Antiviral molded products

Abstract

To provide an antiviral molding composed of a polycarbonate resin having excellent antiviral property, transparency, heat resistance and moldability.SOLUTION: An antiviral molding is formed from a polycarbonate resin comprising a constitutional unit represented by the formula (1) with a glass transition temperature of 40°C or higher and 150°C or lower. (In the formula (1), R1 and R2 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] This invention relates to an antiviral molded article. More specifically, it relates to an antiviral molded article made of polycarbonate resin containing a specific structure. [Background technology]

[0002] In recent years, due to hygiene and a growing emphasis on cleanliness, there has been a demand for materials with antibacterial / antiviral properties for the exteriors of household equipment such as toilets, home appliances such as refrigerators and air conditioners, medical devices, ATMs (automated teller machines) and POS terminals installed in convenience stores, mobile phones, and smartphones. Traditionally, various methods have been used to impart antiviral properties to materials. For example, one method involves mixing and kneading active antiviral substances during the manufacturing process. Methods for imparting antiviral properties to resins include adding inorganic / organic antiviral agents (Patent Documents 1-3). However, these methods use expensive antiviral agents, resulting in high costs despite demonstrating a certain level of antiviral performance. Furthermore, antiviral agents generally possess a certain degree of toxicity, posing safety concerns. Additionally, the inclusion of antiviral agents impairs the transparency of the resin itself, sometimes resulting in insufficient transparency depending on the application. Therefore, there has been a need for resin molded products that exhibit high levels of antiviral properties without containing antiviral agents.

[0003] On the other hand, in recent years, due to concerns about the depletion of petroleum resources and the problem of increasing carbon dioxide in the atmosphere that causes global warming, biomass resources that do not depend on petroleum as raw materials and do not increase carbon dioxide when burned, thus achieving carbon neutrality, have attracted considerable attention. In the field of polymers, biomass plastics produced from biomass resources are being actively developed. As an amorphous polycarbonate resin that uses biomass resources as a raw material and has high heat resistance, polycarbonate resins using raw materials obtained from ether diol residues that can be produced from carbohydrates are being investigated. In particular, the use of isosorbide as a monomer and its incorporation into polycarbonate has been investigated (Patent Document 4). In a series of investigations, it has been reported that polycarbonate containing isosorbide has antibacterial properties as an inherent characteristic of the resin (Non-Patent Document 1). However, antiviral properties have not been investigated. In addition, various PCs using polyethylene glycol as a raw material have been reported, but they were not aimed at improving antiviral properties (Patent Documents 5, 6). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-181227 [Patent Document 2] Japanese Patent Publication No. 2021-165307 [Patent Document 3] International Publication No. 2019 / 045110 [Patent Document 4] International Publication No. 2004 / 111106 [Patent Document 5] Japanese Patent Publication No. 2011-241277 [Patent Document 6] 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

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide an antiviral molded article made of a polycarbonate resin excellent in antiviral properties, transparency, heat resistance, and moldability.

Means for Solving the Problems

[0007] The inventors of the present invention have found that a polycarbonate resin containing a specific structure and having a glass transition temperature (Tg) within a specific range is excellent in antiviral properties, transparency, heat resistance, and moldability, and have completed the present invention. According to the present invention, the above problems are solved by the following invention.

[0008] 1. An antiviral molded article characterized by being molded from 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.

[0009]

Chemical Formula

[0010] (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 antiviral molded article according to item 1 above, wherein the polycarbonate resin further contains a structural unit represented by the following formula (2).

[0011]

Chemical Formula

[0013] [Chemical formula]

[0014] (In the formula (3), R3 represents a hydrogen atom or a methyl group. n is 2 to 150.) <00..​​​​​​​​​The polycarbonate resin used in this invention has excellent antiviral properties, transparency, heat resistance, and moldability, and can therefore be widely used in a variety of applications, including residential equipment such as toilets, home appliances such as refrigerators and air conditioners, medical equipment, ATMs (automated teller machines) and POS terminals installed in convenience stores, mobile phones, smartphones, personal computers, tablets, various packaging materials, wallpaper, various filters, various switches, daily necessities and household goods, sanitary materials, clothing, and various plastic parts related to vehicles, and the industrial effects it provides are exceptional. [Modes for carrying out the invention]

[0016] The following will provide a detailed description of each component of the polycarbonate resin used in this invention, their blending ratios, and preparation methods. <Polycarbonate resin> The polycarbonate resin used in this invention contains a constituent unit represented by the following formula (1).

