Antibacterial molded products

Abstract

To provide an antibacterial molded article using a polycarbonate resin excellent in antibacterial properties, transparency, heat resistance and moldability.SOLUTION: The antibacterial molded article is characterized in that at least a part of the surface of a molded article is coated with a polycarbonate resin containing a constituent 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 a C1-4 aliphatic hydrocarbon; m is 1-4; and n is 2-150.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antibacterial molded article, and more particularly to an antibacterial molded article using a polycarbonate resin containing a specific structure. [Background technology]

[0002] In recent years, due to concerns about hygiene and cleanliness, there has been a demand for materials with antibacterial properties for the exteriors of home appliances such as toilets, home appliances such as refrigerators and air conditioners, medical equipment, and ATMs (automated teller machines), POS terminals, mobile phones, smartphones, and other devices installed in convenience stores. Various methods have traditionally been used to impart antibacterial properties to materials. One example is a manufacturing method in which active antibacterial substances are mixed and kneaded into the material during the manufacturing process. Among these, polycarbonate resin has been widely used in electronic devices, office machines, machinery, automobiles, and other applications due to its excellent heat resistance and impact resistance. Proposed methods for imparting antibacterial properties to polycarbonate (PC) resin include adding various phosphorus-based or phenolic antioxidants, heat stabilizers, and acid-modified olefin waxes to inorganic antibacterial agents (e.g., calcium phosphate, zeolite, zirconium phosphate, etc., carrying antibacterial metal ions such as silver, copper, or zinc) (see Patent Documents 1-3), adding an antibacterial agent containing glass that elutes silver ions (Patent Document 4), and adding an inorganic composite containing zinc as an essential component as an antibacterial component (Patent Document 5). However, these methods require the use of expensive antibacterial agents, resulting in high costs despite achieving a certain level of antibacterial performance. Furthermore, many antibacterial agents themselves generally have a certain degree of toxicity, posing safety concerns. Furthermore, the inclusion of antibacterial agents impairs the transparency of the resin itself, which can result in insufficient transparency depending on the application.

[0003] 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 6). A series of studies has reported that polycarbonates containing isosorbide have inherent bacteriorepellency (Non-Patent Document 1). Non-Patent Documents have shown that the higher the isosorbide ratio, the better the bacteriorepellency, with isosorbide homopolymers exhibiting the highest bacteriorepellency. However, according to the investigations of the present inventors, it was found that the antibacterial properties of isosorbide homopolymer are insufficient for use in antibacterial products. Furthermore, although various PCs made from polyethylene glycol have been reported, they were not intended to improve antibacterial properties (Patent Documents 7 and 8). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-240125 [Patent Document 2] Japanese Patent Application Publication No. 10-168294 [Patent Document 3] Japanese Patent Application Publication No. 11-323117 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-137068 [Patent Document 5] Japanese Patent Application Laid-Open No. 2005-239904 [Patent Document 6] International Publication No. 2004 / 111106 [Patent Document 7] Japanese Patent Application Laid-Open No. 2011-241277 [Patent Document 8] Special Publication No. 2002-522584 [Non-patent literature]

[0005] [Non-Patent Document 1] Kobunshi Ronbunshu (Volume 74, No. 6, pages 631-634, 2017) Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide an antibacterial molded article using a polycarbonate resin that has excellent antibacterial properties, transparency, heat resistance and moldability. [Means for solving the problem]

[0007] The present inventors have discovered that a polycarbonate resin containing a specific structure and having a Tg within a specific range is excellent in antibacterial properties, transparency, heat resistance, and moldability, and have completed the present invention. According to the present invention, the above-mentioned problems are solved by the following inventions.

