JP2020016142A - Ceiling member or wall member of bathroom - Google Patents

Abstract

To provide a ceiling member or a wall member of a bathroom capable of maintaining an antibacterial and a mold resistance function for a log term.SOLUTION: A ceiling member or a wall member of a bathroom of the invention has a resin film including a first organic antimicrobial anti mold agent and a second organic antimicrobial anti mold agent, the first and second organic antimicrobial anti mold agents are melted into a moisture adhered to surfaces of the members and impart an antimicrobial anti mold function to the surfaces of the members, the first organic antimicrobial anti mold agent has a melting speed at 40°C after leaving the ceiling member or the wall member of the bathroom at 45°C for 240 hours the same as its melting speed at 40°C before leaving the ceiling member or the wall member of the bathroom under the same condition, and the second organic antimicrobial anti mold agent always has greater melting speed than that of the first organic antimicrobial anti mold agent at 10°C and 20°C.SELECTED DRAWING: Figure 2

Description

  TECHNICAL FIELD The present invention relates to a ceiling member or a wall member of a bathroom, particularly to a ceiling member or a wall member of a bathroom capable of suppressing the occurrence of bacteria and mold.

  Although the ceiling of the bathroom is a place where there is relatively little adhesion of shower water and splashing water due to bathing, dew condensation may occur, and bacteria and mold may be generated and grow. In addition, the ceiling of the bathroom is a place that is difficult to clean, and it is desired that an antibacterial and antifungal function be added to such a place. For example, Japanese Patent Application Laid-Open No. 62-264249 (Patent Document 1) discloses that an adhesive layer is provided on a ceiling of a bathroom, and a water-absorbing resin is fixed to the adhesive layer. It is disclosed to impregnate and / or mix a fungicide. It is said that this will prevent the formation of mold due to condensation water dropping and moisture generated on the ceiling. Also, the water on the wall of the bathroom basically flows down, but similarly, bacteria and mold are generated and grow.

  In addition to the above-mentioned prior art, there is still a need for a method of more efficiently suppressing the generation of bacteria and mold on the ceiling or wall material of a bathroom.

JP-A-62-264249

  The present inventors have a relationship between the environment to which the ceiling member and the wall member of the bathroom are exposed, and the development of the antibacterial and fungicide action on the ceiling member and the wall member. The relationship between the antimicrobial and antifungal effects of these members was examined.

  As a result, the present inventors have found that by including two types of specific organic antibacterial and fungicide in the ceiling member and wall member of the bathroom having a structure including a film containing the antibacterial and fungicide on the member surface. It has been found that, in an environment where a bathroom is placed by daily use, especially in both high and low temperature environments, the generation of bacteria and mold on these members can be suppressed for a long time. To the knowledge of the present inventors, reports have been made on the development of a fungicidal and fungicidal action of a ceiling member or a wall member of a bathroom in consideration of a temperature change in a bathroom and a temperature change when a bathroom dryer is used. Absent. The present invention has been made based on such knowledge.

  Therefore, an object of the present invention is to provide a ceiling member or a wall member of a bathroom, which can suppress the generation of bacteria and mold for a long time, that is, can maintain antibacterial properties and mold resistance for a long time.

And the ceiling member or the wall member of the bathroom according to the present invention,
A resin film comprising a first organic antibacterial and antifungal agent and a second organic antibacterial and antifungal agent,
The first and second organic antibacterial and antifungal agents are eluted with water attached to the surface of the member, and impart antibacterial and antifungal properties to the surface of the member,
The first organic antibacterial and antifungal agent has an elution rate at 40 ° C. after leaving a ceiling member or a wall member of the bathroom at 45 ° C. for 240 hours, the ceiling member or the wall member of the bathroom. Is the same as its elution rate at 40 ° C. before being left under the above conditions,
The second organic antibacterial / mildewproof agent is characterized by having a higher elution rate at 10 ° C. and 20 ° C. than the first organic antibacterial / mildewproof agent.

It is a schematic diagram which shows a general bathroom unit and its component members. It is a schematic diagram which shows the structure of the ceiling member or wall member of the bathroom by this invention. It is a perspective view of the laminated body sample for the evaluation test which assumed the use of the bathroom dryer prepared in the test 1.

Bathroom ceiling member or wall member FIG. 1 is a schematic diagram showing a general bathroom unit and its constituent members. The bathroom unit 500 of the embodiment shown in FIG. 1 includes a bathtub 510, a floor 520, a counter 531, a mirror 533, a shower 534, wall members 541, 542, 543, 544, and a ceiling member 550. The ceiling member or wall member according to the present invention is used as the ceiling member 550 and the wall members 541, 542, 543, 544 of such a bathroom unit.

  FIG. 2 is a schematic diagram showing a basic configuration of a ceiling member or a wall member of a bathroom according to the present invention. The ceiling member or wall member 1 according to the present invention has a basic structure in which a resin film 10 is provided on a substrate 11. For example, it is a laminate in which the resin film 10 is bonded to the substrate 11. The substrate 11 is a member constituting a ceiling and a wall of the bathroom unit 500. Examples of the substrate 11 include a steel plate, aluminum, and stainless steel, and a steel plate is preferable. Examples of the steel sheet include a cold-rolled steel sheet, a hot-dip zinc-aluminum-magnesium alloy-plated steel sheet, a hot-dip galvanized steel sheet, an electro-galvanized steel sheet, and preferably a hot-dip galvanized steel sheet. Further, the substrate 11 is placed on a gypsum board 12 or the like as a structural material. In the embodiment shown in FIG. 2, the resin film 10 is attached between the substrate 11 and the resin film 10 with, for example, an adhesive (not shown). Note that, in FIG. 2, an arrow indicates a direction inside the bathroom space when viewed from the ceiling member or the wall member 1.

  In the present invention, the resin film contains two kinds of antibacterial and fungicide, and the two kinds of antibacterial and fungicide leave the ceiling member or the wall member provided with this resin film at 45 ° C. for 240 hours. A first organic antibacterial and fungicide having a dissolution rate at 40 ° C. which is the same as the dissolution rate at 40 ° C. before leaving the ceiling or wall member of the bathroom under the above conditions; And at a temperature of 20 ° C., a second organic antibacterial / fungal agent having a higher elution rate than the first organic antibacterial / fungicidal agent. By including such two kinds of antibacterial and fungicide, the ceiling member or wall member of the bathroom according to the present invention can exhibit an excellent antibacterial and fungicide action.

  The ceiling member or wall member according to the present invention has antibacterial and antifungal activity in a wide range of temperatures to which the bathroom is exposed, where there is relatively little water, and where the amount of the antibacterial agent is limited. And the effect of suppressing the generation of fungi and mold over a long period of time is obtained.

  The bathroom is generally at room temperature when not taking a bath, and the internal temperature rises when taking a bath. Also, when a bathroom dryer is provided, the internal temperature rises during use. Further, even when the person is not taking a bath, the person is exposed to a high outside temperature in summer from a low outside temperature in winter. On the other hand, since the antibacterial and fungicide dissolves in water attached to the surface of the member containing the antifungal and exhibits its antibacterial and fungicidal activity, its dissolution must be ensured in a wide temperature range where the bathroom is exposed. There is. That is, it is necessary to be able to dissolve in water even at a low temperature such as a temperature in a state where the bath is not bathed or in the winter, and to exhibit its antibacterial and antifungal activity. In addition, high temperatures such as bathing, summer temperatures and the use of bathroom dryers are advantageous for elution of antibacterial and fungicides into water compared to low temperature environments, while, on the other hand, The antibacterial and antifungal agent cannot stably stay on the resin molded article (resin film) due to heat, and the antibacterial and antifungal activity may be lost after a certain period of time.

  In addition, the ceiling member or the wall member according to the present invention has a configuration in which a resin film is provided on the substrate, and the antibacterial and antifungal agent is contained in the resin film. Since the resin film is a thin film, the amount of the antibacterial and antifungal agent that can be contained in the resin film is limited, and there is a limitation that the activity must be exhibited by a limited amount.

  In such a wide temperature range and in a situation where the amount of the antibacterial and fungicide to be present is limited, the bathroom ceiling or wall member according to the present invention exhibits excellent antibacterial and fungicidal action. This effect is obtained by the fact that the resin film contains both the first organic antibacterial and fungicide and the second organic antibacterial and fungicide. By doing so, the antibacterial and antifungal performance can be maintained for a long period of time, and in a low temperature environment, the second organic antibacterial and antifungal agent can be eluted to maintain the antibacterial and antifungal performance for a long time. I do. That is, a first organic antibacterial / fungal agent which has high temperature resistance but hardly elutes in a low temperature environment, and a second organic antibacterial fungicide which elutes in a low temperature environment but thermally degrades in a high temperature environment. It is considered that by including both, the antibacterial and fungicide can be appropriately eluted in both the high temperature environment and the low temperature environment, and the antibacterial and fungicide performance can be maintained for a long period of time.

