JP7801415B2 - Anti-fungal molded products - Google Patents

Description

The present invention relates to anti-fungal molded articles. More specifically, it relates to anti-fungal molded articles made using polycarbonate resins containing specific structures.

In recent years, due to concerns about hygiene and cleanliness, there has been a demand for materials with antifungal properties for outdoor equipment covers, components used in wet areas such as kitchens, bathrooms, and toilets, as well as for housing equipment, home appliances such as refrigerators and air conditioners, medical equipment, and the exteriors of ATMs (automated teller machines), POS terminals, mobile phones, and smartphones installed in convenience stores. Various methods have traditionally been used to impart antifungal properties to materials. One example is a manufacturing method that involves mixing and kneading an active antifungal substance into the material during the manufacturing process. Among these methods, polycarbonate resin has been widely used in electronic devices, office machines, machinery, and automobiles due to its excellent heat and impact resistance. One proposed method for imparting antifungal properties to polycarbonate (PC) resin is the addition of methylsulfonyltetrachloropyridine (Patent Document 1). However, these methods require the use of expensive antifungal agents, which, while providing a certain level of antifungal performance, can result in high costs and can bleed out during use, gradually reducing the antifungal effect.

On the other hand, in recent years, concerns about the depletion of petroleum resources and the problem of increasing atmospheric carbon dioxide, which causes global warming, have attracted significant attention to biomass resources, which do not rely on petroleum as a raw material and are carbon-neutral (do not increase carbon dioxide when burned). In the field of polymers, biomass plastics produced from biomass resources have also been actively developed. Polycarbonate resins using biomass resources as raw materials and derived from ether diol residues, which can be produced from carbohydrates, as amorphous polycarbonate resins with high heat resistance have been investigated. In particular, the incorporation of isosorbide as a monomer into polycarbonate has been investigated (Patent Document 2). However, there have been no reports to date that discuss the antifungal properties of isosorbide polycarbonate. Furthermore, various PCs made from polyethylene glycol have been reported, but these have not been aimed at improving antifungal properties (Patent Documents 3 and 4).

JP 2014-24886 A WO 2004/111106 JP 2011-241277 A Special Publication No. 2002-522584

The object of the present invention is to provide a molded product made from polycarbonate resin that has excellent moldability, transparency, heat resistance, and moldability.

The inventors discovered that polycarbonate resins containing a specific structure and having a Tg within a specific range have excellent mildew resistance, transparency, heat resistance, and moldability, and completed the present invention. According to the present invention, the above-mentioned problems are solved by the following invention.

1. An anti-fungal molded article, characterized in that at least a portion of the surface of the molded article is coated with a polycarbonate resin containing a structural unit represented by the following formula (1) and having a glass transition temperature of 40°C or higher and 150°C or lower:
(In formula (1), _R1 and _R2 each independently represent a hydrogen atom or an aliphatic hydrocarbon having 1 to 4 carbon atoms. m is 1 to 4, and n is 2 to 150.)
2. The anti-fungal molded article according to the above item 1, wherein the polycarbonate resin further contains a structural unit represented by the following formula (2):
3. The anti-fungal molded article according to the preceding paragraph 1 or 2, wherein the polycarbonate resin contains the structural unit represented by formula (1) in an amount of 1% by weight or more and 80% by weight or less, based on 100% by weight of all structural units.
4. The molded article according to any one of the preceding paragraphs 1 to 3, wherein the polycarbonate resin has a specific viscosity of 0.15 or more and 1.5 or less.
5. The anti-fungal molded article according to any one of the above items 1 to 4, which has a water contact angle of 60° or less.
6. The antifungal molded article according to any one of items 1 to 5 above, wherein the constitutional unit represented by formula (1) is a constitutional unit represented by the following formula (3):
(In formula (3), _R3 represents a hydrogen atom or a methyl group, and n is an integer of 2 to 150.)
7. The anti-fungal molded article according to any one of items 1 to 6 above, which is an anti-fungal molded article for outdoor equipment covers such as outdoor lighting covers and smart meter covers, components and housing equipment used in wet areas such as kitchens, baths, and toilets, home appliances such as refrigerators and air conditioners, ATMs (automated teller machines), POS terminals, mobile phones, smartphones, personal computers, tablets, packaging materials, wallpaper, filters, switches, daily necessities and living materials, sanitary materials, clothing, and vehicles.
8. The antifungal molded article according to any one of the preceding paragraphs 1 to 7, wherein the components constituting the antifungal molded article are in the form of a porous body, fiber, nonwoven fabric, particle, film, sheet, tube, or powder.
9. The anti-fungal molded article according to any one of the above items 1 to 8, wherein the coating has a thickness of 0.1 μm to 1 mm.
10. The molded article according to any one of the preceding paragraphs 1 to 9, wherein the polycarbonate resin is coated by painting, spraying, or dipping.