[0008] 1. An antibacterial 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. [ka] (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 antibacterial molded article according to item 1 above, wherein the polycarbonate resin further contains a structural unit represented by the following formula (2): [ka] 3. An antibacterial molded article according to the preceding paragraph 1 or 2, wherein the polycarbonate resin contains the structural unit represented by the 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 antibacterial molded article according to any one of the preceding items 1 to 3, wherein the polycarbonate resin has a specific viscosity of 0.15 or more and 1.5 or less. 5. The antibacterial molded article according to any one of the preceding items 1 to 4, which has a water contact angle of 60° or less. 6. The antibacterial 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): [ka] (In formula (3), R3 represents a hydrogen atom or a methyl group, and n is 2 to 150.) 7. The antibacterial molded product is an antibacterial molded product according to any one of the preceding paragraphs 1 to 6, which is an antibacterial molded product for housing equipment, refrigerators, 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. 8. The antibacterial molded article according to any one of the preceding items 1 to 7, wherein the components constituting the antibacterial molded article are in the form of a porous body, fiber, nonwoven fabric, particle, film, sheet, tube, or powder. 9. The antibacterial molded article according to any one of the preceding items 1 to 8, wherein the coating has a thickness of 0.1 μm to 1 mm. 10. The antibacterial molded article according to any one of the preceding paragraphs 1 to 9, wherein the polycarbonate resin is coated by painting, spraying, or dipping. [Effects of the Invention]

[0009] The antibacterial molded articles made from the polycarbonate resin used in the present invention have excellent antibacterial properties, transparency, heat resistance and moldability, and can therefore be used in a wide variety of applications, including home appliances such as toilets, home appliances such as refrigerators and air conditioners, medical equipment, ATMs (automated teller machines) installed in convenience stores, POS terminals, mobile phones, smartphones, personal computers, tablets, various packaging materials, wallpaper, various filters, various switches, daily necessities and living materials, sanitary materials, clothing and various plastic parts related to vehicles, and the industrial effects they bring about are exceptional. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, the components of the polycarbonate resin used in the present invention, their blending ratios, preparation methods, etc. will be explained in detail one by one.

[0011] <Polycarbonate resin> The polycarbonate resin used in the present invention contains a structural unit represented by the following formula (1).

[0012] [ka]

[0013] 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.

[0014] The repeating unit in formula (1) is usually 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 antibacterial properties is achieved. Outside this range, transparency may not be achieved or the polyoxyalkylene glycol may become water-soluble, making it unusable as a molded product.

[0015] More specific examples of polyoxyalkylene glycols include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polypropylene glycol.

[0016] In particular, polyoxyalkylene glycols represented by the following formula (3), that is, polyethylene glycol or polypropylene glycol, are preferably used.

[0017] [ka]

[0018] In formula (3), n is 2 to 150, and R3 represents a hydrogen atom or a methyl group. The content of the structural units 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. Such a weight ratio is preferable, as it provides an excellent balance of antibacterial properties, heat resistance, and moldability. The weight ratio can be measured and calculated by proton NMR using a JNM-AL400 manufactured by JEOL Ltd.

[0019] The polycarbonate resin used in the present invention preferably further contains a structural unit represented by formula (2).

[0020] [ka]

[0021] The formula (2) is exemplified by structural units (2-1), (2-2) and (2-3) represented by the following formulae, which are stereoisomers.

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] These are ether diols derived from carbohydrates and can also be 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 and then dehydrating it. Other ether diols can also be obtained by similar reactions, except for the starting material.

[0026] Among isosorbide, isomannide and isoidide, the structural unit derived from isosorbide (1,4;3,6-dianhydro-D-sorbitol) is particularly preferred because of its ease of production and excellent heat resistance.

[0027] 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. Such a weight ratio is preferable because it provides an excellent balance of antibacterial properties, heat resistance, moldability, and biomass content. The weight ratio can be measured and calculated using proton NMR using a JNM-AL400 manufactured by JEOL Ltd.

[0028] 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 any of aliphatic diol compounds, alicyclic diol compounds, and 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.

[0029] Examples of 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, and the like.

[0030] Examples of the alicyclic diol compound include cyclohexanedimethanol, tricyclodecane dimethanol, 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, norbornane dimethanol, and cyclopentane-1,3-dimethanol.