  According to one aspect of the present invention, the ceiling member or wall member according to the present invention can be advantageously used in a bathroom provided with a bathroom dryer. This is because good antibacterial and antifungal effects can be exhibited even in a high temperature environment.

Resin Film In the present invention, the resin film 10 is a resin molded product containing a resin as a main component, a first organic antibacterial and antifungal agent, and a second organic antibacterial and antifungal agent. Here, the main component means that the resin occupies preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 85% by mass or more and 97% by mass or less of the resin film. By setting the resin composition of the resin film to such a value, a resin film having good moldability and appearance can be obtained.

Either a thermosetting resin or a thermoplastic resin may be used as the resin constituting the resin resin film.

  As the thermosetting resin, at least one selected from urea resins, melamine resins, phenol resins, unsaturated polyester resins, epoxy resins, and silicon resins can be used.

  As thermoplastic resins, polyolefins such as polypropylene resin (PP) and 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), polytriene One or more selected from methylene terephthalate resin (PTT), polycarbonate resin (PC), and polytetrafluoroethylene-tetrafluoroethylene resin (PTFE) can be used.

  In the present invention, it is preferable to use a thermoplastic resin as the resin. The use of the thermoplastic resin makes it easier for the first and second organic antibacterial and fungicide agents to elute on the surface of the resin film, thereby making it possible to suppress the growth of bacteria and mold for a long time. Among the thermoplastic resins, it is more preferable to use one or more selected from PP, PE, POM, PBT, PVC, ABS, PPS, PET, PMMA, PA, and PC. Still more preferably, it is at least one selected from PP, PE, PBT, PVC, and PET.

  The thickness of the resin film is preferably from 20 μm to 300 μm. By setting the thickness of the resin film in this range, the antibacterial and antifungal performance of the organic antibacterial and antifungal agent contained in the resin film can be secured.

First and second organic antibacterial and fungicide agents In the present invention, the first and second organic antibacterial and fungicide agents contained in the resin film are defined as a dictionary of antibacterial and antifungal agents-original edition- The term refers to an organic drug having an MIC (minimum inhibitory concentration) against bacteria and fungi described in the Journal of the Society of Fungi and Fungi, 1998, Vol.

  The first and second organic antibacterial and antifungal agents are eluted with moisture adhering to the surface of the ceiling member or wall member of the bathroom, and impart antibacterial and antifungal properties to the surface of these members. That is, the antibacterial and antifungal effect is exhibited by contact of bacteria and fungi with the first and second organic antibacterial and antifungal agents that elute into the water attached to the surface of the ceiling member or the wall member of the bathroom.

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

A resin molded body having an area of S and ultrapure water having a volume of L are put in a container, and the resin molded body is immersed in water, and is allowed to stand at a constant temperature for a constant time (T). Thereafter, the resin molded body is taken out of the container, and the concentration (M) of the antibacterial and antifungal agent eluted from the resin molded body at a constant temperature for a predetermined time (T) is calculated using an analyzer. The analyzer can be selected according to the amount and type of the antibacterial and antifungal agent contained in the resin molded product. For example, GC / MS, ICP-MS, HPLC, or the like 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 following formula, the dissolution rate (V) of the antibacterial and fungicide based on the concentration (M) of the antibacterial and fungicide eluted from the resin molded article, the area (S) of the resin molded article, and the dissolution time (T) Ask for.
Elution rate of antibacterial and fungicide V (g / cm ² / h) = concentration of antibacterial and fungicide eluted from resin molded article M (g / ml) x amount of solvent L (ml) / (area of resin molded article S (Cm ² ) × elution time T (h))

  In the present invention, the dissolution rate refers to a dissolution rate calculated in a state of being substantially unused after the resin molded article is manufactured. Here, the “virtually unused state” refers to a state in which the resin molded body is manufactured and then used, for example, as a water surrounding member, or a state where the resin molded body is constructed as a bathroom, and furthermore, when the resin molded body is further used. No state.

First organic antibacterial and antifungal agent The first organic antibacterial and antifungal agent leaves a ceiling member or a wall member of a bathroom (hereinafter, may be simply referred to as a “member”) at 45 ° C. for 240 hours (hereinafter, referred to as “the member”). Heat treatment (or heat exposure) ", the rate of elution into water at 40 ° C. after standing (240 hours) is the same as the rate of elution into water at 40 ° C. before standing (0 hours). Is a drug. In the present invention, the expression that the dissolution rate is "identical" indicates that the first organic antibacterial and fungicide is stably eluted even after standing (240 hours). Specifically, it means that the rate of change of the dissolution rate before and after the heat treatment represented by the following formula is ± 100% or less. The rate of change is more specifically ± 70%, and even more specifically ± 65% or less.
Rate of change (%) = (elution rate of heat-treated member−elution rate of non-heat-treated member) / elution rate of non-heat-treated member × 100

  The first organic antibacterial and antifungal agent does not deteriorate even after heat treatment, that is, it has high temperature resistance or heat resistance, and is stably eluted in water in a high temperature environment where a bathroom can be placed, and exhibits a fungicidal effect. can do. In the present invention, the high temperature environment means a temperature environment of 25 ° C. or more, specifically, a temperature environment of 40 ° C. or more, more specifically, a temperature environment of 45 ° C. or more.

  In the present invention, it is preferable to use a first organic antibacterial and fungicide having a molecular weight of 190 or more and a melting point of 50 ° C or more. By having such physical properties, the first organic antibacterial and antifungal agent can stably stay on the resin molded article, and exhibit an antibacterial and antifungal effect on the surface of the resin molded article for a long time under a high temperature environment. It is possible to do.

  According to a preferred embodiment of the present invention, the first organic antibacterial and fungicide includes a pyridine antibacterial and fungicide, an imidazole and antifungal and antifungal agents, a triazole and antifungal and antifungal agents, an iodine and antifungal antifungal agent, and an arsenic and antifungal agent. Antibacterial and antifungal agents, ether antibacterial and antifungal agents, organochlorine and antifungal agents, biguanide and antifungal agents, sulfamide and antifungal agents, quaternary ammonium chloride and antifungal agents, aldehyde antifungal agents At least one selected from the group consisting of an agent, a carboxylic acid-based antibacterial and fungicide, an ester-based antibacterial and antifungal, and a phenol-based antibacterial and antifungal is used. By using these antibacterial and fungicide agents having a specific chemical structure in the molecule as the first organic antibacterial and fungicide agents, their elution rates can be kept unchanged at high temperatures. As a result, even when the bathroom is in a high temperature environment, the antifungal effect can be exerted for a long time.

  Pyridine antibacterial fungicides include zinc pyrithione (ZPT: bis (2-pyridithio-1-oxide) zinc), densyl (2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine), kappa One or more kinds selected from pyrithione (CPT: bis (2-pyridithio-1-oxide) copper) can be used. The pyridine-based antibacterial and fungicide can, for example, invade the cell membrane of bacteria and fungi, inhibit ATP synthesis by restricting membrane transport by inhibiting a proton pump, and suppress the growth of bacteria and fungi.

The structural formula of ZPT is shown below.

  As the imidazole antibacterial fungicide, at least one selected from thiabendazole (TBZ: 2- (4-thiazolyl) -benzimidazole) and carbendazim (MBC or BCM: methyl-2-benzimidazole carbamate) may be used. it can.

  Examples of the triazole antibacterial fungicide include tebuconazole ((±) -α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1. -Ethanol) and the like.

  As the iodine-based antibacterial and antifungal agent, at least one selected from diiodomethyl paratolyl sulfone, polyvinylpyrrolidone iodine, and 3-iodo-2-propynylbutylcarbamate (IPBC) can be used.

  As the arsenic antibacterial and antifungal agent, 10,10'-oxybis-10H-phenoxyarsine (OBPA) or the like can be used.

  Triclosan or the like can be used as the ether antibacterial and antifungal agent.

  Examples of organochlorine antibacterial and antifungal agents include triclocarban (3,4,4′-trichlorocarbanilide), halocarban (4,4-dichloro-3- (3-fluoromethyl) -carbanilide) and chlorothalonil (TPN). : 2,4,5,6-tetrachloroisophthalonitrile), dichloroisocyanuric acid and trichloroisocyanuric acid. Among them, TPN is preferably used.

  As the biguanide-based antibacterial and fungicide, at least one selected from chlorhexidine gluconate, chlorhexidine hydrochloride, polypiguanide hydrochloride, and polyhexamethylenepiguanide can be used.

  As the sulfamide antibacterial and antifungal agent, one or more selected from diclofluanid and trifluanid can be used.