[0017] [ka]

[0018] 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.

[0019] The repeating units in formula (1) are usually derived from polyoxyalkylene glycol. The number-average molecular weight of the polyoxyalkylene glycol used is preferably 100 to 20000, more preferably 100 to 5000, and particularly preferably 200 to 2000. Within this range, an excellent balance of flexibility, heat resistance, and antiviral properties is obtained. Outside this range, transparency may not be obtained, or the material may become water-soluble and unsuitable for use as a molded article.

[0020] More specifically, examples of polyoxyalkylene glycols include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polypropylene glycol.

[0021] In particular, polyoxyalkylene glycol represented by the following formula (3), i.e., polyethylene glycol or polypropylene glycol, is preferably used.

[0022] [ka]

[0023] In formula (3), n is between 2 and 150, and R3 represents a hydrogen atom or a methyl group. The content of the constituent 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, based on 100% by weight of all constituent 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. This weight ratio is preferable because it provides an excellent balance of antiviral properties, heat resistance, and moldability. The weight ratio can be measured and calculated using proton NMR with JEOL Ltd.'s JNM-AL400.

[0024] The polycarbonate resin used in the present invention preferably further contains the constituent unit represented by formula (2).

[0025] [ka]

[0026] Examples of the constituent units (2-1), (2-2), and (2-3) represented by the following formulas, which are stereoisomers of formula (2), are given by formula (2-1), (2-2), and (2-3).

[0027] [ka]

[0028] These are carbohydrate-derived ether diols, substances that can also be obtained from natural biomass, and are considered a renewable resource. The constituent 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 be obtained by a similar reaction, except for the starting materials.

[0029] Among isosorbide, isomannide, and isoidide, the constituent units derived from isosorbide (1,4;3,6-dianhydro-D-sorbitol) are particularly preferred due to their ease of manufacture and excellent heat resistance.

[0030] The content of the constituent 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 constituent 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 is preferable because it provides an excellent balance of antiviral properties, heat resistance, moldability, and biomass content. The weight ratio can be measured and calculated using proton NMR with JEOL Ltd.'s JNM-AL400.

[0031] The polycarbonate resin used in the present invention may contain other structural units derived from various diol compounds other than those represented by formulas (1) and (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, and examples include the diol compounds described in International Publication No. 2004 / 111106 and International Publication No. 2011 / 021720. These may be used alone or in combination of two or more. Representative specific examples of diol components are shown below, but the invention is not limited thereto.

[0032] 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, and 2-n-butyl-2-ethyl-1 Examples include 3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexaneglycol, 1,2-octylglycol, 2-ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol.

[0033] 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'-spirobindan-6,6'-diol, decalin-2,6-dimethanol, norbornanedimethanol, and cyclopentane-1,3-dimethanol.

[0034] The aforementioned 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), and 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-diphenyl Luorene, 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 s(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(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 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.

[0035] (Method of manufacturing polycarbonate resin) The polycarbonate resin used in this invention is produced by conventional, self-known reaction methods for producing polycarbonate resins, such as reacting a diol component with a carbonate precursor such as a diester carbonate. The basic methods for these production methods will now be briefly described.

[0036] Transesterification reactions using diester carbonate as a carbonate precursor are carried out by heating a predetermined proportion of the diol component with the diester carbonate under an inert gas atmosphere while stirring, 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 usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the beginning, while distilling off the resulting alcohol or phenol. End-terminating agents, antioxidants, etc., may also be added as needed.

[0037] Examples of diester carbonates used in the transesterification reaction include esters such as aryl groups and aralkyl groups having 6 to 12 carbon atoms, which may be substituted. Specifically, diphenyl carbonate, ditrile carbonate, bis(chlorophenyl) carbonate, and m-cresyl carbonate are examples. Among 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 1 mole of the total dihydroxy compounds.