The molded articles made from the polycarbonate resin used in this invention have excellent moldability, transparency, heat resistance, and moldability, and can therefore be used in a wide variety of applications, including outdoor lighting covers, smart meter covers, and other outdoor equipment covers; components used in wet areas such as kitchens, baths, and toilets; housing equipment; home appliances such as refrigerators and air conditioners; medical equipment; ATMs (automated teller machines) installed in convenience stores; POS terminals; mobile phones, smartphones, PCs, tablets; various packaging materials; wallpaper; various filters; various switches; daily necessities and household materials; sanitary materials; clothing; and various plastic parts for vehicles, offering exceptional industrial benefits.

The following describes in detail each component of the polycarbonate resin used in the present invention, their blending ratios, preparation methods, etc.

<Polycarbonate resin>
The polycarbonate resin used in the present invention contains a structural unit represented by the following formula (1).

In formula (1), m is 1 to 4, n is 2 to 150, and _R1 and _R2 each independently represent a hydrogen atom or an aliphatic hydrocarbon having 1 to 4 carbon atoms. Among these, m is preferably 2 to 4, and particularly preferably 2. The degree of polymerization n is preferably 2 to 100, more preferably 2 to 50, and particularly preferably 2 to 35.

The repeating unit in formula (1) is typically derived from a polyoxyalkylene glycol. The number-average molecular weight of the polyoxyalkylene glycol used is preferably 100 to 20,000, more preferably 100 to 5,000, and particularly preferably 200 to 2,000. Within this range, an excellent balance of flexibility, heat resistance, and mildew resistance is achieved. If the molecular weight is outside this range, transparency may be lost or the product may become water-soluble, making it unusable as a molded product.

More specific examples of polyoxyalkylene glycols include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polypropylene glycol.

In particular, polyoxyalkylene glycols represented by the following formula (3), i.e., polyethylene glycol or polypropylene glycol, are preferably used.

In formula (3), n is 2 to 150, and _R3 represents a hydrogen atom or a methyl group. The content of the structural unit represented by formula (1) or (3) is preferably 1% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, and particularly preferably 15% by weight or more, relative to 100% by weight of all structural units. The upper limit of the content is preferably 80% by weight or less, more preferably 70% by weight or less, even more preferably 50% by weight or less, and particularly preferably 30% by weight or less. Setting this weight ratio is preferable, as it provides an excellent balance of anti-fungal properties, heat resistance, and moldability. The weight ratio can be measured and calculated using a proton NMR spectrometer, JNM-AL400, manufactured by JEOL Ltd.

The polycarbonate resin used in the present invention preferably further contains a structural unit represented by formula (2).

Examples of formula (2) include structural units (2-1), (2-2), and (2-3) represented by the following formulas, which are stereoisomers.

These are ether diols derived from carbohydrates, and are substances obtained from natural biomass, making them one of the renewable resources. The structural units (2-1), (2-2), and (2-3) are called isosorbide, isomannide, and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch, followed by dehydration. Other ether diols can also be obtained by similar reactions, excluding the starting material.