  As the quaternary ammonium chlorine-based antibacterial and antifungal agent, one or more selected from benzotonium chloride and cetylpyridinium chloride can be used.

  BCA (α-bromocinnamaldehyde) and the like can be used as the aldehyde-based antibacterial and antifungal agent.

  As the carboxylic acid antibacterial and antifungal agent, at least one selected from magnesium dihydrogen bismonoperoxyphthalate and zinc undecylenate can be used.

  As the ester antibacterial and antifungal agent, lauricidin (glycerol laurate) or the like can be used.

  As the phenolic antibacterial and antifungal agent, at least one selected from butylparaben (butyl-p-hydroxybenzoate) and sodium orthophenylphenol can be used.

  According to a preferred embodiment of the present invention, pyridine zinc pyrithione (ZPT) and kappa pyrithione (CPT), imidazole thiabendazole (TBZ) and carbendazim (MBC), triazole series Tebuconazole, quaternary ammonium chloride benzotonium chloride and cetylpyridinium chloride, arsenic oxybisphenoxyarsine (OBPA), ether triclosan, organochlorine chlorothalonil (TPN), iodine diiodomethylpara One or more selected from the group consisting of tolylsulfone and 3-iodo-2-propynylbutyl carbamate (IPBC) are used.

Second organic antibacterial / fungicide The second organic antibacterial / fungicide always has a higher elution rate than the first organic antibacterial / fungicide in a low-temperature environment where a bathroom can be placed, that is, elutes in water. It is a drug that is easy to do. In the present invention, the low temperature environment means a temperature environment of 25 ° C. or lower, specifically, a temperature environment of 0 ° C. or higher and 25 ° C. or lower, more specifically, a temperature environment of 10 ° C. or higher and 25 ° C. or lower. I do. The second organic antibacterial and fungicide can be stably eluted in water under a low-temperature environment and exhibit a fungicidal effect.

  In the present invention, it is preferable to use a second organic antibacterial and fungicide having a molecular weight of less than 190 or a melting point of 25 ° C. or less. By having such physical properties, the second organic antibacterial and fungicide can be easily eluted into the dew or adhered water, and the growth of bacteria and fungi can be promoted over a long period of time in a low-temperature environment such as the rainy season when mold can easily grow. It becomes possible to suppress.

In one embodiment of the present invention, for example, it is preferable that the elution rate of the second organic antibacterial fungicide in low-temperature water at 10 ° C. is higher than 1 × 10 ⁻¹⁰ g / cm ² / h. When the dissolution rate is larger than this value, the resin film according to the present invention can maintain the antifungal performance in a low-temperature environment for a long time.

In one embodiment of the present invention, for example, the dissolution rate of the second organic antibacterial and fungicide into water at 10 ° C. is preferably 1 × 10 ⁻¹⁰ g / cm ² / h or more, preferably 1 × 10 ⁻¹⁰ g / cm ² / h. It is more preferably at least 10 ⁻⁹ g / cm ² / h. In addition, the second organic antibacterial and fungicide has an elution rate of 20 ° C in water at least twice as high as that of 10 ° C as the water temperature increases from 10 ° C to 20 ° C. It is preferred that it be larger. In the low-temperature region, the dissolution rate is promoted with the increase in temperature, for example, throughout the year, including places where water droplets have remained on the ceiling and walls of the bathroom in summer, and during the rainy season when mold tends to breed For a long time, it is possible to suppress the growth of fungi and mold.

  According to a preferred embodiment of the present invention, as the second organic antibacterial and fungicide, a thiazoline antibacterial and antifungal agent, a triazine and antifungal and antifungal agent, a thiazole and antifungal and antifungal agent, a phenol and antifungal and antifungal agent, At least one selected from the group consisting of antibacterial and fungicide agents, peroxide-based and antifungal agents, pyridine and antifungal agents, carboxylic acid and antifungal agents, aldehyde and antifungal agents, and alcohol-based antifungal agents Can be used. By using these antibacterial and fungicides having a specific chemical structure in the molecule as the second organic antibacterial and fungicide, they can be relatively easily eluted even at a low temperature. As a result, even when the bathroom is in a low-temperature environment, the antifungal effect can be exerted for a long time.

  Examples of the thiazoline antibacterial and antifungal agents include OIT (2-n-octyl-4-isothiazolin-3-one), MIT (2-methyl-4-isothiazolin-3-one), and CMI (5-chloro-2-methyl). -4-isothiazolin-3-one), BIT (1,2-benzoisothiazolone), and n-butyl BIT (Nn-butyl-1,2-benzoisothiazolone-3) may be used. it can. The thiazoline antibacterial and antifungal agent, for example, invades the cell membrane of bacteria and mold, inhibits ATP synthesis by inhibiting TCA cycle dehydrogenase, and can suppress the growth of bacteria and mold.

The structural formula of OIT is shown below.

The structural formula of MIT is shown below.

The structural formula of CMI is shown below.

The structural formula of BIT is shown below.

  Hexahydro-1,3,5-trimethyl-1,3,5-triazine, 2,4-dichloro-6-methoxy-1,3,5-triazine and the like can be used as the triazine antibacterial fungicide. .

  As the thiazole antibacterial and antifungal agent, one or more selected from 2- (thiocyanomethylthio) benzothiazole (TCMTB), tricyclazole, and benzothiazole can be used.

  Examples of phenolic antibacterial and antifungal agents include thymol (2-isopropyl-5-methylphenol), biosol (3-methyl-4-isopropylphenol), OPP (orthophenylphenol), phenol, and ethyl paraben (ethyl-p-hydroxy). Benzoate), methyl paraben (methyl-p-hydroxybenzoate), propylparaben (propyl-p-hydroxybenzoate), meta-cresol, ortho-cresol, para-cresol, chlorocresol (2-methyl-3-chlorophenol) The above can be used.

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

  As the peroxide-based antibacterial and antifungal agent, peracetic acid and the like can be used.

  As the pyridine-based antibacterial and antifungal agent, sodium pyrithione can be used.

  The carboxylic acid antibacterial fungicide is selected from benzoic acid, sorbic acid, caprylic acid, propionic acid, 10-undecylenic acid, potassium sorbate, potassium propionate, calcium propionate, sodium benzoate, and sodium propionate. One or more types can be used.

  As the aldehyde-based antibacterial and antifungal agent, at least one selected from glutaraldehyde and formaldehyde can be used.

  As the alcohol-based antibacterial and fungicide, at least one selected from ethanol, isopropanol, propanol, trisnitro (trishydroxymethylnitromethane), and chlorobutanol (1,1,1-trichloro-2-methyl-2-propanol). Can be used.

  According to a preferred embodiment of the present invention, as the second organic antibacterial and fungicide, thiazoline octylisothiazolinone (OIT), methylisothiazolinone (MIT), chloromethylisothiazolinone (CMI), benzisothi Azolinone (BIT) and n-butyl BIT, thiazole thiocyanomethylthiobenzothiazole (TCMTB), tricyclazole and benzothiazole, carboxylic acid benzoic acid, sorbic acid, caprylic acid, propionic acid, 10-undecylenic acid, sorbin Potassium, potassium propionate, calcium propionate, sodium benzoate and sodium propionate, aldehyde-based glutaraldehyde and formaldehyde, phenol-based orthophenylphenol (OPP) and biosol One or more one selected from Ranaru group is used.

In the present invention, as the combination of the first and second organic antibacterial and antifungal agents, for example, at least one combination selected from the following group is preferable:
A combination of pyridine zinc pyrithione (ZPT) and thiazoline octylisothiazolinone (OIT),
A combination of an imidazole-based thiabendazole (TBZ) and a thiazoline-based octylisothiazolinone (OIT);
A combination of pyridine zinc pyrithione (ZPT) and thiazole benzothiazole,
A combination of ether triclosan and thiazoline octylisothiazolinone (OIT);
A combination of iodine-based 3-iodo-2-propynylbutylcarbamate (IPBC) and thiazoline-based octylisothiazolinone (OIT);
A combination of pyridine zinc pyrithione (ZPT) and thiazole tricyclazole;
A combination of pyridine zinc pyrithione (ZPT) and thiazole thiocyanomethylthiobenzothiazole (TCMTB);
A combination of pyridine-based copper pyrithione (CPT) and thiazoline-based octylisothiazolinone (OIT);
A combination of pyridine-based copper pyrithione (CPT) and thiazole-based benzothiazole,
A combination of an imidazole thiabendazole (TBZ) and a thiazole benzothiazole,
A combination of triazole tebuconazole and thiazoline octylisothiazolinone (OIT);
A combination of triazole tebuconazole and thiazole benzothiazole,
A combination of iodine-based 3-iodo-2-propynylbutylcarbamate (IPBC) and thiazole-based benzothiazole,
-Combination of ether triclosan and thiazole benzothiazole.