[0031] Examples of the aromatic dihydroxy compound 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-hexafluoro Propane (bisphenol AF), biphenol, 1,1-bis(4-hydroxyphenyl)decane, bis(2-hydroxyethoxy)naphthalene, 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 fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-1,8-diphenylfluorene, 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 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)-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, 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,Examples of such hydroxynaphthyl compounds include 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, and dihydroxynaphthalene.

[0032] (Manufacturing method of 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.

[0033] The transesterification reaction using a carbonate diester as a carbonate precursor is carried out by stirring a predetermined ratio of diol components with the carbonate diester under heating in an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is typically in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning of the reaction to distill off the resulting alcohol or phenol. If necessary, a terminal capping agent, antioxidant, etc. may also be added.

[0034] The carbonic acid diester used in the transesterification reaction includes esters of an aryl group or an aralkyl group having 6 to 12 carbon atoms, which may be substituted. 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 mol, more preferably 1.00 to 1.06 mol, per mol of the total amount of dihydroxy compounds.

[0035] In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of such a polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

[0036] As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, etc. of alkali metals or alkaline earth metals are preferably used, and these compounds can be used alone or in combination.

[0037] 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 salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, and lithium salt of phenol.

[0038] 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.

[0039] 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.

[0040] Examples of metal compounds include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc. These compounds may be used alone or in combination of two or more.

[0041] The amount of the polymerization catalyst used is preferably 1×10 -9 ~1×10 -2 equivalent, preferably 1 x 10 -8 ~1×10 -5 equivalent, more preferably 1 x 10 -7 ~1×10 -3 It is selected within the range of equivalents.

[0042] A catalyst deactivator can also be added in the latter stage of the reaction. Known catalyst deactivators are effectively used as the catalyst deactivator, 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 more preferred.

[0043] Preferred examples of 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. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used.

[0044] 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 mol, more preferably 0.5 to 10 mol, and even more preferably 0.8 to 5 mol, per mol of the catalyst.

[0045] (Specific viscosity:η SP ) Specific viscosity of polycarbonate resin (η SP ) 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.

[0046] The specific viscosity referred to in the present invention is determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls]

[0047] The 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 matter is collected by filtration through Celite. After removing the solution, the mixture 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.

[0048] (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 antibacterial materials are used. The glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20°C / min.

[0049] (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.

[0050] (water contact angle) The water contact angle of the antibacterial 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 antibacterial properties.

[0051] (Total light transmittance) The antibacterial 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. A total light transmittance within the above range is particularly useful because it is excellent in transparency and therefore provides excellent visibility inside the molded article. The term "total light transmittance" as used in connection with the present invention denotes the level of transparency and means the ratio of transmitted light to incident light according to method E308 of ASTM-D1003-61.

[0052] (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, antibacterial agents, ultraviolet absorbers, mold release agents, and the like, within the scope of not impairing the antibacterial properties.

[0053] <Antibacterial molded products> The antibacterial molded article of the present invention can be obtained by coating at least a portion of the surface of the molded article with the polycarbonate resin. Here, the "antibacterial molded article" can be suitably used for household appliances such as 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.

[0054] (antibacterial activity value) The antibacterial activity of the antibacterial molded article of the present invention is preferably 2.0 or more, more preferably 3.0 or more, as measured in accordance with JIS Z2801 of the JIS standard, when a polycarbonate resin made from bisphenol A is used as an untreated sample. If the antibacterial activity value is less than 2, it cannot be said that bacterial growth can be inhibited.

[0055] (shape) In the present invention, the material and shape of the members constituting the antibacterial 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.

[0056] (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 antibacterial properties, and can be used to make various molded articles.

[0057] The polycarbonate resin used in the present invention can also be extruded to produce various profile extrusions, sheets, films, etc. For forming sheets and films, methods such as inflation, calendaring, and casting can also be used. Furthermore, it can be molded into heat-shrinkable tubing by a specific stretching operation. The polycarbonate resin used in the present invention can also be molded into molded articles by rotational molding, blow molding, etc.