Among isosorbide, isomannide, and isoidide, structural units derived from isosorbide (1,4;3,6-dianhydro-D-sorbitol) are particularly preferred due to their ease of production and excellent heat resistance.

The content of the structural unit represented by formula (2) is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more, particularly preferably 50% by weight or more, and most preferably 70% by weight or more, based on 100% by weight of all structural units. The upper limit of the content is preferably 99% by weight or less, more preferably 95% by weight or less, even more preferably 92% by weight or less, and particularly preferably 90% by weight or less. This weight ratio provides an excellent balance of anti-fungal properties, heat resistance, moldability, and biomass content, which is preferable. The weight ratio can be measured and calculated using a proton NMR spectrometer, JNM-AL400, manufactured by JEOL Ltd.

The polycarbonate resin used in the present invention may contain other structural units derived from various diol compounds other than the structural units represented by formula (1) and formula (2). The content of these other structural units is preferably 30% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight or less, and particularly preferably 5% by weight or less, based on 100% by weight of all structural units. Such diol compounds (diol monomers) may be aliphatic diol compounds, alicyclic diol compounds, or aromatic dihydroxy compounds, including the diol compounds described in WO 2004/111106 and WO 2011/021720. These may be used alone or in combination of two or more. Representative examples of diol components are shown below, but the present invention is not limited thereto.

The aliphatic diol compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1 ,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc.

Examples of the alicyclic diol compounds include cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecanedimethanol, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2,4,4-tetramethylcyclobutanediol, 1,1'-spirobiindane-6,6'-diol, decalin-2,6-dimethanol, norbornanedimethanol, and cyclopentane-1,3-dimethanol.

The aromatic dihydroxy compounds include α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (bisphenol M), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, bisphenol A, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (bisphenol AF), biphenol, 1,1-bis(4-hydroxyphenyl)-m-diisopropylbenzene ... 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-1,8-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-1,8-diphenyl fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1,8-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl) phenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2 ,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-3,6-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-3,6-diphenylfluorene, 9,9-bis (4-hydroxy-3-methylphenyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-4,5-diphenylfluorene fluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-4,5-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-diphenylfluorene , 2,2'-bis(2-hydroxyethoxy)-3,3'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-3,3'-dimethyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-dimethyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-dimethyl-1,1'-binaphthyl, 1,1'-bi-2-naphthol, dihydroxynaphthalene, etc.

(Method for producing polycarbonate resin)
The polycarbonate resin used in the present invention is produced by a reaction means known per se for producing ordinary polycarbonate resins, for example, a method of reacting a diol component with a carbonate precursor such as a carbonic acid diester. The basic means for these production methods will now be briefly described.

Transesterification reactions using a carbonate diester as a carbonate precursor are carried out by heating and stirring a specified proportion of diol components with the carbonate diester under an inert gas atmosphere, and then distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol. If necessary, a terminal capping agent, antioxidant, etc. may also be added.

The carbonate diester used in the transesterification reaction includes esters of optionally substituted aryl groups and aralkyl groups having 6 to 12 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 moles, more preferably 1.00 to 1.06 moles, per mole of the total dihydroxy compounds.

In addition, in melt polymerization methods, a polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

Preferred compounds of this type include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, and quaternary ammonium hydroxides of alkali metals and alkaline earth metals, and these compounds can be used alone or in combination.

Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium, dipotassium, dicesium, and dilithium salts of bisphenol A, and sodium, potassium, cesium, and lithium salts of phenol.

Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, barium diacetate, and barium stearate.

Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Other examples include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Other examples include bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

Examples of metal compounds include zinc-aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds. These compounds may be used alone or in combination.

The amount of these polymerization catalysts used is selected from the range of preferably 1×10 ⁻⁹ to 1×10 ⁻² equivalents, preferably 1×10 ⁻⁸ to 1×10 ⁻⁵ equivalents, more preferably 1×10 ⁻⁷ to 1×10 ⁻³ equivalents per mole of the diol component.