  In the present invention, as for the combination of the first and second organic antibacterial and antifungal agents, it is preferable that one contains a basic skeleton or a basic functional group and the other contains an acidic skeleton or an acidic functional group. . That is, a substance containing a basic skeleton or a basic functional group is selected as the first organic antibacterial / fungicide, and an acidic skeleton or acidic functional group is used as the second organic antibacterial / fungicide. Or a substance containing an acidic skeleton or an acidic functional group as the first organic antibacterial / fungicide, and a basic skeleton or basic functional as the second organic antibacterial / fungicide. It is preferred to select those containing groups. As described above, by specifying the combination of the first and second organic antibacterial and fungicide agents based on the electrical or ionic properties, the elution of the second organic antibacterial and fungicide agent can be performed in a low-temperature environment. Accordingly, it is considered that the first organic antibacterial and fungicide can be eluted. As a result, the first organic antibacterial and fungicide can be more easily eluted in a low-temperature environment than in the case where only the first organic antibacterial and fungicide are contained in the resin molded article. In addition, since the first organic antibacterial fungicide and the second organic antibacterial antifungal having high electrical or ionic affinity with the first organic antibacterial fungicide are present in the resin molded article, the high temperature environment Below, it is considered that the second organic antibacterial fungicide can be prevented from moving from the resin molded product into the gas phase due to volatilization or the like. As a result, the second organic antibacterial / fungicide can be stably retained in the resin molded body under a high-temperature environment as compared with the case where only the second organic antibacterial / fungicide is included in the resin molded article. . In the present invention, for example, the first organic antibacterial and fungicide is a pyridine zinc pyrithione containing a basic skeleton or a basic functional group, and the second organic antibacterial and fungicide is an acidic skeleton. Or a combination of thiazoline octylisothiazolinones containing an acidic functional group. Further, the first organic antibacterial and fungicide is an organic chlorinated dichloroisocyanuric acid containing an acidic skeleton or an acidic functional group, and the second organic antibacterial and fungicide is a basic skeleton or a base. And a pyridine-based sodium pyrithione containing an acidic functional group.

  In the present invention, it is preferable that the first organic antibacterial and fungicide and the second organic antibacterial and fungicide are supported on an inorganic compound. By being supported on an inorganic compound, the heat resistance of the organic antibacterial and antifungal agent can be improved, and it is possible to suppress the generation of gas during heat molding. Further, since the rate at which the organic antibacterial and fungicide is eluted from the resin molded article can be controlled, it is possible to suppress the growth of bacteria and mold in the long term.

  As the inorganic compound, it is possible to use one or more selected from zeolite, glass, talc, silica gel, silicate, mica, sepiolite, clay minerals, and metal oxides, but it is not limited thereto.

  In the present invention, the first organic antibacterial and antifungal agent and the second organic antibacterial and antifungal agent are preferably contained in the resin molded body in an amount of 0.01% by mass or more and 10% by mass or less. When the content is within this range, it is possible to impart antibacterial and antifungal properties to the resin molded article. It is more preferably 0.01% by mass to 5% by mass, still more preferably 0.05% by mass to 3% by mass, and still more preferably 0.05% by mass to 2% by mass. Thereby, the moldability at the time of heat molding of the resin molded body is good, and it is possible to suppress the growth of bacteria and mold in a long term.

  The resin molded article according to the present invention preferably contains 0.05% by mass or more of the first and second organic antibacterial and antifungal agents on the surface.

  The amount of the organic antibacterial and antifungal agent contained in the surface of the resin molded product and the resin molded product can be obtained by the following method.

  As an analytical method for obtaining the amount of the organic antibacterial fungicide contained in the resin molded product, gas chromatography mass spectrometry (GC / MS), high performance liquid chromatography (HPLC), high performance liquid chromatography mass spectrometry (LC / MS) MS), high performance liquid chromatography tandem mass spectrometry (LC / MS / MS) and the like, and can be appropriately selected according to the type of the organic antibacterial and antifungal agent.

  Analytical methods for obtaining the amount of the organic antibacterial and fungicide contained on the surface of the resin molded product include X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), electron beam microanalyzer (EPMA), and glow discharge. Examples include an emission spectrometer (GD-OES), a glow discharge mass spectrometer (GD-MS), and a total reflection infrared absorption method (ATR-IR), which are appropriately selected according to the type of the organic antibacterial and antifungal agent. can do.

It is also possible to obtain the amount of the organic antibacterial and fungicide contained in the surface of the resin molded product by using the amount of the organic antibacterial and fungicide contained in the resin molded product obtained by the analytical method. That is, the rate at which the organic antibacterial and fungicide is eluted from the resin molded article is measured, and from the elution rate and the elution time of this organic antibacterial and fungicide, the organic antibacterial and fungicidal agent contained on the surface of the resin molded article is measured. The quantity can be determined.
Surface concentration of organic antibacterial / fungicide N (g / cm ² ) = elution rate of organic antibacterial / fungicide V (g / cm ² / h) × elution time T (h))

Inorganic antibacterial agent In the present invention, the resin film may further include an inorganic antibacterial agent in addition to the first organic antibacterial and antifungal agent. The inorganic antibacterial agent is described in the dictionary of antibacterial and antifungal agents-the original edition-(Journal of the Japan Society of Antifungal and Antifungal Activities, 1998, Vol. 26) and has an MIC (minimum inhibitory concentration) against at least bacteria. ) Means an inorganic drug having

  As such an inorganic antibacterial agent, it is possible to use one or more selected from silver-based antibacterial agents, zinc-based antibacterial agents, and copper-based antibacterial agents. Thereby, an antibacterial effect against a wide variety of bacteria can be imparted to the ceiling member or the wall member, and the production of a biofilm produced by the proliferation of bacteria can be suppressed. Therefore, it is possible to suppress the growth of mold that adheres to the ceiling member or the wall member using the biofilm as a scaffold. For example, silver-based antibacterial agents can destroy cell membranes by binding silver ions to -SH groups or disulfide bonds in bacterial cell membrane proteins and denaturing the membrane proteins.

  In the present invention, it is possible to use, as the inorganic antibacterial agent, one in which at least one selected from silver ions, zinc ions and copper ions is supported on an inorganic compound. As the inorganic compound, it is possible to use one or more selected from zeolite, glass, talc, silica gel, silicate, mica, and sepiolite. When a plurality of ion species are used, each ion may be carried 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. When a plurality of ion species are used, each ion may be supported by 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, a complex of silver and an inorganic oxide other than silver can be used as the silver-based antibacterial agent. Specifically, a silver - zirconium phosphate: _{"(Ag x H y Na z Zr} 2 (PO) 4) 3 (x + y + z = 1) ", a silver chloride - titanium oxide: "AgCl / TiO _2", silver - phosphorus calcium zinc: _{"(Ag-Ca x Zn y Al} z (PO) 4) 6 (x + y + z = 10) ", a silver zinc aluminosilicate (mixture): _{"αAg 2 O · βZnO · γ (} NH 4) 2 · _{δNa 2 O · Al 2 O 3} · 2SiO 2 · XH 2 O (α + β + γ + δ = 1) it is possible to use one or more kinds selected from ".

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

  In the present invention, N-stearolyl-L-glutamate AgCu salt or the like can be used as the copper-based antibacterial agent.

  In the present invention, it is preferable to use a silver-based antibacterial agent as the inorganic antibacterial agent. More preferably, a composite of silver and an inorganic oxide other than silver is preferably used. Thereby, since the excessive elution of silver on the surface of the resin molded body can be suppressed, it is possible to suppress the growth of bacteria for a long time.

  In the present invention, the resin film preferably contains 0.0001% by mass or more and 0.1% by mass or less of the inorganic antibacterial agent, and more preferably 0.0005% by mass or more and 0.01% by mass or less. This makes it possible to suppress the growth of bacteria and the formation of biofilm over a long period of time.

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

  In the present invention, a design property may be imparted to the surface of the resin film depending on the use. For example, the surface of the resin film may be subjected to a patterning process such as mirror finishing or embossing, or a pattern may be provided. The design is imparted to the resin film by a known method.

  In the present invention, a colorant may be included in the resin film to impart design properties. As the colorant, an inorganic pigment or an organic pigment can be used. As the inorganic pigment, titanium oxide, talc, silica and the like can be used. Examples of the organic pigment 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: 2, and Pigment Blue 15: 2. , Pigment Green 36 and the like can be used.

In one embodiment of the present invention, a layer may be provided on the resin film for the purpose of protecting the resin film, as long as the dissolution of the organic antibacterial and fungicide from the resin film is not hindered.
Production Method In the present invention, the following method can be used as a method for producing a resin molded body, but is not limited to this method.