[0058] (Surface treatment) The antibacterial 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 part of the surface of the antibacterial molded article. Methods for retaining the polycarbonate resin used in the present invention on the surface of the antibacterial molded article include coating, spraying, dipping, etc., and any of these methods can be used without any particular limitation. The film thickness is preferably 0.1 μm to 1 mm. [Example]

[0059] The present invention will be further explained below with reference to examples. However, the present invention is not limited to these examples. In the examples, parts are parts by weight and % is % by weight. Evaluations were made according to the following methods.

[0060] (Evaluation of polycarbonate resin) (1) Polymer composition ratio (NMR) Measurement was carried out by proton NMR using JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated. (2) Specific viscosity (η sp ) The pellets were dissolved in methylene chloride to a concentration of approximately 0.7 g / dL, and the specific viscosity (η) was measured at 20°C using an Ostwald viscometer (device name: RIGO AUTO VISCOSIMETER TYPE VMR-0525 PC). sp was calculated from the following formula: η sp =t / t o -1 t: Time in seconds for the sample solution to fall to : Number of seconds for methylene chloride to fall (3) Glass transition temperature (Tg) Using a TA Instruments DSC (Model DSC2910), approximately 10 mg of pellets were heated at a heating rate of 20°C / min for measurement. (4)5% weight loss temperature Using a TGA (model TGA2950) manufactured by TA Instruments, approximately 10 mg of pellets were heated at a temperature increase rate of 20°C / min and the measurement was carried out.

[0061] (Evaluation of molded products) (1) Formability Molded articles that were visually inspected for good appearance were rated ◯, and molded articles that had insufficient drying or poor appearance were rated x. (2) Total light transmittance A 2 mm section 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 resulting molded article was measured using a DM-501Hi manufactured by Kyowa Interface Science. (4) Antibacterial properties In accordance with JIS Z2801, a 2 mm thick portion of the molded product obtained by the method described below was cut off and used to conduct the test under the following conditions. *Bacterial liquid concentration: 1 / 500NB (NB: Nutrient Borth liquid basal medium) *Bacteria liquid dropping amount: 0.4ml *Storage temperature: 35±1℃ *Storage humidity: 90% or more *Storage time: 24±1 hours *Bacteria used: Staphylococcus aureus (NBRC12732), Escherichia coli (NBRC3972) [Antibacterial evaluation criteria] The antibacterial activity value was used as the evaluation standard for antibacterial properties. Antibacterial activity value = Log (viable bacteria count of untreated sample: polycarbonate made from bisphenol A) - Log (viable bacteria count of antibacterial sample) A: Antibacterial activity value = 3.0 or more (significant antibacterial effect compared to untreated sample) B: Antibacterial activity value = 2.0 or more (antibacterial effect compared to untreated sample) C: Antibacterial activity value = less than 2.0 (not considered to have antibacterial effect)

[0062] [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 barium stearate as a catalyst. -3 The resin was heated to 180°C under a nitrogen atmosphere and melted. After melting was confirmed, the EI reaction process was initiated. After depressurization began, the pressure was reduced over 40 minutes while adjusting the final vacuum level to 8.0 kPa. After reaching 8.0 kPa, the vacuum level 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 220°C. After reaching 220°C, the pressure was reduced to 1.0 kPa and the resin temperature was maintained at 220°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 process (early stage) was initiated. The temperature was raised at a rate of 0.5°C / min until the final resin temperature reached 230°C. In parallel with the temperature increase, the pressure was reduced over 60 minutes until the final vacuum level reached 1 kPa. Subsequently, the PA reaction process (late stage) was initiated. In the late stage, the temperature was raised at a rate of 1°C / min until the final resin temperature reached 240°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 the predetermined stirring power value was reached, and the resin was discharged from the bottom of the reaction vessel under nitrogen pressure. While cooled in a water bath, the resin was cut into pellets using a pelletizer. Various evaluations were performed using the obtained resin, and the evaluation results are shown in Table 1.