A catalyst deactivator can also be added in the latter stages of the reaction. Known catalyst deactivators are effectively used, but among these, ammonium salts and phosphonium salts of sulfonic acid are preferred. Salts of dodecylbenzenesulfonic acid, such as tetrabutylphosphonium dodecylbenzenesulfonate, and salts of paratoluenesulfonic acid, such as tetrabutylammonium paratoluenesulfonate, are even more preferred.

Preferably used sulfonic acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, octyl paratoluenesulfonate, and phenyl paratoluenesulfonate. Among these, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used.

When at least one polymerization catalyst selected from alkali metal compounds and/or alkaline earth metal compounds is used, the amount of these catalyst deactivators used is preferably 0.5 to 50 moles per mole of the catalyst, more preferably 0.5 to 10 moles, and even more preferably 0.8 to 5 moles.

(Specific viscosity: _ηSP )
The specific viscosity (η _SP ) of the polycarbonate resin has a lower limit of preferably 0.15 or more, more preferably 0.2 or more, even more preferably 0.25 or more, and particularly preferably 0.3 or more. The upper limit is preferably 1.5 or less, more preferably 1.0 or less, even more preferably 0.8 or less, particularly preferably 0.6 or less, and most preferably 0.5 or less. When the specific viscosity is in the above range, the strength and moldability of the molded article are good.

The specific viscosity referred to in the present invention is determined by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]

Specific viscosity can be measured, for example, as follows: First, polycarbonate resin is dissolved in methylene chloride in an amount 20 to 30 times its weight, and the soluble portion is collected by filtration through Celite. After removing the solution, the residue is thoroughly dried to obtain a solid soluble in methylene chloride. 0.7 g of this solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined using an Ostwald viscometer.

(Glass transition temperature: Tg)
The upper limit of the glass transition temperature (Tg) of the polycarbonate resin is 150° C. or lower, preferably 140° C. or lower, more preferably 130° C. or lower, even more preferably 125° C. or lower, and particularly preferably 120° C. or lower. The lower limit is 40° C. or higher, preferably 50° C. or higher, more preferably 60° C. or higher, even more preferably 65° C. or higher, and particularly preferably 70° C. or higher. A Tg within the above range is preferable because of good moldability and is more suitable for environments in which anti-fungal materials are used.
The glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Co., Ltd. at a temperature rise rate of 20° C./min.

(5% weight loss temperature: Td)
The lower limit of the 5% weight loss temperature of the polycarbonate resin is preferably 280°C, more preferably 300°C, even more preferably 330°C, and particularly preferably 350°C. The upper limit of the 5% weight loss temperature is preferably 400°C, more preferably 390°C, and even more preferably 380°C. Therefore, the 5% weight loss temperature (Td) of the polycarbonate resin (component A) is preferably 280 to 400°C. If the 5% weight loss temperature is within the above range, there is almost no decomposition of the resin when molding using the polycarbonate resin composition of the present invention, which is preferable. The 5% weight loss temperature is measured using a TGA (model TGA2950) manufactured by TA Instruments.

(water contact angle)
The water contact angle of the antifungal molded article of the present invention is preferably 60° or less, more preferably 58° or less, and even more preferably 56° or less. When the water contact angle is 60° or less, the surface is sufficiently hydrophilic, which is preferable for the expression of antifungal properties.

(Total light transmittance)
The antifungal molded article of the present invention has a total light transmittance at a thickness of 2 mm of preferably 80% or more, more preferably 85% or more, even more preferably 88% or more, and particularly preferably 90% or more. When the total light transmittance is in the above range, the molded article is particularly useful because it has excellent transparency and therefore excellent visibility inside the molded article.
The term "total light transmittance" as used in connection with the present invention indicates the level of transparency and means the ratio of transmitted light to incident light according to method E308 of ASTM-D1003-61.