  First, raw materials necessary for forming a resin molded body are prepared. The resin raw material, the first organic antibacterial and fungicide, and the second organic antibacterial and fungicide are weighed and mixed to a desired amount, and mixed. As a method for mixing the resin raw material, the first organic antibacterial and fungicide, and the second organic antibacterial and fungicide, a compound or a masterbatch can be used.

  The compound is prepared by adding and mixing a predetermined amount of the first organic antibacterial and antifungal agent and the second organic antibacterial and antifungal agent and, if necessary, an inorganic antibacterial agent in a state where the resin material is heated and melted, For example, it can be formed into a pellet and used.

  The masterbatch is obtained by concentrating a resin, a first organic antibacterial and fungicide, a second organic antibacterial and fungicide, and other additives, for example, into a pellet. A master batch prepared in advance can be mixed with an appropriate amount of a resin raw material at the time of molding and used.

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

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

  The heating temperature during extrusion molding or calendar molding can be selected according to the type of resin. For example, when a polyolefin resin is used as the resin, the temperature is preferably 180 ° C. or more and 300 ° C. or less. Since the organic antibacterial and antifungal agent is decomposed by heat when the resin molding temperature is high, the resin molding temperature is preferably lower.

  In the present invention, the ceiling member or the wall member 1 is attached to a base material such as a gypsum board via an adhesive to produce a ceiling panel or a wall panel. To the ceiling or wall.

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

The following materials were used as raw materials.
-Organic antibacterial and fungicide A: A thiazoline antibacterial and fungicide OIT (2-n-octyl-4-isothiazolin-3-one) supported on talc at a ratio of 1: 9-Organic antibacterial Antifungal agent B: ZPT (zinc pyrithione), which is a pyridine antibacterial antifungal agent, supported on an inorganic compound at a ratio of 1: 4. Organic antifungal antifungal agent C: Benzothiazole, a thiazole antifungal antifungal agent. -Organic antibacterial and fungicide D: TBZ which is an imidazole antibacterial and fungicide
-Organic antibacterial and fungicide E: triclosan, which is an ether antibacterial fungicide-Organic antibacterial and fungicide F: IPBC, which is an iodine antibacterial and fungicide
・ Inorganic antibacterial agent: Silver antibacterial agent (silver ion and zinc ion supported on inorganic compound)
Pigment: Titanium oxide (surface-treated, for example, one or two or more silica layers containing silica and / or alumina layers containing alumina on the surface of titanium oxide)

Example 1
The thermoplastic resin was heated and melted, and an organic antibacterial / antifungal agent A, an organic antibacterial / antifungal agent B, and an inorganic antibacterial agent were added and mixed to prepare a pellet-shaped master batch. Next, the obtained master batch, a polypropylene resin, and a pigment were mixed so as to have a ratio as shown in Table 1, and a resin molded body having a thickness of 145 μm was produced using a calender molding machine. In addition, polyethylene resin was used as the thermoplastic resin.

Example 2
The polypropylene resin was heated and melted, and an organic antibacterial / antifungal agent A, an organic antibacterial / antifungal agent B, and an inorganic antibacterial agent were added and mixed to prepare a pellet-shaped master batch. Next, the obtained master batch, a polypropylene resin, and a pigment were mixed so as to have a ratio as shown in Table 1, and a resin molded body having a thickness of 120 μm was produced using a calender molding machine.

Example 3
The polypropylene resin was heated and melted, and an organic antibacterial / antifungal agent A and an organic antibacterial / antifungal agent D were kneaded and compression-molded to produce a resin molded body having a thickness of 150 μm.

Example 4
The polypropylene resin was heated and melted, and an organic antibacterial / antifungal agent C and an organic antibacterial / antifungal agent B were kneaded and compression-molded to produce a resin molded body having a thickness of 150 μm.

Example 5
The polypropylene resin was heated and melted, and an organic antibacterial / antifungal agent A and an organic antibacterial / antifungal agent E were kneaded and compression-molded to produce a resin molded body having a thickness of 150 μm.

Example 6
The thermoplastic resin was heated and melted, and an organic antibacterial / antifungal agent A, an organic antibacterial / antifungal agent B, and an inorganic antibacterial agent were added and mixed to prepare a pellet-shaped master batch. Next, the obtained master batch, a mixture of a polypropylene resin and a pigment, and a mixture of a polypropylene resin and a pigment were co-extruded with an extruder so as to have a ratio as shown in Table 1. A resin molded body was formed by laminating a resin layer containing an antibacterial and fungicide having a thickness of 40 μm and a resin layer containing no antibacterial and fungicide having a thickness of 60 μm. In addition, polyethylene resin was used as the thermoplastic resin. The surface layer of the obtained resin molded product is a resin layer containing an antibacterial and antifungal agent.

Example 7
The thermoplastic resin was heated and melted, and an organic antibacterial / antifungal agent A, an organic antibacterial / antifungal agent B, and an inorganic antibacterial agent were added and mixed to prepare a pellet-shaped master batch. Next, a mixture of the polypropylene resin and the pigment, and a mixture of the obtained master batch, the polypropylene resin, and the pigment were co-extruded with an extruder so as to have a ratio as shown in Table 1. A resin molded body was prepared in which a 60 μm-thick antibacterial / fungicide-free resin layer and a 40 μm-thick antibacterial / fungicide-containing resin layer were laminated. In addition, polyethylene resin was used as the thermoplastic resin. The surface layer of the obtained resin molded article is a resin layer containing no antibacterial and antifungal agent.

Example 8
The polypropylene resin was heated and melted, and an organic antibacterial / antifungal agent A and an organic antibacterial / antifungal agent F were kneaded and compression-molded to produce a resin molded body having a thickness of 150 μm.

Comparative Example 1
The thermoplastic resin was heated and melted, and an organic antibacterial and fungicide B was added thereto and mixed to prepare a pellet-shaped master batch. Next, the master batch, the polypropylene resin, and the pigment were mixed so as to have a ratio as shown in Table 1, and a resin molded body having a thickness of 120 μm was produced using a calender molding machine. In addition, polyethylene resin was used as the thermoplastic resin.

Comparative Example 2
The thermoplastic resin was heated and melted, and an organic antibacterial and fungicide B was added thereto and mixed to prepare a pellet-shaped master batch. Next, the master batch, the polypropylene resin, and the pigment were mixed so as to have a ratio as shown in Table 1, and a resin molded body having a thickness of 125 μm was produced using a calender molding machine. In addition, polyethylene resin was used as the thermoplastic resin.

Comparative Example 3
The polypropylene resin was heated and melted, and an organic antibacterial / antifungal agent A and an organic antibacterial / antifungal agent C were kneaded and compression-molded to produce a resin molded body having a thickness of 150 μm.

Evaluation The obtained resin molded body was evaluated by the following method.
Thickness of Resin Molded Body (Resin Film) The thickness of the obtained resin molded body (Examples 1 to 8 and Comparative Examples 1 to 3) was measured by the following procedure. In the resin molded product, ten A4 size regions were arbitrarily selected. The thickness at each of the four vertexes and the center in each region was measured using a micrometer (accuracy: 0.01 mm, manufactured by Nippon Fujikoshi Co., Ltd.). The average value of the thickness of the five regions was defined as the thickness of each region, and the average value of the thickness of the ten regions was defined as the thickness of the resin molded body.

Test 1: Heat resistance and dissolution test under high temperature environment Second organic antibacterial fungicide (OIT) and first organic antibacterial agent in high temperature environment (for example, assuming use of a bathroom dryer) The heat resistance and the dissolution property in water of the antifungal agent (ZPT) were evaluated as follows.
Preparation of heat-degraded sample A heat-degraded sample was prepared by the following procedure. A resin molded body 700 (2.5 cm × 2.5 cm) made of PET resin without an organic antibacterial and antifungal agent was coated on one entire surface of the resin molded body 600 (2.5 cm × 2.5 cm, thickness 145 μm) of Example 1. And a thickness of 1 mm) using a double-sided tape (for example, Nystack (manufactured by Nichiban Co., Ltd.)) to obtain a laminate sample 800 as shown in FIG. The obtained laminate sample 800 was placed flat on the resin plate 900 such that the resin molded body 600 containing the organic antibacterial and antifungal agent was facing upward (atmosphere side). The resin plate 900 on which the laminate sample 800 was placed was placed in the center of a 45 ° C. constant temperature bath, and allowed to stand for 6, 10, and 72 days to produce heat-degraded samples S ₆ , S _10, and S ₇₂ . . On the other hand, a laminate sample 800 itself was used as a non-heat-treated sample _{S 0.} The following tests were performed using these heat-degraded samples S ₆ , S ₁₀ and S ₇₂ and the non-heat-treated sample S ₀ .

