibacterial agent in which silver ions are supported on an inorganic compound, and the total concentration of the OIT and the ZPT in the resin molded product is 0.17% by mass or more. 3. The concentration of the silver element of the silver-based antibacterial agent is 9.5 × 10 ^-4 % by mass or more, which is 59 % by mass or less. It is 4 × 10 ^-3 % by mass or less. As a result, the organic antibacterial antifungal agent and the inorganic antibacterial agent can continue to elute from the surface of the resin molded product for a long period of time. Therefore, it is possible to suppress the growth of bacteria and molds in the long term.

Resin In the present invention, the resin is contained in the resin molded product as a main component. Here, the main component is preferably 50% by mass or more, more preferably 60% by mass or more in the resin molded product. This makes it possible to obtain good moldability and appearance.

In the present invention, either a thermosetting resin or a thermoplastic resin can be used as the resin. When the resin molded body is large and high strength and heat resistance are required, it is preferable to use a thermosetting resin. On the other hand, when the resin molded body is small and has a complicated shape, it is preferable to use a thermoplastic resin.

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 silicon resin can be used.

In the present invention, as the thermoplastic resin, 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), poly It is possible to use one or more selected from trimethylene terephthalate resin (PTT), polycarbonate resin (PC), and polytetrafluoroethylene tetrafluoroethylene resin (PTFE).

In the present invention, it is preferable to use a thermoplastic resin as the resin. More preferably, as the resin, one or more selected from PP, PE, POM, PBT, PVC, ABS, PPS, PET, PMMA, PA and PC is used. Even more preferable among these is one or more selected from PP, POM, and PE.

Organic Antibacterial and Antifungal Agent In the present invention, the organic antibacterial and antifungal agent is described in the Antibacterial and Antifungal Agent Dictionary-Original Edition- (Journal of the Japanese Society of Antibacterial and Antifungal Agents, 1998, Vol. 26). , Means an organic drug having a MIC (minimum growth inhibitory concentration) against bacteria and fungi.

In the present invention, as the organic antibacterial fungicide, for example, alcohol-based antibacterial fungicide, aldehyde-based antibacterial fungicide, thiazolin-based antibacterial fungicide, imidazole-based antibacterial fungicide, ester-based antibacterial fungicide, chlorine. Antibacterial antifungal agent, peroxide antibacterial antifungal agent, carboxylic acid antibacterial antifungal agent, carbamate antibacterial antifungal agent, sulfamide antibacterial antifungal agent, tetraammonium salt antibacterial antifungal agent, biguanide antibacterial agent It is possible to use one or more selected from antifungal agents, pyridine antibacterial fungicides, phenol antibacterial fungicides, iodine antibacterial fungicides, and triazole antibacterial fungicides.

In the present invention, specifically, the following can be used as the organic antibacterial and antifungal agent.

Alcohol-based antibacterial fungicides include ethanol, isopropanol, propanol, trisnitro (trishydroxymethylnitromethane), chlorobutanol (1,1,1-trichloro-2-methyl-2-propanol), and bronopol (2-bromo-2). One or more selected from −nitropropane-1,3-diol) can be used.

As the aldehyde-based antibacterial fungicide, one or more selected from glutaraldehyde, formaldehyde, and BCA (α-bromocinnamaldehyde) can be used.

Examples of thiazolin-based antibacterial fungicides include OIT (2-n-octyl-4-isothiazolin-3-one), MIT (2-methyl-4-isothiazolin-3-one), and CMI (5-chloro-2-methyl). One or more selected from -4-isothiazolin-3-one), BIT (1,2-benzoisothiazolinone), n-butyl BIT (Nn-butyl-1,2-benzoisothiazolin-3-one) Can be used.

The structural formula of OIT is shown in Equation 1.

The structural formula of MIT is shown in Equation 2.

The structural formula of CMI is shown in Equation 3.

The structural formula of BIT is shown in Equation 4.

As the imidazole-based antibacterial fungicide, one or more selected from TBZ (2- (4-thiazolyl) -benzimidazole) and BCM (methyl-2-benzimidazole carbamate) can be used.

As the ester-based antibacterial fungicide, lauricidin (glycerol laurate) or the like can be used.

Chlorine-based antibacterial fungicides include triclocarban (3,4,4'-trichlorocarbanilide), halocarban (4,54-dichloro-3- (3-fluoromethyl) -carbanilide), 2,4. One or more selected from 5,6-tetrachloroisophthalonitrile, sodium hypochlorite, dichloroisocyanuric acid, and trichloroisocyanuric acid can be used.

As the peroxide-based antibacterial fungicide, one or more selected from hydrogen peroxide, chlorine dioxide, and peracetic acid can be used.

Carboxylic acid-based antibacterial and antifungal agents include benzoic acid, sorbic acid, caprylic acid, propionic acid, 10-undecylene acid, potassium sorbate, potassium propionate, calcium propionate, sodium propionate, sodium propionate, and magnesium dihydrogen One or more selected from bismonoperoxyphthalate and zinc undecylene can be used.