(additives, etc.)
The polycarbonate resin used in the present invention may be blended with polymers other than the polymer of the present invention, heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antifungal agents, ultraviolet absorbers, mold release agents, and the like, within the range that does not impair the antifungal properties.

<Anti-fungal molded products>
The antifungal molded article of the present invention can be obtained by coating at least a portion of the surface of a molded article with the polycarbonate resin. Here, the "antifungal molded article" is suitably used for outdoor equipment covers such as outdoor lighting covers and smart meter covers, components and housing equipment used in wet areas such as kitchens, baths, and toilets, home appliances such as refrigerators and air conditioners, ATMs (automated teller machines) installed in convenience stores, POS terminals, mobile phones, smartphones, personal computers, tablets, various packaging materials, wallpaper, various filters, switches, daily necessities and living materials, sanitary materials, clothing, various plastic parts related to vehicles, etc.

(shape)
In the present invention, the material and shape of the members constituting the antifungal molded article are not particularly limited, and may be, for example, any of porous bodies, fibers, nonwoven fabrics, particles, films, sheets, tubes, powders, and the like.

(Molding method)
The polycarbonate resin used in the present invention can be molded by any method, such as injection molding, compression molding, extrusion molding, solution casting, electrospinning, etc. The polycarbonate resin used in the present invention has excellent moldability, heat resistance, and mold resistance, and can be used to produce various molded articles.

The polycarbonate resin used in the present invention can also be extruded to produce various profile extrusions, sheets, films, etc. Sheets and films can also be formed using methods such as inflation, calendaring, and casting. It can also be molded into heat-shrinkable tubing using a specific stretching procedure. The polycarbonate resin used in the present invention can also be molded into molded articles using methods such as rotational molding and blow molding.

(Surface treatment)
The antifungal molded article of the present invention may be one in which the polycarbonate resin used in the present invention is coated on at least a portion of the surface of the antifungal molded article. Methods for retaining the polycarbonate resin used in the present invention on the surface of the antifungal molded article include coating, spraying, dipping, etc., and any of these methods can be used without particular limitation. The film thickness is preferably 0.1 μm to 1 mm.

The present invention will be further explained below with reference to the following examples. However, the present invention is in no way limited to these examples. In the examples, parts are parts by weight and percentages are percentages by weight. Evaluations were performed using the following methods.

(Evaluation of polycarbonate resin)
(1) Polymer composition ratio (NMR)
The polymer composition ratio (molar ratio) was calculated by measuring with a proton NMR spectrometer, JNM-AL400, manufactured by JEOL Ltd.
(2) Specific viscosity (η _sp )
The pellets were dissolved in methylene chloride to a concentration of approximately 0.7 g/dL, and the viscosity was measured using an Ostwald viscometer (device name: RIGO AUTO VISCOSIMETER TYPE VMR-0525 PC) at 20° C. The specific viscosity η _sp was calculated using the following formula:
η _sp =t/t _o −1
t: flow time of sample solution; t _o : flow time of solvent only; (3) glass transition temperature (Tg)
The measurement was carried out using a DSC (model DSC2910) manufactured by TA Instruments, with approximately 10 mg of pellets being heated at a temperature increase rate of 20° C./min.
(4) 5% Weight Loss Temperature: This was measured using a TGA (Model TGA2950) manufactured by TA Instruments, by heating about 10 mg of pellets at a temperature increase rate of 20° C./min.

(Evaluation of molded products)
(1) Moldability Molded articles that were visually inspected for good appearance were rated ◯, and molded articles that were poorly dried or had poor appearance were rated x.
(2) Total Light Transmittance A 2 mm portion of the obtained molded article was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
(3) Water Contact Angle The water contact angle of the surface of the obtained molded article was measured using DM-501Hi manufactured by Kyowa Interface Science.
(4) Mold Resistance According to JIS Z2911 of the JIS standard, a 2 mm thick portion of a molded product obtained by the following method was cut off and used to carry out a test under the following conditions.