Elution speed of second organic antibacterial and antifungal agent (OIT) 5 ml of ultrapure water was put into a glass bottle, and the temperature was kept at 40 ° C. The entire surface (2.5 cm × 2.5 cm) of the heat-degraded samples S ₆ , S ₁₀ and S ₇₂ and the non-heat-treated sample S ₀ on the side of the resin molded product layer containing the organic antibacterial and antifungal agent is in contact with hot water at 40 ° C. The sample was floated on a warm water surface as described above. The glass bottle was sealed with a lid, and the sample was allowed to stand at 40 ° C. for 1 hour. Thereafter, the sample was removed from the glass bottle. Next, 1.5 ml (L _H ) of hexane was added to the glass bottle, the lid was closed and sealed, and the mixture was thoroughly stirred, and the OIT eluted in water was extracted into hexane. The concentration of OIT of hexane solution _{(O A)} was calculated by GC / MS. The laboratory equipment such as a glass bottle was used after being cleaned in advance with an alkaline cleaning agent (for example, Contaminone B manufactured by Wako Pure Chemical Industries, Ltd.).

On the other hand, instead of the resin molded article of Example 1 (2.5 cm × 2.5 cm, thickness 145 μm) containing an organic antibacterial / fungicide, a resin molded article made of polypropylene resin without containing an organic antibacterial / fungicide ( 2.5 cm × 2.5 cm, except for using the thickness 145 .mu.m), in the same procedure as for the thermal degradation samples were prepared laminate sample _{S B.} This for samples _{S B,} it was measured at GC / MS under the same conditions as above, and calculate the concentration of the OIT of operation blank _{(O B).}

From the following formula, the elution rate ( _VOIT ) of _OIT eluted from the resin molded body was determined.
_{V OIT = O S × L H} / (S × T) = (O A -O B) × L H / (S × T)
V _OIT : elution rate of OIT eluted from the resin molded product (g / cm2 / h)
O _S: concentration of OIT eluted from the resin molded body _{(g / ml) = O A} -O B
O _A : OIT concentration of hexane solution (g / ml)
O _B : OIT concentration of operation blank (g / ml)
L _H : amount of hexane (1.5 ml)
S: Resin molded body area (2.5 × 2.5 cm ² )
T: elution time (hour)

Elution rate of the first organic antibacterial and antifungal agent (ZPT) Two polypropylene bottles were prepared for each of the thermally degraded samples S ₆ , S ₁₀ and S ₇₂ and the non-heat-treated sample S ₀ , and ultrapure water was used for each bottle. 20 ml (L _W ) was charged and kept at 40 ° C. The entire surface (2.5 cm × 2.5 cm) of the sample (S ₆ , S ₁₀ , S ₀ ) on the side of the resin molded product layer containing the organic antibacterial and antifungal agent comes into contact with hot water at 40 ° C. in one bottle. As above, the sample was floated on a warm water surface. One bottle was sealed with a lid, and the sample was allowed to stand at 40 ° C. for 1 hour (first time). Then, the sample was taken out from one bottle, and the sample was floated on the hot water surface such that the entire surface that was brought into contact with the hot water for the first time came into contact with the hot water at 40 ° C. in the other bottle. The other bottle was sealed with a lid, and the sample was allowed to stand at 40 ° C. for 1 hour (second time). Thereafter, the sample was taken out from the other bottle, and ultrapure nitric acid was added to the other bottle to which the second contact was performed so that the concentration of nitric acid was 5 vol%. The zinc ion concentration (Zn _A ) of this nitric acid solution was calculated by ICP-MS. Experimental equipment such as a polypropylene bottle was previously cleaned with a 2 mol / L nitric acid aqueous solution, and resin tweezers were used to avoid contamination of metal and the like.

  The present inventors have found through experiments that the second organic antibacterial and antifungal agent (ZPT) tends to segregate in the vicinity of the surface of the resin molded article due to heat or the like during the production of the resin molded article. Therefore, the second organic antibacterial and antifungal agent segregated near the surface by the first contact was eluted and removed in advance. After the second contact, the second organic antimicrobial fungicide will elute from the sample at a stable elution rate. The operation for confirming the stable dissolution rate is carried out as required for any organic antibacterial and fungicide.

On the other hand, the laminate samples _{S B,} was measured by ICP-MS with the same conditions as above, and calculate the concentration of zinc ions in operation blank (Zn _B).

From the following formula, the elution rate ( _VZn ) of zinc ions eluted from the resin molded body was determined.
V _Zn = Zn _S × L _W / (S × T) = (Zn _A −Zn _B ) × L _W / (S × T)
V _Zn : dissolution rate of zinc ions eluted from the resin molded product (g / cm ² / h)
Zn _S: Concentration of the eluted zinc ion from the resin molded body _{(g / ml) = Zn A} -Zn B
Zn _A : concentration of zinc ion in nitric acid solution (g / ml)
Zn _B : concentration of zinc ion in operation blank (g / ml)
L _W : amount of ultrapure water (20 ml)
S: Resin molded body area (2.5 × 2.5 cm ² )
T: elution time (hour)

The dissolution rate of _ZPT (V _ZPT ) was determined from the following equation.
V _ZPT = V _Zn / Zn atomic weight × ZPT molecular weight

Result The second organic antibacterial and antifungal agent (OIT) in a thermally deteriorated sample obtained by exposing the resin molded product of Example 1 to heat at 45 ° C. for 6 days, 10 days and 72 days. Table 2 shows the elution rate of the first organic antibacterial and fungicide (ZPT) at 40 ° C. The elution rate of the second organic antibacterial fungicide (OIT) was changed (decreased) by about 13 times before and after the heat treatment (for example, between day 0 and day 6 to day 10). On the other hand, the dissolution rate of the first organic antibacterial and antifungal agent (ZPT) hardly changed before and after the heat treatment (for example, comparison between day 0 and days 6 to 10). Specifically, the elution rate changed (increased) from only about 1.05 fold to about 1.60 fold. It was confirmed that the first organic antibacterial agent did not deteriorate even after the heat treatment, that is, it had heat resistance and stably eluted in water under a high temperature environment.

Test 2: Dissolution test under low-temperature environment In a low-temperature environment of 25 ° C or lower (for example, during the rainy season or autumn when mold easily grows), the second organic antibacterial fungicide (OIT) and the first organic antifungal agent are used. The dissolution property of the antibacterial antifungal agent (ZPT) in water was evaluated as follows.

Dissolution rate of the second organic antibacterial and antifungal agent (OIT) 5 ml of ultrapure water was put into a glass bottle and kept at 10 ° C, 15 ° C, 20 ° C or 25 ° C. The resin molding was performed such that the entire surface (2.5 cm × 2.5 cm, thickness 120 μm) of the resin molding of Comparative Example 1 containing only the second organic antibacterial and fungicide (OIT) was in contact with the low-temperature water. I floated my body above the cold water surface. The glass bottle was closed with a lid, and the resin molded body was allowed to stand at 10 ° C., 15 ° C., 20 ° C. or 25 ° C. for 24 hours. Thereafter, the resin molded body was taken out of the glass bottle. Next, 1.5 ml (L _H ) of hexane was added to the glass bottle, the lid was sealed, the mixture was stirred well, and the OIT eluted in water was extracted into hexane. The concentration of OIT of hexane solution _{(O A)} was calculated by GC / MS. The laboratory equipment such as a glass bottle was used after being cleaned in advance with an alkaline cleaning agent (for example, Contaminone B manufactured by Wako Pure Chemical Industries, Ltd.).

On the other hand, instead of the resin molded article (2.5 cm × 2.5 cm, thickness 120 μm) of Comparative Example 1 containing only the second organic antibacterial / fungicide (OIT), polypropylene containing no organic antibacterial / fungicide was used. Using a resin molded body (2.5 cm × 2.5 cm, thickness 145 μm) made of resin, measurement was performed by GC / MS under the same conditions as above, and the OIT concentration (O _B ) of the operation blank was calculated.