[0038] Furthermore, in the molten polymerization method, a polymerization catalyst can be used to accelerate the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.

[0039] Preferred examples of such compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, and quaternary ammonium hydroxides of alkali metals and alkaline earth metals. These compounds can be used individually or in combination.

[0040] 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 phenyl phosphate, disodium, dipotassium, dicesium, and dilithium salts of bisphenol A, and sodium, potassium, cesium, and lithium salts of phenol.

[0041] 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.

[0042] 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. Furthermore, examples include ammonia, bases or basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0043] Examples of metallic compounds include zinc-aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds. These compounds may be used individually or in combination of two or more.

[0044] The amount of these polymerization catalysts used is preferably 1 × 10 per mole of diol component. -9 ~1 × 10 -2 Equivalent, preferably 1 × 10 -8 ~1 × 10 -5 Equivalent, more preferably 1 × 10 -7 ~1 × 10 -3 Selected within the range of equivalents.

[0045] Furthermore, a catalyst deactivator can be added in the later stages of the reaction. Known catalyst deactivators can be effectively used, and among these, ammonium salts and phosphonium salts of sulfonic acid are preferred. Even more preferred are salts of dodecylbenzenesulfonic acid, such as tetrabutylphosphonium dodecylbenzenesulfonate, and salts of p-toluenesulfonic acid, such as tetrabutylammonium p-toluenesulfonate.

[0046] Furthermore, as esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate are preferably used. Among these, tetrabutylphosphonium dodecylbenzenesulfonate is the most preferably used.

[0047] When using at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds, the amount of these catalyst deactivators used is preferably 0.5 to 50 moles, more preferably 0.5 to 10 moles, and even more preferably 0.8 to 5 moles per mole of catalyst.

[0048] (Specific viscosity:η SP ) Specific viscosity (η) of polycarbonate resin SP The specific viscosity has a lower limit of preferably 0.15 or higher, more preferably 0.2 or higher, even more preferably 0.25 or higher, and particularly preferably 0.3 or higher. The upper limit is preferably 1.5 or lower, more preferably 1.0 or lower, even more preferably 0.8 or lower, particularly preferably 0.6 or lower, and most preferably 0.5 or lower. When the specific viscosity is within the above range, the strength and moldability of the molded product are good.

[0049] 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 a polycarbonate resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t - t0) / t0 [t0 is the dropping seconds of methylene chloride, t is the dropping seconds of the sample solution] In addition, as a specific measurement of the specific viscosity, it can be carried out, for example, in the following manner. First, the polycarbonate resin is dissolved in methylene chloride at 20 to 30 times its weight, and the soluble component is collected by celite filtration. Then, the solution is removed and dried thoroughly to obtain a solid of the methylene chloride-soluble component. The specific viscosity at 20°C is determined from a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride using an Ostwald viscometer.

[0050] (Glass transition temperature: Tg) The glass transition temperature (Tg) of the polycarbonate resin has an upper limit of 150°C or lower, preferably 140°C or lower, more preferably 130°C or lower, still more preferably 125°C or lower, and particularly preferably 120°C or lower. Also, the lower limit is 40°C or higher, preferably 50°C or higher, more preferably 60°C or higher, still more preferably 65°C or higher, and particularly preferably 70°C or higher. When Tg is within the above range, the moldability is good and preferable, and it becomes more suitable in an environment where an antiviral material is used.

[0051] The glass transition temperature (Tg) is measured using a 2910-type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20°C / min.

[0052] (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. When 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.

[0053] (water contact angle) The water contact angle of the antiviral molded article formed from the polycarbonate resin of the present invention is preferably 60° or less, more preferably 58° or less, and even more preferably 56° or less. A water contact angle of 60° or less is desirable for the surface to become sufficiently hydrophilic, which is favorable for the expression of antiviral properties. The lower limit of the water contact angle is not particularly limited, but is preferably 20° or more, and more preferably 30° or more.

[0054] (Total light transmittance) The antiviral molded article made from the polycarbonate resin of the present invention preferably has a total light transmittance of 80% or more, more preferably 85% or more, even more preferably 88% or more, and particularly preferably 90% or more at a thickness of 2 mm. A total light transmittance within the above range is particularly useful because it provides excellent transparency and thus excellent visibility of the inside of the molded article.