As the carbamate-based antibacterial and antifungal agent, sodium N-methyldithiocarbamate or the like can be used.

As the sulfamide-based antibacterial antifungal agent, one or more selected from diclofluanide and trifluanide can be used.

Examples of the quaternary ammonium salt-based antibacterial fungicide include 4,4'-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium boromid), benzalkonium chloride, benzotonium chloride, acetylammonium bromide, N, One or more selected from N'-hexamethylenebis (4-carbonyl-1-decylpyridinium bromide) and cetylpyridinium chloride can be used.

As the biguanide antibacterial antifungal agent, one or more selected from chlorhexidine gluconate, chlorhexidine hydrochloride, polypiguanide hydrochloride, and polyhexamethylene piganaid can be used.

Pyridine-based antibacterial fungicides include sodium pyrithione, zinc pyrithione (ZPT: bis (2-pyridthio-1-oxide) zinc), and densyl (2,3,5,6, -tetrachloro-4- (methylsulfonyl) pyridine. ), Copper pyrithione (bis (2-pyridithio-1-oxide) copper) can be used.

The structural formula of ZPT is shown in Equation 5.

Phenolic antibacterial and antifungal agents include timol (2-isopropyl-5-methylphenol), cresol (3-methyl-4-isopropylphenol), OPP (orthophenylphenol), phenol, and butylparaben (butyl-p-hydroxy). Benzoate), ethylparaben (ethyl-p-hydroxybenzoate), methylparaben (methyl-p-hydroxybenzoate), propylparaben (propyl-p-hydroxybenzoate), metacresol, orthocresol, paracresol, orthophenylphenol sodium, chloro One or more selected from phen (2-benzyl-4-chlorophenol) and chlorocresol (2-methyl-3-chlorophenol) can be used.

Examples of iodine-based antibacterial fungicides include amical 48 iodine (diiodomethyl-p-tolyl-sulphon), polyvinylpyrrolidone iodine, p-chlorophenyl-3-iodopropagilformal, 3-bromo-2,3-diiodo-propenylethyl carbonate. , 3-Iodine-2-propynylbutyl-carbonate can be used at least one selected from.

As a triazole-based antibacterial fungicide, tebuconazole ((±) -α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1 -Ethyl) and the like can be used.

In the present invention, it is possible to use two or more kinds of organic antibacterial and antifungal agents. This makes it possible to further suppress the growth of bacteria and molds.

In the present invention, it is possible to use at least two or more kinds of organic antibacterial and antifungal agents having different dissolution rates as the organic antibacterial and antifungal agent. This makes it possible to suppress the growth of bacteria and molds for a longer period of time.

In the present invention, when two kinds of organic antibacterial and antifungal agents are used, the resin molded product contains a first organic antibacterial and antifungal agent and a second organic antibacterial and antifungal agent. The first organic antibacterial fungicide preferably has an elution rate of ^10-9 g / cm ² / h or more, and more preferably ^10-8 g / cm ² / h or more. The elution rate of the second organic antibacterial antifungal agent is preferably 5 times or more, more preferably 10 times or more, the elution rate of the first organic antibacterial antifungal agent. As a result, the second organic antibacterial antifungal agent is rapidly eluted on the surface of the resin molded product, so that it is possible to suppress the growth of bacteria and mold at the beginning of use of the resin molded product. In addition, since the first organic antibacterial and antifungal agent elutes at a slower rate than the second organic antibacterial and antifungal agent, it is possible to suppress the growth of bacteria and molds over a long period of time.

In the present invention, the elution rate of the antibacterial fungicide can be determined by the following method.

A resin molded product having an area of S and ultrapure water having a volume of L are placed in a container, and the entire resin molded product is immersed in water and allowed to stand at 40 ° C. for a certain period of time (T). Then, the resin molded product is taken out from the container, and the concentration (M) of the antibacterial and antifungal agent eluted from the resin molded product is calculated using an analyzer at a certain time (T). The analyzer can be selected according to the amount and type of the antibacterial and antifungal agent contained in the resin molded product, and for example, GC / MS or ICP-MS can be used. At this time, the concentration (M) of the antibacterial and antifungal agent is determined in consideration of the influence of contamination and the like. As shown in the formula below, the elution rate (V) of the antibacterial fungicide based on the concentration (M) of the antibacterial fungicide eluted from the resin molded product, the area (S) of the resin molded product, and the elution time (T). Ask for.