From the following formula, the elution rate ( _VOIT ) of _OIT eluted from the resin molded body was determined.
_{V OIT = O S × L H} / (S × T) = (O A -O B) × L H / (S × T)
V _OIT : elution rate of OIT eluted from the resin molded product (g / cm2 / h)
O _S: concentration of OIT eluted from the resin molded body _{(g / ml) = O A} -O B
O _A : OIT concentration of hexane solution (g / ml)
O _B : OIT concentration of operation blank (g / ml)
L _H : amount of hexane (1.5 ml)
S: Resin molded body area (2.5 × 2.5 cm ² )
T: elution time (hour)

Elution rate of the first organic antibacterial and antifungal agent (ZPT) Two polypropylene bottles are prepared, 20 ml (L _W ) of ultrapure water is put in each bottle, one bottle is set at 40 ° C., and the other bottle is set at 40 ° C. The temperature was kept at 10 ° C, 15 ° C, 20 ° C or 25 ° C. One side of the entire resin surface (2.5 cm × 2.5 cm) of the resin molded product (2.5 cm × 2.5 cm, thickness 125 μm) of Comparative Example 2 containing only the first organic antibacterial / antifungal agent (ZPT) is one bottle The resin molded body was floated on the water surface so as to come into contact with water at 40 ° C. One bottle was sealed with a lid, and the resin molded body was allowed to stand at 40 ° C. for 1 hour (first time). Thereafter, a sample was taken from one bottle and the first time the entire surface contacted with water at 40 ° C. was brought into contact with water kept at 10 ° C., 15 ° C., 20 ° C. or 25 ° C. in the other bottle, The sample was floated on the water surface. The other bottle was sealed with a lid, and the resin molded body was allowed to stand at 10 ° C., 15 ° C., 20 ° C., or 25 ° C. for 1 hour (second time). Thereafter, the resin molded product was taken out from the other bottle, and ultrahigh-purity nitric acid was added to the other bottle to which the second contact was performed so that the concentration of nitric acid was 5 vol%. The zinc ion concentration (Zn _A ) of this nitric acid solution was calculated by ICP-MS.

On the other hand, instead of the resin molded product (2.5 cm × 2.5 cm, thickness 125 μm) of Comparative Example 2 containing the first organic antibacterial / fungicide (ZPT), a polypropylene resin containing no organic antibacterial / fungicide was used. Was measured by ICP-MS under the same conditions as above using a resin molded body (2.5 cm × 2.5 cm, thickness 125 μm), and the zinc ion concentration (Zn _B ) of the operation blank was calculated.

From the following formula, the elution rate ( _VZn ) of zinc ions eluted from the resin molded body was determined.
V _Zn = Zn _S × L _W / (S × T) = (Zn _A −Zn _B ) × L _W / (S × T)
V _Zn : dissolution rate of zinc ions eluted from the resin molded product (g / cm ² / h)
Zn _S: Concentration of the eluted zinc ion from the resin molded body _{(g / ml) = Zn A} -Zn B
Zn _A : concentration of zinc ion in nitric acid solution (g / ml)
Zn _B : concentration of zinc ion in operation blank (g / ml)
L _W : amount of ultrapure water (20 ml)
S: Resin molded body area (2.5 × 2.5 cm ² )
T: elution time (hour)

The dissolution rate of _ZPT (V _ZPT ) was determined from the following equation.
V _ZPT = V _Zn / Zn atomic weight × ZPT molecular weight

Results Table 3 shows the dissolution rates of the second organic antibacterial and fungicide (OIT) and the first organic antibacterial and fungicide (ZPT) in a low-temperature environment. The first organic antibacterial agent (ZPT) hardly elutes in water at 10 ° C., 15 ° C., 20 ° C. and 25 ° C., while the second organic antibacterial agent The mold agent (OIT) could be eluted in any of water at 10 ° C, water at 15 ° C, water at 20 ° C, and water at 25 ° C. That is, the second organic antibacterial and fungicide (OIT) is lower in temperature (10 ° C., 15 ° C., 20 ° C. and 25 ° C.) than the first organic antibacterial and fungicide (ZPT). The rate of dissolution into water was always high, and it was confirmed that the substance eluted in low-temperature water in an amount capable of suppressing the growth of mold. In the second organic antibacterial and antifungal agent (OIT), for example, the dissolution rate in water at 25 ° C. is more than 9 times larger than the dissolution rate in water at 15 ° C., and the dissolution rate is 20 ° C. Was more than 7 times greater than the elution rate in water at 10 ° C.

Test 3: As a sample for evaluating the antifungal properties in dissolution and under fungus resistance test <br/> specimen a high temperature environment in the environment of high temperature and low temperature both thermal deterioration sample S ₆ prepared in Test 1 And S ₁₀ , and a thermally degraded sample S _{21 and a} non-heat-treated sample S ₀ which were produced by standing still in a thermostat at 45 ° C. for 21 days were used. Further, using the resin molded products of Examples 2 to 8, a heat-degraded sample was prepared and used in the same procedure as in Test 1. Furthermore, the resin molded products of Examples 1 to 8 and Comparative Examples 1 to 3 were used as samples for evaluating the dissolution property and antifungal property of the organic antibacterial fungicide in a low-temperature environment. These samples were immersed in disinfecting alcohol for about 1 minute, dried in a clean bench for 30 minutes or more, and subjected to a cleaning treatment, and used as test specimens.

Mold Resistance Test The resin molded articles of Examples 1 to 8 and Comparative Examples 1 to 3 were tested for mold resistance in a high-temperature environment with reference to JIS Z2911 test method B for plastic products. All samples, equipment, reagents and the like used in the test were sterilized.
Pre-incubation of test mold and preparation of test spore solution
The Cladosporium cladosporioides NBRC6348, following planting the slants of potato dextrose agar, after 7 days of culture at 25 ° C., inorganic salt solutions the number of spores using (fungus resistance test method prescribed in ^{JIS Z2911) 1 × 10 6 cfu} / The solution adjusted to ml was used as a test spore solution.

Preparation of culture medium on which test piece is placed Agar is added to the inorganic salt solution at a rate of 20 g / L, and D (+)-glucose (JIS K8824 standard) is added at a rate of 30 ± 1 g / L, and 120 ± 1. Autoclaved at 30 ° C. for 30 minutes. Thereafter, if necessary, the pH was adjusted to 6.0 to 6.5 with a sterilized 0.01 mol / L sodium hydroxide solution. 20 ml was dispensed into a Petri dish manufactured by Nipro Corporation to produce a glucose-added inorganic salt agar medium.

Inoculation and culture of test spores on test piece 0.1 ml of test spore solution was dropped on a glucose-added inorganic salt agar medium and spread with a con large. A test piece was placed thereon, and 9 drops of 11.1 μl of the test spore solution were inoculated at equal intervals on the test piece, and cultured in an environment at a temperature of 28 ° C. and a relative humidity of 97% or more.

Evaluation method of test 3 (mold resistance test) The growth state of the mold on the test piece was judged by a microscope and visually according to the following judgment criteria, and the judgment result after 4 weeks was determined as the final judgment result.
Judgment Criteria The following 0 to 3 were accepted (shown by ○ in Table 4), and 4 and 5 were failed (shown by × in Table 4):
0: No mold growth was observed with the naked eye and a microscope 1: Mold growth was not observed with the naked eye, but mold growth was observed with the microscope 2: Mold growth was observed with the naked eye Mold covers the liquid surface of less than 3 drops out of 9 drops 3: Mold growth is observed with the naked eye, and mold covers the liquid surface of less than 5 drops out of 9 drops of inoculated test spore liquid 4: Mycelium Mold grows well and covers more than 5 drops of liquid in 9 drops of inoculated test spore liquid 5: Mycelium grows vigorously, and mold covers all 9 drops of inoculated test spore liquid

Dissolution test in low-temperature environment As in Test 2, the resin molded products of Examples 1 to 8 and Comparative Examples 1 to 3 were tested for dissolution into low-temperature water and evaluated according to the following criteria.

Evaluation method of Test 2 In the resin molded article after the test, the dissolution rate of at least the second organic antibacterial fungicide into water at 10 ° C. was 1 × 10 ⁻¹⁰ g / cm ² / h or more. Was evaluated as a good one that satisfies the standard 1 for dissolution in a low-temperature environment, and "し た" is given in Table 4. Furthermore, as the water temperature increased from 10 ° C. to 20 ° C., the elution rate in water at 20 ° C. was at least twice as high as that in water at 10 ° C. The sample was evaluated as satisfactory, satisfying the criterion 2 of Table 2, and "表" was added to Table 4. On the other hand, when the dissolution rate of the second organic antibacterial and fungicide into water at 10 ° C. was less than 1 × 10 ⁻¹⁰ g / cm ² / h, it was evaluated as not satisfying the dissolution standard 1. In Table 4, "x" was added. In addition, as the water temperature increased from 10 ° C. to 20 ° C., the elution rate in water at 20 ° C. was less than twice that in water at 10 ° C. It was evaluated as not satisfying, and "x" was added to Table 4.
In the present invention, a resin molded product that satisfies at least criterion 1 passes the dissolution test in a low-temperature environment, and one that does not satisfy criterion 1 fails (even if criterion 2 is satisfied). The resin molded products satisfying the criteria 1 and 2 were evaluated to have very good dissolution properties in a low-temperature environment.

The results were as shown in Table 4.