[0063] <Polycarbonate resin molding> The obtained pellets were dried under vacuum at 50°C for 12 hours, and then molded using an injection molding machine (Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 200°C, a mold temperature of 40°C for each mold, and a molding cycle of 50 seconds into a three-tiered plate having a width of 50 mm, a length of 90 mm, and thicknesses of 3.0 mm (20 mm length), 2.0 mm (45 mm length), and 1.0 mm (25 mm length) from the gate side, and an arithmetic mean roughness (Ra) of 0.03 μm. The evaluation results are shown in Table 2.

[0064] [Example 2] <Production of polycarbonate resin> ISS501.3 parts, PEG1000 70.0 parts, DPC757.3 parts, and barium stearate 3.7 x 10 as a catalyst -3 The same operations and evaluations as in Example 1 were carried out except that the same parts 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.

[0065] [Example 3] <Production of polycarbonate resin> ISS 460.3 parts, polyethylene glycol (molecular weight 400, hereinafter abbreviated as PEG400) 140.0 parts, DPC 757.3 parts, and barium stearate 3.7 × 10 as a catalyst -3 The same operations and evaluations as in Example 1 were carried out except that the same parts 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.

[0066] [Example 4] <Production of polycarbonate resin> ISS 363.2 parts, triethylene glycol (hereinafter abbreviated as TEG) 152.4 parts, DPC 757.3 parts, and barium stearate 3.7 × 10 as a catalyst -3 The same operations and evaluations as in Example 1 were carried out except that the same parts 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.

[0067] [Comparative Example 1] <Production of polycarbonate resin> 511.5 parts of ISS, 757.3 parts of DPC, and 3.7 x 10 barium stearate as a catalyst -3 The same operations and evaluations as in Example 1 were carried out except that the same parts 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 operations and evaluations as in Example 1 were carried out.

[0068] Comparative Example 2 <Production of polycarbonate resin> 799.0 parts of bisphenol A, 757.3 parts of DPC, and 2.0 x 10 sodium hydroxide as a catalyst -4 The resin was heated to 200°C under a nitrogen atmosphere using a pressure regulator to melt the resin. After confirming that the resin had melted, the EI reaction process was initiated. After the pressure reduction began, the pressure was reduced over 20 minutes, adjusting the final vacuum to 8.0 kPa. After reaching 8.0 kPa, the vacuum was maintained. Simultaneously with the start of the pressure reduction, the temperature was increased at a rate of 30°C / hr until the final resin temperature reached 240°C. After reaching 240°C, the pressure was reduced to 1.0 kPa and the resin temperature was maintained at 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 process (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 process (late stage) was initiated. In the late stage, the temperature was increased at a rate of 1°C / min until the final resin temperature reached 300°C. Concurrently 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 vessel under nitrogen pressure, cooled in a water bath, and cut into pellets using a pelletizer. The same operations and evaluations as in Example 1 were carried out.

[0069] <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 operations and evaluations as in Example 1 were carried out.

[0070] Comparative Example 3 <Production of polycarbonate resin> ISS 429.7 parts, PEG 1000 560.0 parts, DPC 757.3 parts, and barium stearate 3.7 x 10 as a catalyst -3 The same operations and evaluations as in Example 1 were carried out except that the same parts were used. <Polycarbonate resin molding> The pellets were dried at 23°C under vacuum for 12 hours, but they fused together and could not be molded. Furthermore, when the pellets were molded undried at a molding temperature of 180°C and mold temperatures of 40°C, silver staining occurred, resulting in a poor appearance.

[0071] Comparative Example 4 <Production of polycarbonate resin> 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 barium stearate as a catalyst -3 Except for using the same part, the same operation as in Example 1 was carried out. The polymer was cloudy and brittle, and various evaluations were impossible.