Elution rate of antibacterial and antifungal agent V (g / cm ² / h) = Concentration of antibacterial and antifungal agent eluted from resin molded body M (g / ml) × Solvent amount L (ml) / (Area S of resin molded body (Cm ² ) / Elution time T (h))

In the present invention, it is preferable to use one or more selected from thiazolin-based antibacterial and antifungal agents and pyridine-based antibacterial and antifungal agents as the organic antibacterial and antifungal agent. This makes it possible to further suppress the growth of bacteria and molds around water. It is more preferable to use a thiazolin-based antibacterial fungicide and a pyridine-based antibacterial fungicide as the organic antibacterial fungicide.

In the present invention, the organic antibacterial fungicide is supported on an inorganic compound. This makes it possible to control the rate at which the organic antibacterial fungicide elutes from the resin molded product, and it is possible to suppress the growth of bacteria and molds over a long period of time.

As the inorganic compound, one or more selected from zeolite, glass, talc, silica gel, silicate, mica, and sepiolite can be used. Of these, it is preferable to use one or more selected from zeolite, talc, and glass.

In the present invention, the organic antibacterial and antifungal agent is used in a resin molded product in an amount of 1% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less, and further. More preferably, it contains 0.03% by mass or more and 0.7% by mass or less, and even more preferably 0.1% by mass or more and 0.7% by mass or less. This makes it possible to impart antibacterial and antifungal properties to the resin molded product. This makes it possible to obtain long-term antibacterial and antifungal properties.

The resin molded product according to the present invention preferably contains an organic antibacterial fungicide on the surface in an amount of 0.1% by mass or more, more preferably 0.3% by mass or more.

Inorganic antibacterial agent In the present invention, the antibacterial agent is described in the Dictionary of Antibacterial and Antifungal Agents-Original Edition- (Journal of the Japan Society for Antibacterial and Antifungal Agents, 1998, Vol. 26), and at least MIC against bacteria. It means an inorganic drug having (minimum inhibitory concentration).

In the present invention, as the inorganic antibacterial agent, one or more selected from silver-based antibacterial agents, zinc-based antibacterial agents, and copper-based antibacterial agents can be used. This makes it possible to suppress the production of biofilm produced by the growth of bacteria by imparting an antibacterial effect to a wide variety of bacteria, so that the growth of mold that adheres to the biofilm as a scaffold also also occurs. It can be suppressed.

In the present invention, as the inorganic antibacterial agent, one in which one or more selected from silver ion, zinc ion and copper ion is supported on an inorganic compound can be used. As the inorganic compound, one or more selected from zeolite, glass, talc, silica gel, silicate, mica, and sepiolite can be used. When a plurality of ion species are used, each ion may be supported on the same inorganic compound. Specifically, it is possible to use an inorganic antibacterial agent in which silver ions and zinc ions are supported on glass. Further, when a plurality of ion species are used, each ion may be supported on a different inorganic compound. Specifically, it is possible to use 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.

In the present invention, it is preferable to use a composite of silver and an inorganic oxide other than silver as the silver-based antibacterial agent. Specifically, silver-silver phosphate zirconium (Ag _{x Hy} Na _z Zr ₂ (PO) ₄ ) ₃ ) (x + y + z = 1), silver chloride-titanium oxide (AgCl / TiO ₂ ), silver-zinc calcium phosphate (Ag-Ca _x Zn _y Al _z (PO) ₄ ) ₆ (x + y + z = 10), silver-zinc aluminum silicate (mixture) M _{2 / n} · Na ₂ O · 2SiO ₂ · xH ₂ O (M: Ag , Zn, NH ₄ ))), and one or more selected from them can be used.

In the present invention, zinc oxide / silver / zirconium phosphate (ZnO, Ag _{x Hy} Na _z Zr ₂ (PO) ₄ ) ₃ ) or the like can be used as the zinc-based antibacterial agent.

In the present invention, it is possible to use N-stearolyl-L-gratamic acid AgCu salt or the like as the copper-based antibacterial agent.

In the present invention, it is preferable to use a silver antibacterial agent as the inorganic antibacterial agent. More preferably, it is preferable to use a composite of silver and an inorganic oxide other than silver. As a result, excessive elution of silver on the surface of the resin molded product can be suppressed, so that the growth of bacteria can be suppressed for a long period of time.

The resin molded product according to the present invention preferably contains an inorganic antibacterial agent in an amount of 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and 0.1% by mass or more. It is even more preferable to contain 1% by mass or less, and even more preferably 1.0 × 10. ^-4 Mass% or more 3.6 × 10 ^-3 Mass% or less, even more preferably 1.0 × 10 ^-3 Mass% or more 3.6 × 10 ^-3 Including mass% or less. This makes it possible to suppress the growth of bacteria and the production of biofilms over a long period of time.

The resin molded product according to the present invention preferably contains an inorganic antibacterial agent in an amount of 0.01% by mass or more on the surface, and more preferably 0.03% by mass or more. This makes it possible to impart an antibacterial effect to a wide variety of bacteria.