  As shown in Table 4, the resin molded articles of Examples 1 to 4 and 8 exhibited good mold resistance test results even when heat-treated at 45 ° C for 6, 10, and 21 days, and The organic antibacterial and fungicide was eluted in low-temperature water. That is, according to the resin film containing the first and second organic antibacterial and fungicide agents of the present invention, even after the heat treatment, the first organic antibacterial and fungicide agents do not deteriorate and are stably exposed to high-temperature water. It is eluted and exhibits antifungal performance in a high-temperature environment, and as can be seen from satisfying both criteria 1 and 2 of Test 2, an amount of the second organic substance capable of suppressing the growth of mold even in low-temperature water. It was confirmed that the antibacterial agent was eluted and exhibited very good elution performance even under a low temperature environment, that is, antifungal performance. Although the result of the mold resistance test of the resin molded article of Example 5 when heat-treated at 45 ° C. for 21 days was not good, the result of the mold resistance test when heat-treated at 45 ° C. for 6 days and 10 days was not obtained. The results were good, and exhibited the antifungal performance in a high temperature environment required for the present invention.

  In Example 6, which is a resin molded article having a two-layer structure in which a resin layer containing an antibacterial and fungicide is laminated on a resin layer not containing an antibacterial and fungicide, the result of the mold resistance test before heat treatment is passed. Met. Even on the surface of the resin layer containing the antimicrobial antifungal agent which is a thin film having a thickness of 40 μm, the results of the mold resistance test are good after heat treatment at 45 ° C. for 6, 10, and 21 days, and The organic antibacterial and fungicide eluted even in low-temperature water.

  In Example 7, which is a resin molded article having a two-layer structure in which a resin layer containing no antibacterial and fungicide is laminated on a resin layer containing an antibacterial and fungicide, the result of the mold resistance test before heat treatment is passed. Met. Also, in an embodiment in which a resin layer containing no antibacterial and fungicide is provided as the uppermost layer of a resin film on the surface of the resin layer containing an antibacterial and fungicide, also at 45 ° C. for 6, 10 and 21 days After the heat treatment, the result of the mold resistance test is good, and the lowermost resin layer containing the antibacterial and fungicide from the lower resin layer to the uppermost layer of the resin film (not containing the antibacterial and fungicide) It was confirmed that the dissolution of the antibacterial and fungicide was maintained on the surface of the resin layer, and the antibacterial and fungicide effect was exhibited while protecting the lower resin layer containing the antibacterial and fungicide from damage.

  On the other hand, the resin molded product of Comparative Example 1 containing only the second organic antibacterial and antifungal agent failed the mold resistance test after heat treatment at 45 ° C. for 6, 10, and 21 days. It was confirmed that a sufficient antifungal effect could not be exhibited in a high temperature environment assuming the use of a dryer. In addition, the resin molded product of Comparative Example 2 containing only the first organic antibacterial and fungicide did not satisfy the criteria 1 of Test 2, and it was found that the organic antibacterial and fungicide was hardly eluted in low-temperature water. It was confirmed that in a low-temperature environment of 25 ° C. or less, such as during the rainy season when the breeding is easy to breed, a sufficient antifungal effect could not be exhibited. Further, similarly to Comparative Example 1, the resin molded article of Comparative Example 3 containing only a plurality of the second organic antibacterial and antifungal agents showed a mold resistance test result when heat-treated at 45 ° C. for 6, 10, and 21 days. It was rejected, and it was confirmed that a sufficient antifungal effect could not be exhibited in a high temperature environment.

1: ceiling member or wall member of a bathroom, 10: resin film, 11: substrate, 12: gypsum board, 500: bathroom unit, 510: bathtub, 520: floor, 531: counter, 533: mirror, 534: shower, 541 , 542, 543, 544: wall member, 550: ceiling member

Claims (13)

A ceiling member or a wall member of a bathroom including a resin film,
The resin film comprises a first organic antibacterial and antifungal agent and a second organic antibacterial and antifungal agent,
The first and second organic antibacterial and antifungal agents are eluted with water attached to the surface of the member, and impart antibacterial and antifungal properties to the surface of the member,
The first organic antibacterial and antifungal agent has an elution rate at 40 ° C. after leaving a ceiling member or a wall member of the bathroom at 45 ° C. for 240 hours, the ceiling member or the wall member of the bathroom. Is the same as its elution rate at 40 ° C. before being left under the above conditions,
The second organic antibacterial and fungicide has a higher elution rate than the first organic antibacterial and fungicide at a temperature of 10 ° C. and 20 ° C., and the ceiling of a bathroom. Member or wall member.   The first organic antibacterial and fungicide has a molecular weight of 190 or more and a melting point of 50 ° C or more, and the second organic antibacterial and fungicide has a molecular weight of less than 190 or a melting point of 25 ° C or less. The ceiling member or the wall member of the bathroom according to claim 1, comprising:   The bathroom ceiling member or wall member according to claim 1 or 2, wherein the resin film is a thermoplastic resin film.   The first organic antibacterial and fungicide includes pyridine, imidazole, triazole, iodine, arsenic, ether, organochlorine, biguanide, sulfamide, quaternary ammonium chloride, aldehyde, The ceiling member or wall member of a bathroom according to any one of claims 1 to 3, wherein the member is at least one selected from the group consisting of carboxylic acid-based, ester-based, and phenol-based antibacterial fungicides.   The first organic antibacterial and antifungal agent is zinc pyrithione (ZPT), copper pyrithione (CPT), thiabendazole (TBZ), carbendazim (MBC), tebuconazole, benzotonium chloride, cetylpyridinium chloride, oxybisphenoxyarsine (OBPA) 5.) The compound according to claim 4, wherein the compound is one or more compounds selected from the group consisting of triclosan, chlorothalonil (TPN), diiodomethylparatolyl sulfone, and 3-iodo-2-propynylbutylcarbamate (IPBC). Bathroom ceiling or wall members.   The second organic antibacterial and antifungal agent is a thiazoline, triazine, thiazole, phenol, carbamate, peroxide, pyridine, carboxylic acid, aldehyde, or alcohol organic antibacterial agent. The bathroom ceiling member or wall member according to any one of claims 1 to 5, which is one or more members selected from a group consisting of a fungicide.   The second organic antibacterial and antifungal agent is octylisothiazolinone (OIT), methylisothiazolinone (MIT), chloromethylisothiazolinone (CMI), benzisothiazolinone (BIT), n-butyl BIT, Thiocyanomethylthiobenzothiazole (TCMTB), tricyclazole, benzothiazole, benzoic acid, sorbic acid, caprylic acid, propionic acid, 10-undecylenic acid, potassium sorbate, potassium propionate, calcium propionate, sodium benzoate, sodium propionate The bathroom ceiling member or wall member according to claim 6, which is one or more members selected from the group consisting of glutaraldehyde, formaldehyde, orthophenylphenol (OPP), and biosol. The combination of the first and second organic antibacterial and antifungal agents,
A combination of pyridine zinc pyrithione (ZPT) and thiazoline octylisothiazolinone (OIT),
A combination of an imidazole-based thiabendazole (TBZ) and a thiazoline-based octylisothiazolinone (OIT);
A combination of pyridine zinc pyrithione (ZPT) and thiazole benzothiazole,
A combination of ether triclosan and thiazoline octylisothiazolinone (OIT);
A combination of iodine-based 3-iodo-2-propynylbutylcarbamate (IPBC) and thiazoline-based octylisothiazolinone (OIT);
A combination of pyridine zinc pyrithione (ZPT) and thiazole tricyclazole;
A combination of pyridine zinc pyrithione (ZPT) and thiazole thiocyanomethylthiobenzothiazole (TCMTB);
A combination of pyridine-based copper pyrithione (CPT) and thiazoline-based octylisothiazolinone (OIT);
A combination of pyridine-based copper pyrithione (CPT) and thiazole-based benzothiazole,
A combination of an imidazole thiabendazole (TBZ) and a thiazole benzothiazole,
A combination of triazole tebuconazole and thiazoline octylisothiazolinone (OIT);
A combination of triazole tebuconazole and thiazole benzothiazole,
At least one member selected from the group consisting of iodine-based 3-iodo-2-propynylbutylcarbamate (IPBC) and thiazole-based benzothiazole; and ether-based triclosan and thiazole-based benzothiazole. The bathroom ceiling member or wall member according to any one of claims 1 to 7, which is a combination.   The bathroom according to any one of claims 1 to 8, wherein the first organic antibacterial and antifungal agent and the second organic antibacterial and antifungal agent are each supported by an inorganic compound. Ceiling members or wall members.   The ceiling member or wall member of a bathroom according to any one of claims 1 to 9, wherein the resin film is disposed on an outermost surface.   The bathroom ceiling member or wall member according to any one of claims 1 to 10, which is used as a bathroom ceiling member or wall member further comprising a bathroom dryer.   A bathroom unit comprising the member according to any one of claims 1 to 11. The bathroom unit according to claim 12, further comprising a bathroom dryer.

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