[Preparation of test spore solution]
The test fungi were inoculated onto potato dextrose agar medium and cultured at 25°C for 14 days. Spores were harvested using sterilized water containing 0.05% Tween 80. A spore solution was prepared using a solution prepared to make a 10% glucose peptone liquid medium so that the spore count was ^10-6 /ml. Equal amounts of each fungus species were mixed to prepare the test spore solution.
Each test sample was inoculated with the test spore liquid and cultured at 26°C ± 2°C and a relative humidity of 95 to 99% for 4 weeks.
[Test mold]
Aspergillus niger, Penicillium citrinum, Rhizopus oryzae, Cladosporium cladosporioides, Chaetomium globosum
[Criteria for determining mold resistance]
〇: No growth of hyphae is visible to the naked eye ×: Growth of hyphae is visible

[Example 1]
<Production of Polycarbonate Resin>
491.0 parts of isosorbide (hereinafter abbreviated as ISS), 140.0 parts of polyethylene glycol (molecular weight 1000, hereinafter abbreviated as PEG1000), 757.3 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and 3.7 × 10 ^-3 parts of barium stearate as a catalyst were heated to 180 ° C under a nitrogen atmosphere and melted. After confirming melting, the EI reaction step was initiated. After the start of depressurization, the pressure was reduced over 40 minutes while adjusting the final vacuum to 8.0 kPa, and after reaching 8.0 kPa, the vacuum was maintained at that level. Simultaneously with the start of depressurization, the temperature was increased at a rate of 30 ° C / hr until the final resin temperature reached 220 ° C. After reaching 220 ° C, the pressure was maintained at a vacuum of 1.0 kPa and a resin temperature of 220 ° C for 10 minutes until 80% of the theoretical amount of phenol was distilled off. After confirming that 80% had distilled off, the PA reaction step (early stage) was initiated. The temperature was increased at a rate of 0.5°C/min so that the final resin temperature was 230°C. In parallel with the temperature increase, the pressure was reduced over 60 minutes to a final vacuum of 1 kPa. Subsequently, the PA reaction process (later process) was initiated. In the later process, the temperature was increased at a rate of 1°C/min so that the final resin temperature was 240°C. In parallel with the temperature increase, the pressure was reduced over 20 minutes until the final vacuum reached 134 Pa. The reaction was terminated when a predetermined stirring power value was reached, and the mixture was discharged from the bottom of the reaction tank under nitrogen pressure. While cooling in a water tank, the mixture was cut into pellets using a pelletizer. Various evaluations were performed using the obtained resin, and the evaluation results are shown in Table 1.

<Polycarbonate resin molding>
The obtained pellets were dried under vacuum at 50°C for 12 hours, and then an injection molding machine (manufactured by The Japan Steel Works, Ltd., JSW J-75EIII) was used to mold a three-stage plate having a width of 50 mm, a length of 90 mm, and thicknesses of 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm) from the gate side, with an arithmetic mean roughness (Ra) of 0.03 μm, at a molding temperature of 200°C, a mold temperature of 40°C, and a molding cycle of 50 seconds. The evaluation results are shown in Table 2.

[Example 2]
<Production of Polycarbonate Resin>
The same procedures and evaluations as in Example 1 were carried out except that 1.3 parts of ISS 50, 70.0 parts of PEG 1000, 757.3 parts of DPC, and 3.7×10 ⁻³ parts of barium stearate as a catalyst were used.
<Polycarbonate resin molding>
The same procedures and evaluations as in Example 1 were carried out except that molding was carried out at a molding temperature of 230°C and a mold temperature of 70°C.

[Example 3]
<Production of Polycarbonate Resin>
The same procedures and evaluations as in Example 1 were carried out except that 460.3 parts of ISS, 140.0 parts of polyethylene glycol (molecular weight 400, hereinafter abbreviated as PEG400), 757.3 parts of DPC, and 3.7×10 ⁻³ parts of barium stearate as a catalyst were used.
<Polycarbonate resin molding>
The same procedures and evaluations as in Example 1 were carried out except that molding was carried out at a molding temperature of 190°C and a mold temperature of 40°C.