[0055] The term "total light transmittance" used in connection with this invention indicates the level of transparency and means the ratio of transmitted light to incident light according to method E308 of ASTM-D1003-61.

[0056] (Additives, etc.) The polycarbonate resin used in this invention may be blended with polymers other than the polymer of the present invention, as well as heat stabilizers, plasticizers, light stabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antiviral agents, ultraviolet absorbers, mold release agents, etc., to the extent that it does not impair the antiviral properties.

[0057] <Antiviral molded product> The antiviral molded article of the present invention can be obtained by molding the above polycarbonate resin. Here, "antiviral molded article" refers to a molded article having antiviral properties that can be suitably used in housing equipment 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 goods, sanitary materials, clothing, and various plastic parts related to vehicles.

[0058] (Antiviral activity value) The antiviral properties of the antiviral molded article of the present invention are preferably such that the antiviral activity value is 2.0 or higher, and more preferably 2.5 or higher, compared to the antiviral activity value of a polycarbonate resin composed of bisphenol A as an untreated sample, according to the ISO standard ISO 21702. If the antiviral activity value is less than 2.0, it cannot be said that the viral infectivity titer can be suppressed.

[0059] (shape) In the present invention, the material and shape of the components constituting the antiviral molded article are not particularly limited and may be, for example, porous materials, fibers, nonwoven fabrics, particles, films, sheets, tubes, powders, etc.

[0060] (Molding method) The antiviral molded articles produced from the polycarbonate resin of the present invention can be molded by any method, such as injection molding, compression molding, extrusion molding, solution casting, or electrospinning. The polycarbonate resin used in the present invention has excellent moldability, transparency, heat resistance, and antiviral properties, and can therefore be used in a variety of molded articles.

[0061] Furthermore, the polycarbonate resin used in this invention can be manufactured into various irregularly shaped extruded products, sheets, and films by extrusion molding. Inflation molding, calendering, and casting methods can also be used for forming sheets and films. It is also possible to form it into heat-shrinkable tubes through specific stretching operations. Additionally, the polycarbonate resin used in this invention can be molded into products by rotational molding or blow molding. [Examples]

[0062] The present invention will be further described below with reference to examples. However, the present invention is not limited in any way to these examples. Also, parts in the examples are parts by weight, and % are weight percent. The evaluation was carried out by the following method.

[0063] (Evaluation of polycarbonate resin) (1) Polymer composition ratio (NMR) The polymer composition ratio (molar ratio) was calculated by measuring it using a JEOL JNM-AL400 proton NMR spectrometer. (2) Specific viscosity (η sp ) The pellet was dissolved in methylene chloride to a concentration of approximately 0.7 g / dL, and measured at 20°C using an Ostwald viscometer (instrument name: RIGO AUTO VISCOSIMETER TYPE VMR-0525·PC). The specific viscosity η was also measured. sp This was obtained from the following formula. η sp = t / t0-1 t: Flow time of the sample solution t0: Flow time of solvent only (3) Glass transition temperature (Tg) The measurement was performed by heating approximately 10 mg of pellets at a heating rate of 20°C / min using a TA Instruments DSC (model DSC2910). (4)5% weight loss temperature The measurement was performed using a TA Instruments TGA (model TGA2950) by heating approximately 10 mg of pellet at a heating rate of 20°C / min.