In the resin molded product of the present invention, the elution rate of the inorganic antibacterial agent is preferably 5 times or more slower than that of the first organic antibacterial antifungal agent, and more preferably 10 times or more slower. As a result, the dissolution rate is slower than that of the first and second organic antibacterial and antifungal agents, so that even after the first and second organic antibacterial and antifungal agents are eluted on the surface of the resin molded body. , The elution of the inorganic antibacterial agent continues. This makes it possible to suppress the growth of bacteria and molds over a long period of time. The elution rate of the inorganic antibacterial agent can also be measured according to the above.

The amount of the resin molded product and the inorganic antibacterial agent and the organic antibacterial antifungal agent contained on the surface of the resin molded product can be obtained by the method shown below.

Gas chromatograph mass spectrometry (GC / MS), high performance liquid chromatography (HPLC), and high performance liquid chromatography mass spectrometry (LC / MS) are used as analytical methods for obtaining the amount of antibacterial and antifungal agent contained in the resin molded body. , High Performance Liquid Chromatograph Tandem Mass Spectrometry (LC / MS / MS) and the like, which can be appropriately selected depending on the type of antibacterial and antifungal agent.

As an analysis method for obtaining the amount of antibacterial and antifungal agent contained on the surface of the resin molded body, X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), electron probe microanalyzer (EPMA), glow discharge emission analysis An apparatus (GD-OES), a glow discharge mass spectrometer (GD-MS), a total reflection infrared absorption method (ATR-IR), and the like can be appropriately selected according to the type of antibacterial and antifungal agent. ..

It is also possible to obtain the amount of the antibacterial antifungal agent contained on the surface of the resin molded article by using the amount of the antibacterial antifungal agent contained in the resin molded article obtained by the analysis method. That is, the rate at which the antibacterial fungicide elutes from the resin molded product can be measured, and the amount of the antibacterial fungicide contained on the surface of the resin molded product can be determined from the elution rate and elution time of the antibacterial fungicide. ..
Surface concentration of antibacterial fungicide N (g / cm ² ) = Elution rate of antibacterial fungicide V (g / cm ² / h) x Elution time T (h))

In the present invention, it is preferable to select organic antibacterial antifungal agents and inorganic antibacterial agents having different mechanisms of action. For example, according to one preferred embodiment of the present invention, it is preferable to use an organic antibacterial antifungal agent that inhibits the metabolism of bacteria and molds, and as an inorganic antibacterial agent, an agent that inhibits the cell membrane of bacteria is used. Is preferable. With such a combination, the inorganic antibacterial agent destroys the cell membrane of bacteria and molds, and the organic antibacterial fungicide easily invades the cells, and as a result, the growth of bacteria and molds is more effective. The advantage that it can be suppressed is obtained.

Further, according to a preferred embodiment of the present invention, an isothiazolin-based organic antibacterial antifungal agent is used as the organic antibacterial antifungal agent. The isothiazoline-based organic antibacterial antifungal agent invades the cell membrane of bacteria and fungi, inhibits ATP synthesis by inhibiting the dehydrogenase of the TCA cycle, and can suppress the growth of bacteria and fungi.

Further, according to another aspect, in the present invention, it is preferable to use a pyridine-based organic antibacterial antifungal agent as the organic antibacterial antifungal agent. More preferably, it has a pyrithion skeleton. As a result, it is possible to invade the cell membrane of bacteria and molds, inhibit membrane transport by inhibiting the proton pump, inhibit ATP synthesis, and suppress the growth of bacteria and molds.

Further, according to another aspect of the present invention, it is preferable to use a silver antibacterial agent as the inorganic antibacterial agent. As a result, silver ions can bind to -SH groups and disulfide bonds in bacterial cell membrane proteins and denature the membrane proteins, thereby destroying the cell membrane.

Silicone compound In the present invention, the resin molded product can contain a silicone compound. This makes it possible to improve the water repellency of the surface of the resin molded product and prevent the adhesion of residual water and dirt.

In the present invention, the resin molded product preferably contains the silicone compound in an amount of 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and 2% by mass or more and 4% by mass or less. It is even more preferable to include the following. As a result, the organic antibacterial antifungal agent and the inorganic antibacterial agent tend to stay on the surface of the resin molded product together with the silicone, so that the growth of bacteria and mold can be suppressed in the long term.

Reactive Silicone In the present invention, reactive silicone can be used as the silicone compound. As the reactive silicone, a silicone resin in which one end of the molecular chain is sealed with one selected from a dimethylvinylsiloxane group, an acryloyl group, and a methacryloyl group can be used. Specific examples thereof include one-ended modified acrylic silicone and one-ended modified methacrylic silicone.

In the present invention, the reactive silicone is preferably used as a silicone graft resin obtained by graft-polymerizing the reactive silicone on the resin. As a result, the reactive silicone can be immobilized on the resin, so that the water repellency can be maintained for a long period of time.