[Example 4]
<Production of Polycarbonate Resin>
The same procedures and evaluations as in Example 1 were carried out except that 363.2 parts of ISS, 152.4 parts of triethylene glycol (hereinafter abbreviated as TEG), 757.3 parts of DPC, and 3.7×10 ⁻³ parts of barium stearate as a catalyst were used.
<Polycarbonate resin molding>
The same procedures and evaluations as in Example 1 were carried out except that molding was carried out at a molding temperature of 190°C and a mold temperature of 40°C.

[Comparative Example 1]
<Production of Polycarbonate Resin>
The same procedures and evaluations as in Example 1 were carried out except that 511.5 parts of ISS, 757.3 parts of DPC, and 3.7×10 ⁻³ parts of barium stearate as a catalyst were used.
<Polycarbonate resin molding>
After drying at a drying temperature of 100°C for 8 hours, the mixture was molded at a molding temperature of 250°C and at a mold temperature of 90°C, and the same procedures and evaluations as in Example 1 were carried out.

[Comparative Example 2]
<Production of Polycarbonate Resin>
799.0 parts of bisphenol A, 757.3 parts of DPC, and 2.0 × 10 ^-4 parts of sodium hydroxide as a catalyst were heated to 200 °C under a nitrogen atmosphere and melted. After confirming melting, the EI reaction step was initiated. After the start of depressurization, the pressure was reduced over 20 minutes while adjusting the final vacuum to 8.0 kPa, and after reaching 8.0 kPa, this vacuum was maintained. Simultaneously with the start of depressurization, the temperature was raised at a rate of 30 °C/hr until the final resin temperature reached 240 °C. After reaching 240 °C, the pressure was maintained at a vacuum of 1.0 kPa and a resin temperature of 240 °C for 10 minutes until 80% of the theoretical amount of phenol had distilled off. After confirming that 80% had distilled off, the PA reaction step (early stage) was initiated. The pressure was reduced over 1.0 °C/60 minutes until the final resin temperature reached 280 °C. Subsequently, the PA reaction step (late stage) was initiated. In the latter step, the temperature was increased at a rate of 1°C/min so that the final resin temperature would be 300°C. In parallel with the temperature increase, the pressure was reduced over 20 minutes until the final reduced pressure reached 134 Pa. The reaction was terminated when a predetermined stirring power value was reached, and the mixture was discharged from the bottom of the reaction tank under nitrogen pressure. While cooled in a water tank, the mixture was cut into pellets using a pelletizer. The same operations and evaluations as in Example 1 were carried out.

<Polycarbonate resin molding>
After drying at a drying temperature of 100°C for 8 hours, the mixture was molded at a molding temperature of 280°C and at a mold temperature of 90°C, and the same procedures and evaluations as in Example 1 were carried out.

[Comparative Example 3]
<Production of Polycarbonate Resin>
The same procedures and evaluations as in Example 1 were carried out except that 429.7 parts of ISS, 560.0 parts of PEG1000, 757.3 parts of DPC, and 3.7×10 ⁻³ parts of barium stearate as a catalyst were used.
<Polycarbonate resin molding>
The pellets were dried at 23°C under vacuum for 12 hours, but the pellets fused together and could not be molded. Furthermore, when the pellets were molded without drying at a molding temperature of 180°C and a mold temperature of 40°C, silver staining occurred, resulting in a poor appearance.

[Comparative Example 4]
<Production of Polycarbonate Resin>
The same procedure as in Example 1 was carried out except that 507.4 parts of ISS, 168.0 parts of polyethylene glycol (molecular weight 6000, hereinafter abbreviated as PEG6000), 757.3 parts of DPC, and 3.7 × ¹⁰ parts of barium stearate as a catalyst were used. The polymer was cloudy and brittle, and various evaluations were impossible.