[0064] (Evaluation of molded products) (1) Formability Products with a good visual appearance were marked with ○, while those with drying defects or other appearance defects were marked with ×. (2) Total light transmittance A 2mm section of the obtained molded product was measured using a Hitachi U-3310 spectrophotometer. (3) Water contact angle The water contact angle of the surface of the obtained molded product was measured using a DM-501Hi manufactured by Kyowa Interface Science. (4) Antiviral In accordance with the ISO standard ISO 21702, a 2mm thick section of the molded product obtained by the following method was cut and used, and the test was conducted according to the following procedure. (i) Drop 0.4 mL of virus solution onto a 5 cm square test piece and cover with a 4 cm square film. (ii) Leave the test specimen at 25°C for 24 hours. (iii) After standing, the virus on the test piece is washed out and collected, and the viral infectivity titer is measured. (iv) Calculate the antiviral activity value from the obtained viral infectivity titer. [Criteria for evaluating antiviral activity] Antiviral activity levels were used as the evaluation criterion for antiviral activity. Antiviral activity value = Log(Viral infectivity titer of untreated sample after 24 hours of standing: polycarbonate composed of bisphenol A) - Log(Viral infectivity titer of test sample after 24 hours of standing) A: Antiviral activity value = 2.5 or higher (significant antiviral effect compared to untreated sample) B: Antiviral activity value = 2.0 or higher (shows antiviral effect compared to untreated sample) C: Antiviral activity value = less than 2.0 (cannot be said to have antiviral effect)

[0065] [Example 1] <Manufacturing 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 × 10⁻¹⁶ parts of barium stearate as a catalyst. -3 The mixture was heated to 180°C under a nitrogen atmosphere and melted. After confirming that it had melted, the EI reaction process (transesterification reaction process) was started. After starting to reduce the pressure, the pressure was reduced over 40 minutes, adjusting it until the final pressure level reached 8.0 kPa, and then maintained at that level. 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 220°C. After reaching 220°C, the mixture was maintained at a pressure 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 been distilled off, the PA reaction process (early polymerization process) was started. The temperature was increased at a rate of 0.5°C / min until the final resin temperature reached 230°C. In parallel with the heating, the pressure was reduced over 60 minutes until the final pressure level reached 1 kPa. Subsequently, the PA reaction process (late polymerization process) was started. In the later polymerization step, the resin temperature was increased at a rate of 1°C / min until the final resin temperature reached 240°C. Simultaneously with the heating, 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 cooling in a water tank, the resin was cut with a pelletizer to obtain pellets. Various evaluations were performed using the obtained resin, and the evaluation results are shown in Table 1.

[0066] <Molding of polycarbonate resin> The obtained pellets were dried under vacuum at 50°C for 12 hours. Then, using an injection molding machine (JSW J-75EIII, manufactured by Japan Steel Works, Ltd.), a three-stage plate with a width of 50 mm, a length of 90 mm, and thicknesses of 3.0 mm (20 mm), 2.0 mm (45 mm), and 1.0 mm (25 mm) from the gate side, and an arithmetic mean roughness (Ra) of 0.03 μm was molded at a molding temperature of 200°C, a mold temperature of 40°C for each die, and a molding cycle of 50 seconds, and the evaluation results are shown in Table 2.

[0067] [Example 2] <Manufacturing of polycarbonate resin> ISS50 1.3 parts, PEG1000 70.0 parts, DPC75 7.3 parts, and barium stearate 3.7 × 10⁻¹⁴ as catalyst -3 Except for the use of a specific part, the operation and evaluation were exactly the same as in Example 1. <Molding of polycarbonate resin> Except for molding at a molding temperature of 230°C and a mold temperature of 70°C, the procedure and evaluation were exactly the same as in Example 1.

[0068] [Example 3] <Manufacturing of polycarbonate resin> ISS460.3 parts, polyethylene glycol (molecular weight 400, hereafter abbreviated as PEG400) 140.0 parts, DPC 757.3 parts, and barium stearate 3.7 × 10 as a catalyst -3 Except for the use of a specific part, the operation and evaluation were exactly the same as in Example 1. <Molding of polycarbonate resin> Except for molding at a molding temperature of 190°C and a mold temperature of 40°C, the procedure and evaluation were exactly the same as in Example 1.