In the present invention, the silicone graft resin can be obtained by binding, for example, a silicone resin in which one end of a molecular chain is sealed with a kind selected from a dimethylvinylsiloxane group, an acryloyl group, and a methacryloyl group to the main chain of the resin. You can. Specific manufacturing methods and the like are known, and can be obtained, for example, according to the description in JP-A-8-127660.

For example, when silicone graft polypropylene is used as the silicone graft resin, silicone graft polypropylene is commercially available, and it can also be used in the present invention. Examples of commercially available silicone graft polypropylene include X-22-2101 (Shin-Etsu Chemical Co., Ltd.) and BY27-201 (Toray Dow Corning Co., Ltd.).

In the present invention, the reactive silicone is preferably contained in the resin molded product in an amount of 0% by mass or more and 10% by mass or less, more preferably 0% by mass or more and 4% by mass or less, and further preferably 2% by mass or more and 4% by mass or less. Is even more preferable.

Non-reactive silicone oil In the present invention, the resin molded product can contain non-reactive silicone oil. Silicone oils are represented by the general formula R ₃ SiO- (R ₂ SiO) n—SiR ₃ (where R represents an alkyl group that may be the same or different, preferably a C _1-6 alkyl group). It is preferably a compound.

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 may be used. It is possible. The viscosity of the silicone oil is generally 0.5 cSt to 1,000,000 cSt, but in the present invention, the viscosity of the silicone oil is preferably 10 to 1,000 cSt in consideration of bleeding of the non-reactive silicone. As a result, the non-reactive silicone oil easily bleeds onto the surface of the resin molded product, and the surface of the resin molded product can be made water repellent.

In the present invention, the non-reactive silicone oil is preferably contained in a resin molded product in an amount of 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 4% by mass or less, and 0.2% by mass or more 2 It is even more preferable to contain less than mass%.

In the present invention, reactive silicone or non-reactive silicone may be used or both may be used as the silicone compound.

Water around member The resin molded product of the present invention can be used as a water around member. The resin molded body can be processed into a desired shape to form a water peripheral member. The water-related member is a member used around water, and examples of the water-related member include a toilet, a washroom, a bathroom, and a kitchen.

In the present invention, the following members can be mentioned as specific water-related members.

Members used in toilets include toilet bowls, toilet seats, toilet lids, cases for local cleaning devices, deodorizing units, remote controls, cleaning nozzles, hand washing machines, paper rolls, wash basins, handrails, toilet bowl eye plates, welfare equipment, and hand drying. Equipment and the like can be mentioned.

Examples of members used in the bathroom include bathtubs, bathroom floors, bathroom walls, bathroom ceilings, handrails, bath chairs, drainage pits, counters, shelves, traps, hair catchers, drainage flanges, water seals, bathroom dryers and the like.

Members used in the washroom include wash bowls, counters, traps, hair catchers, drain flanges, water bottles, drain lids, eye plates, drain plugs, shelves and the like.

Examples of members used in the kitchen include net cages, sinks, drains, traps, drain flanges, water seals, drain lids, eye plates, drain plugs, and counters.

Manufacturing Method In the present invention, the following method can be used as the manufacturing method for manufacturing the resin molded product, but the manufacturing method is not limited to this.

First, the raw materials necessary for forming the resin molded product are prepared. The resin raw material, the organic antibacterial antifungal agent, and the inorganic antibacterial agent are weighed and mixed in a desired amount. As a method of mixing the resin raw material with the organic antibacterial fungicide or the inorganic antibacterial agent, a compound or a masterbatch can be used.

The compound can be used by adding and mixing a predetermined amount of an organic antibacterial antifungal agent and an inorganic antibacterial agent in a state where the resin raw material is heated and melted, and molding the compound into pellets, for example.

The masterbatch is obtained by concentrating a resin and additives such as an organic antibacterial fungicide and an inorganic antibacterial agent into pellets, for example. An appropriate amount of a master batch prepared in advance can be mixed with a resin raw material at the time of molding and used.

In the present invention, the raw material may contain additives such as talc, glass fiber, carbon fiber, cellulose fiber, antioxidant, light stabilizer, ultraviolet absorber, and colorant, depending on the intended purpose.

When considering the design, an inorganic pigment or an organic pigment can be used as the colorant. As the inorganic pigment, titanium oxide, talc, silica and the like can be used. Organic pigments include Pigment Yellow 83, Pigment Red 48: 2, Pigment Red 48: 3, Pigment Violet 23, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Green 7 , Pigment Green 36, etc. can be used.

The mixed raw material is molded into a desired shape. Examples of the molding method include injection molding, extrusion molding, compression molding, transfer molding, calender molding, vacuum molding, blow molding and the like. In the present invention, it is preferable to use injection molding.