[0072] Comparative Example 5 ISS 470.6 parts, PEG 1000 280.0 parts, DPC 757.3 parts, and barium stearate 3.7 × 10 as a catalyst -3 The same operations and evaluations as in Example 1 were carried out except that the same parts were used. <Polycarbonate resin molding> The pellets were dried at 23°C under vacuum for 12 hours, but they fused together and could not be molded. Furthermore, when the pellets were molded undried at a molding temperature of 180°C and mold temperatures of 40°C, silver staining occurred, resulting in a poor appearance.

[0073] Comparative Example 6 99.5 parts of the bisphenol A polycarbonate resin obtained in Comparative Example 2 and 0.5 parts of KM10D2, a silver-based antibacterial agent manufactured by Sinanen Zeomic Co., Ltd., were mixed at a melting temperature of 270°C using a twin-screw extruder (TEX30α manufactured by The Japan Steel Works, Ltd., shaft diameter = 30 mmφ, L / D = 41) to obtain pellets for evaluation. Various evaluations were performed using the obtained resin, and the evaluation results are shown in Table 1.

[0074] <Polycarbonate resin molding> The obtained pellets were dried at 100°C for 12 hours, and then molded using an injection molding machine (Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 280°C, a mold temperature of 90°C, and a molding cycle of 50 seconds into a three-tiered 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, and an arithmetic mean roughness (Ra) of 0.03 μm. The evaluation results are shown in Table 2.

[0075] [Table 1]

[0076] [Table 2]

[0077] As shown in Table 2, it was found that the inclusion of a specific structure in the polycarbonate resin and a Tg within a specific range enable both moldability and antibacterial properties to be achieved. On the other hand, existing polycarbonate resin compositions containing antibacterial agents, such as those in Comparative Example 6, exhibit antibacterial properties, but are inferior in transparency compared to the inherent transmittance of the resin and, because they do not contain biomass raw materials, have a significant environmental impact. The antibacterial molded article of the present invention is particularly suitable for applications such as home appliances such as 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. [Industrial Applicability]

[0078] The polycarbonate resin used in the present invention has excellent antibacterial properties, transparency, heat resistance and moldability, and therefore can be used in a wide variety of applications, including home appliances such as toilets, refrigerators, air conditioners and other home appliances, 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 and various plastic parts related to vehicles.

Claims

1. An antibacterial molded article, characterized in that at least a part of the surface of the molded article is coated with a polycarbonate resin containing constitutional units represented by the following formula (1) and the following formula (2) and having a glass transition temperature of 40°C or higher and 150°C or lower, An antibacterial molded article, wherein the polycarbonate resin contains the structural unit represented by the formula (1) in a proportion of 1% by weight or more and 50% by weight or less, and the structural unit represented by the formula (2) in a proportion of 50% by weight or more and 99% by weight or less, relative to 100% by weight of all structural units. 【Chemistry 1】 (In formula (1), R １ and R ２ each independently represents a hydrogen atom or an aliphatic hydrocarbon having 1 to 4 carbon atoms; m is 1 to 4, and n is 2 to 150. 【Chemistry 2】

2. 2. The antibacterial 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. 3. The antibacterial molded article according to claim 1, wherein the water contact angle is 60° or less.

4. The antibacterial 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): 【Transformation 3】 (In formula (3), R ３ represents a hydrogen atom or a methyl group, and n is a number from 2 to 150.

5. The antibacterial molded article according to any one of claims 1 to 4, which is an antibacterial molded article for use in housing equipment, refrigerators, 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.

6. The antibacterial molded article according to any one of claims 1 to 5, wherein the components constituting the antibacterial molded article are in the form of a porous body, fiber, nonwoven fabric, particle, film, sheet, tube or powder.

7. The antibacterial molded article according to any one of claims 1 to 6, wherein the coating has a film thickness of 0.1 µm to 1 mm.

8. The antibacterial molded article according to any one of claims 1 to 7, wherein the polycarbonate resin is coated by painting, spraying or dipping.

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