[Comparative Example 5]
<Production of Polycarbonate Resin>
The same procedures and evaluations as in Example 1 were carried out except that 470.6 parts of ISS, 280.0 parts of PEG1000, 757.3 parts of DPC, and 3.7×10 ⁻³ parts of barium stearate as a catalyst were used.
<Polycarbonate resin molding>
The pellets were dried at 23°C under vacuum for 12 hours, but the pellets fused together and could not be molded. Furthermore, when the pellets were molded without drying at a molding temperature of 180°C and a mold temperature of 40°C, silver staining occurred, resulting in a poor appearance.

As shown in Table 2, it has been found that by including a specific structure in the polycarbonate resin and having a Tg within a specific range, it is possible to achieve both moldability and mold resistance while maintaining transparency. The molded articles of the present invention are particularly suitable for applications such as outdoor equipment covers such as outdoor lighting covers and smart meter covers, components and housing equipment used in wet areas such as kitchens, baths, and toilets, home appliances such as refrigerators and air conditioners, ATMs (automated teller machines) installed in convenience stores, POS terminals, mobile phones, smartphones, personal computers, tablets, various packaging materials, wallpaper, various filters, switches, daily necessities and household materials, sanitary materials, clothing, and various plastic parts related to vehicles.

The polycarbonate resin used in this invention has excellent moldability, transparency, heat resistance, and mildew resistance, making it suitable for a wide range of applications, including outdoor equipment covers such as outdoor lighting covers and smart meter covers, components used in wet areas such as kitchens, baths, and toilets, housing equipment, home appliances such as refrigerators and air conditioners, ATMs (automated teller machines) installed in convenience stores, POS terminals, mobile phones, smartphones, PCs, tablets, various packaging materials, wallpaper, various filters, switches, daily necessities and household materials, sanitary materials, clothing, and various plastic parts for vehicles.

Claims (9)

An anti-fungal molded article, characterized in that at least a part of the surface of the molded article is coated with a polycarbonate resin containing a structural unit represented by the following formula (1) and having a glass transition temperature of 40°C or higher and 150°C or lower:
The polycarbonate resin is a polycarbonate resin further containing a structural unit represented by the following formula (2):
An anti-fungal molded article containing 10% by weight or more and 30% by weight or less of the structural unit represented by the formula (1) based on 100% by weight of all structural units.
(In formula (1), _R1 and _R2 each independently represent a hydrogen atom or an aliphatic hydrocarbon having 1 to 4 carbon atoms. m is 1 to 4, and n is 2 to 150.)
2. The molded article according to claim 1 , wherein the polycarbonate resin has a specific viscosity of 0.15 or more and 1.5 or less. 3. The molded article according to claim 1, which has a water contact angle of 60° or less. The anti-fungal molded article according to any one of claims 1 to 3 , wherein the constitutional unit represented by the formula (1) is a constitutional unit represented by the following formula (3):
(In formula (3), _R3 represents a hydrogen atom or a methyl group, and n is an integer of 2 to 150.) The anti-fungal molded article according to any one of claims 1 to 4, which is an anti-fungal molded article for outdoor equipment covers , components used around water, housing equipment , home appliances, ATMs (automated teller machines), POS terminals, mobile phones, smartphones, personal computers, tablets , packaging materials, wallpaper, filters, switches, daily necessities and living materials, sanitary materials, clothing, and vehicles. The anti-mold molded product according to claim 5, which is an outdoor equipment cover such as an outdoor lighting cover or a smart meter cover, a component or home equipment used around water such as a kitchen, a bath, or a toilet, or a home appliance such as a refrigerator or an air conditioner. 7. The antifungal molded article according to any one of claims 1 to 6 , wherein the member constituting the antifungal molded article has the shape of a porous body, fiber, nonwoven fabric, particle, film, sheet, tube or powder. The anti-fungal molded article according to any one of claims 1 to 7 , wherein the coating has a thickness of 0.1 µm to 1 mm. The molded article according to any one of claims 1 to 8 , wherein the polycarbonate resin is coated by painting, spraying or dipping.