The heating temperature during injection molding can be selected according to the type of resin. For example, when a polypropylene resin or a polyacetal resin is used as the resin, it is preferably 160 ° C. or higher and 220 ° C. or lower, and more preferably 180 ° C. or higher and 210 ° C. or lower.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The following were used as raw materials.
Antibacterial fungicide A: Thiazoline-based antibacterial fungicide OIT (2-n-octyl-4-isothiazolin-3-one) supported on talc at a ratio of 1: 9 Antibacterial fungicide B: pyridine ZP (zinc pyrithione), which is an antibacterial antifungal agent, supported on zeolite at a ratio of 1: 4. Antibacterial agent A: Silver antibacterial agent (silver ions are supported on glass, and silver ions are 0.48 mass by mass. % Including)
Antibacterial agent B: Zinc-based antibacterial agent (zinc oxide)
Reactive silicone: PP graft silicone Non-reactive silicone oil: Dimethyl silicone

Example 1
The amount of polyacetal resin shown in Table 1 was heated and melted at 200 ° C. A pellet was prepared by compounding the amount of the antibacterial and antifungal agent A shown in Table 1, the antibacterial and antifungal agent B, and the antibacterial agent A. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Example 2
The amounts of talc and polypropylene resin shown in Table 1 were heated and melted at 180 ° C. Pellets were prepared by compounding the amounts shown in Table 1 with the antibacterial and antifungal agent A, the antibacterial and antifungal agent B, the antibacterial agent A, the reactive silicone, and the non-reactive silicone oil. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Example 3
The amount of polypropylene resin shown in Table 1 was heated and melted at 180 ° C. Pellets were prepared by compounding the amounts shown in Table 1 with the antibacterial and antifungal agent A, the antibacterial and antifungal agent B, the antibacterial agent A, the reactive silicone, and the non-reactive silicone oil. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Reference example 1000 g of polypropylene resin was heated and melted at 180 ° C. To this, 600 g of the antibacterial and antifungal agent A, 200 g of the antibacterial and antifungal agent B, and 120 g of the antibacterial agent A were added and mixed. Then, a pellet-shaped masterbatch was prepared. Next, the masterbatch, polypropylene resin, reactive silicone, non-reactive silicone oil, and glass fiber as a filler are mixed with a tumbler mixer so that the ratios are as shown in Table 1, and then the temperature is 200 ° C. by an injection molding machine. A plate was prepared by molding with.

Example 5
The amount of polyethylene resin shown in Table 1 was heated and melted at 180 ° C. To this, the amounts of the antibacterial and antifungal agent A, the antibacterial and antifungal agent B, and the antibacterial agent A shown in Table 1 were compounded to prepare pellets. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Example 6
The amounts of talc and polypropylene resin shown in Table 1 were heated and melted at 180 ° C. Pellets were prepared by compounding the amounts shown in Table 1 with the antibacterial and antifungal agent A, the antibacterial and antifungal agent B, the antibacterial agent A, the reactive silicone, and the non-reactive silicone oil. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Example 7
The amounts of talc and polypropylene resin shown in Table 1 were heated and melted at 180 ° C. To this, the amounts of the antibacterial antifungal agent A, the antibacterial antifungal agent B, and the antibacterial agent A shown in Table 1 were compounded to prepare pellets. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Examples 8-9, Comparative Examples 10-13, Example 14
The amount of polypropylene resin shown in Table 1 or 2 was heated and melted at 180 ° C. Pellets were prepared by compounding the amount of the antibacterial and antifungal agent A shown in Table 1 or 2 , the antibacterial and antifungal agent B, and the antibacterial agent A. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Comparative Example 1
Pellets prepared by heating and melting the amount of polypropylene resin shown in Table 2 at 180 ° C. were injection-molded at 200 ° C. to prepare a plate.

Comparative Example 2
The amount of polypropylene resin shown in Table 2 was heated and melted at 180 ° C. Pellets were prepared by compounding the amount of antibacterial fungicide B shown in Table 2 with this. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Comparative Example 3
The polypropylene resin shown in Table 2 was heated and melted at 180 ° C. Pellets were prepared by compounding the amount of antibacterial agent A shown in Table 2 with this. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Comparative Example 4
The amounts of talc and polypropylene resin shown in Table 2 were heated and melted at 180 ° C. Pellets were prepared by compounding the amounts of the antibacterial and antifungal agent A shown in Table 2 , the antibacterial and antifungal agent B, the reactive silicone, and the non-reactive silicone. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

Comparative Example 5
The amount of polypropylene resin shown in Table 2 was heated and melted at 180 ° C. Pellets were prepared by compounding the amount of antibacterial fungicide C shown in Table 2 with this. The prepared pellets were injection molded at 200 ° C. to prepare a plate.

The obtained plate was evaluated by the following method.

Pre-test preparation All plates, equipment, and reagents used in the test were sterilized.

In order to evaluate the production durability of the deteriorated plate, a deteriorated plate (plate B) was prepared by immersing the prepared plate in ultrapure water at 90 ° C. for 19 hours. All of the following tests were performed on this plate B and the untreated initial plate (plate A). In the following description of the test method, the "plate" refers to "plate A" and "plate B".

Reference test: Mold resistance test Using plate A of Comparative Example 1, the relationship between the thickness of the biofilm and the number of spores adhering to the biofilm was discussed.

Preparation of spore suspension From the original strain of Cladosporium sp. Collected from the drain of a washroom in a general household, it was inoculated on a slope medium of potato dextrose agar medium using a loop loop and cultured for 7 days. 10 ml of 0.005% nonionic surfactant was added to the cultured slant. In addition, spores were suspended by blowing air into the slant with a dropper to prepare a spore suspension at a concentration of 1 × 10 ⁶ cfu / mL. At this time, it was confirmed that the spores had a specified concentration using a hemocytometer.

The spore suspension prepared with the test bacterial solution and the Tsapec-Dogs liquid medium diluted to a concentration of 1/5 with purified water were mixed at a ratio of 1: 1 to prepare a test bacterial solution.

Pseudo-biofilm Assuming a biofilm formed around water, a 3% xanthan gum aqueous solution close to the viscosity of the biofilm formed around water was used.

Test method
A pseudo-biofilm of a specific thickness was placed on a plate cut into 50 mm squares and spread evenly using a spatula. Then, 200 μL of the test bacterial solution was added dropwise to a total of 16 drops on the entire surface of the plate. The pseudo biofilms having thicknesses of 0.2 mm, 0.4 mm, 0.8 mm and 1.0 mm were used.

Next, the entire surface of the plate was washed with 10 ml of purified water using an electric pipettor. The washed plate placed in a 90φ petri dish was placed in a vat adjusted to a humidity of 99% and cultured in an incubator at 28 ° C. for 1 week.

The cultured sample was placed in a stomacher bag, and 5 mL of 0.005% nonionic surfactant was added by pipette. This was thoroughly rubbed by hand to wash out the test bacteria. This liquid was used as a washout liquid. The entire amount of the washout solution was placed in a test tube.

0.5 mL of the washout solution in a test tube was collected with a pipette, added to a test tube containing 4.5 ml of 0.005% nonionic surfactant, and mixed using a vortex. Further, 0.5 ml of this test tube was pipetted, placed in another test tube containing 4.5 ml of 0.005% nonionic surfactant, and mixed using vortex. This operation was repeated in sequence to prepare a 10-fold dilution series diluent.

1 ml of the washout solution and each diluted solution was collected with a pipette. The collected liquids were added to each 90φ petri dish by pipette. 20 ml of standard agar medium kept at 48 ° C was added to each petri dish and mixed. After that, each petri dish was covered and left at room temperature. After the medium had solidified, each petri dish was inverted and cultured at a temperature of 28 ± 1 ° C. for 1 week.

After the evaluation culture, the number of petri dishes in the dilution series in which 30 to 300 colonies appeared was measured. The number of petri dishes was calculated by visually 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.
Number of fungi (cfu / cm ² ) = number of petri dishes x 5 ml / 16 cm ²

The horizontal axis of FIG. 2 shows the thickness of the attached pseudobiofilm, and the vertical axis shows the number of fungi for each thickness of the pseudobiofilm. As shown in FIG. 2, it was found that as the thickness of the pseudobiofilm simulating the biofilm produced by the fungus increased, the number of attached mold spores increased. From this, it can be seen that it is important to suppress the thickness of the biofilm as a factor for suppressing the growth of mold.

Test 1: Bacterial growth suppression test
Adjustment of bacterial solution
Microbacterium sp. Cultured at 35 ° C. for about 16 hours and 1/500 NB (NB: ordinary bouillon medium) were mixed so that the bacterial concentration was 1.25 × 10 ⁸ cfu / mL to prepare a bacterial solution.

Test method
JIS Z 2801 (2010) Antibacterial processed product-Antibacterial test method ・ The test was conducted based on the antibacterial effect. 50 μL of the culture solution was added dropwise to a 2.5 × 2.5 cm ² plate cleaned with 90% ethanol. This was covered with a polyethylene film 1.5 × 1.5 cm ² and placed in a petri dish, and cultured at a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more for 24 hours. After culturing, the cells were placed in a stomacher bag, 10 mL of SCDLP medium was added, and the cells were thoroughly rubbed to wash out the test bacteria. This washout solution was appropriately diluted with physiological saline. Dilutions 1mL cultured in SMA (standard agar medium) was determined number of living bacteria on plates (N _A).

2.5 for polyethylene film × 2.5 cm ^2, subjected to the same test as above was determined number of living bacteria on film (N _B).

The resulting N _A and N _B are substituted into the following equation to determine the antibacterial activity value (R). The antibacterial activity value (R) was evaluated according to the following evaluation criteria. The results are shown in Table 2.
_{R = log (N B / N} A)

Evaluation Criteria The following evaluation criteria were used for evaluation.
2 or more: A
1 or more: B
Less than 1: C

Test 2: Biofilm production test
Preparation of culture medium Tsapec-Dog's medium diluted to 1/10 with purified water, and Microbacterium sp, Methylobacterium.sp. And Pseudomonas.sp. Collected from the washroom, isolated and cultured for 16 hours. The culture medium was prepared by mixing so that the bacterial solution concentration was about 1.0 × 10 ⁴ cfu / mL.

Test method A 2.3 x 2.3 cm ² plate was attached to the inner wall of the flow cell. The culture solution was passed through this flow cell at a flow rate of 0.9 ml / L using a pump, and left at 30 ° C. for 2 or 3 days to form a biofilm on the plate.

The thickness of the biofilm formed on the evaluation plate was measured with a laser microscope. The obtained thickness was evaluated using the following evaluation criteria. The results are shown in Table 2.

Evaluation criteria・ Less than 35 μm: A
・ Less than 45 μm: B
・ 45 μm or more: C

Test 3: Mold resistance test (Z2911)

Preparation of spore suspension
Aspergillus niger (NBRC105649), Penicillium pinophilum (NBRC33285), Paecilomyces variotii (NBRC33284), Trichoderma virens (NBRC6355), Chaetomium globosum (NBRC6347) were used to prepare spore suspensions in the same manner as described above.

Test method
The test was conducted based on JIS 2911 Test Method B for plastic products. Glucose / inorganic salt agar medium was added to a φ90 petri dish and allowed to stand at room temperature to solidify the medium. A plate was attached on the medium and the spore suspension was sprayed. The petri dish was placed in a vat adjusted to a humidity of 99% and cultured in an incubator at 29 ± 1 ° C for 4 weeks at 28 ° C.

Evaluation
The growth state of mold on the plate was judged weekly with a microscope and visually, and the judgment result after 4 weeks was used as the final judgment result. The results are shown in Table 2.

Evaluation Criteria・ The following is defined as A 0: Mold growth is not observed with the naked eye and under a microscope 1: Mold growth is not observed with the naked eye but is observed under a microscope ・ The following is defined as B 2: Mold growth Growth is within 25% of the plate area ・ C is the following 3: Mold growth is 25 to 50% of the plate area
・ The following is set as D 4: Mold growth is 50 to 100% of the plate area
5: Mycelium grows violently and covers the entire sample

Test 4: Biofilm production test (shaking test)
Preparation of culture medium
Tsapec-Dog's medium and Microbacterium sp, Methylobacterium.sp. And Pseudomonas.sp. Collected from the washroom and cultured for 16 hours so that the bacterial solution concentration is about 3.0 × 10 ⁴ cfu / mL, respectively. To prepare a culture solution.

Test method
A 1.1 x 2.3 cm ² plate was placed in a plastic tube. The culture solution was placed in this tube, the entire plate was immersed in the culture solution, and the plate was shaken at a shaking speed of 120 r / min at 30 ° C. for 3 weeks to form a biofilm on the plate.

Evaluation
After washing the plate with purified water, it was allowed to dry at room temperature. This was immersed in a 0.2% crystal violet solution for 30 minutes to stain the biofilm formed on the plate. After washing this plate with purified water, it was left at room temperature to dry. After rinsing with 1 mL of 99% ethanol, the mixture was centrifuged at 5000 rpm for 1 minute to separate into a supernatant and a precipitate. The absorption of the supernatant ethanol was measured at a wavelength of 590 nm using a spectrophotometer. The obtained values were evaluated using the following evaluation criteria. The results are shown in Table 2.

Evaluation criteria・ 0.09 or less: A
Greater than 0.09 and less than 0.1: B
・ 0.1 or more: C

1: Resin molded body 2: Dirt 3: Fungi 4: Biofilm 5: Mold

Claims (4)

With resin
Organic antibacterial fungicide and
A resin molded product containing an inorganic antibacterial agent.
The organic antibacterial antifungal agent is one in which 2-n-octyl-4-isothiazolin-3-one (OIT) is supported on an inorganic compound, and one in which zinc pyrithione (ZPT) is supported on an inorganic compound.
The inorganic antibacterial agent is a silver antibacterial agent in which silver ions are supported on an inorganic compound.
In the resin molded product, the total concentration of the OIT and the ZPT is 0.17% by mass or more. 59 % by mass or less,
2. The concentration of silver element in the silver antibacterial agent is 9.5 × 10 ^-4 % by mass or more. A resin molded product having a size of 4 × 10 ^-3 % by mass or less. The resin molded product according to claim 1, wherein the resin is a thermoplastic resin. The resin molded product according to claim 1 or 2, wherein the inorganic compound is at least one selected from the group consisting of zeolite, glass, talc, silica gel, silicate, mica, and sepiolite. A water-surrounding member made of the resin molded product according to any one of claims 1 to 3.

Images