[0069] [Comparative Example 1] <Manufacturing of polycarbonate resin> 799.0 parts bisphenol A, 757.3 parts DPC, and 2.0 × 10⁻¹⁶ parts sodium hydroxide as a catalyst -4The material was heated to 200°C under a nitrogen atmosphere using a special container and melted. After confirming that it had melted, the EI reaction process (transesterification reaction process) was started. After starting to reduce the pressure, the pressure was reduced over 20 minutes, adjusting it until the final pressure level reached 8.0 kPa, and then maintained at that level. 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 to 240°C, and the mixture was maintained for 10 minutes until 80% of the theoretical amount of phenol was distilled off. After confirming that 80% had been distilled off, the PA reaction process (early polymerization process) was started. The pressure was reduced at a rate of 1.0°C / 60 minutes until the final resin temperature reached 280°C. Subsequently, the PA reaction process (late polymerization process) was started. In the late polymerization process, the temperature was increased at a rate of 1°C / min until the final resin temperature reached 300°C. In addition, while raising the temperature, 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 mixture was discharged from the bottom of the reaction vessel under nitrogen pressure. Pelletizers were obtained by cutting the mixture while cooling it in a water tank. The exact same procedure and evaluation as in Example 1 were performed. <Molding of polycarbonate resin> The procedure and evaluation were exactly the same as in Example 1, except that the product was dried at a drying temperature of 100°C for 8 hours, then molded at a molding temperature of 280°C with each mold at 90°C.

[0070] [Comparative Example 2] <Manufacturing of polycarbonate resin> ISS4 29.7 parts, PEG1000 560.0 parts, DPC 757.3 parts, and barium stearate 3.7 × 10⁻¹⁴ as catalyst. -3 Except for the use of a specific part, the operation and evaluation were exactly the same as in Example 1. <Molding of polycarbonate resin> When dried at a drying temperature of 23°C under vacuum for 12 hours, the pellets fused together, making molding impossible. Furthermore, when molded at a molding temperature of 180°C and individual mold temperatures of 40°C without drying, silver formation occurred, resulting in a poor appearance.

[0071] [Comparative Example 3] <Manufacturing of polycarbonate resin> ISS507.4 parts, polyethylene glycol (molecular weight 6000, hereinafter abbreviated as PEG6000) 168.0 parts, DPC 757.3 parts, and barium stearate 3.7 × 10 as a catalyst -3 Aside from using a specific part, the procedure was exactly the same as in Example 1. The polymer was cloudy and brittle, making various evaluations impossible.

[0072] [Comparative Example 4] ISS470.6 parts, PEG1000 280.0 parts, DPC757.3 parts, and barium stearate 3.7 × 10⁻¹⁴ parts as catalyst. -3 Except for the use of a specific part, the operation and evaluation were exactly the same as in Example 1. <Molding of polycarbonate resin> When dried at a drying temperature of 23°C under vacuum for 12 hours, the pellets fused together, making molding impossible. Furthermore, when molded at a molding temperature of 180°C and individual mold temperatures of 40°C without drying, silver formation occurred, resulting in a defective appearance.

[0073] [Table 1]

[0074] [Table 2]

[0075] As shown in Table 2, it was found that both moldability and antiviral properties can be achieved by including a specific structure in the polycarbonate resin and having a Tg within a specific range. Furthermore, the inclusion of isosorbide increases the biomass content. The antiviral molded articles of the present invention are particularly suitable for applications such as residential equipment like toilets, home appliances like refrigerators and air conditioners, ATMs (automated teller machines) and POS terminals installed in convenience stores, mobile phones, smartphones, personal computers, tablets, various packaging materials, wallpaper, various filters, switches, daily necessities and household goods, sanitary materials, clothing, and various plastic parts related to vehicles. [Industrial applicability]

[0076] The polycarbonate resin used in this invention has excellent antiviral properties, transparency, heat resistance, and moldability, and can therefore be widely used in a variety of applications, including residential equipment such as toilets, home appliances such as refrigerators and air conditioners, ATMs (automated teller machines) and POS terminals installed in convenience stores, mobile phones, smartphones, personal computers, tablets, various packaging materials, wallpaper, various filters, switches, daily necessities and household goods, sanitary materials, clothing, and various plastic parts related to vehicles.

Claims

1. A molded article for use against influenza viruses, characterized by being molded from a polycarbonate resin having a glass transition temperature of 40°C or higher and 150°C or lower, and containing a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (2). 【Chemistry 1】 (In equation (1), R １ and R ２ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon with 1 to 4 carbon atoms. m is 1 to 4, and n is 2 to 150. 【Chemistry 2】

2. The molded article for use against influenza viruses according to claim 1, comprising 1% or more and 80% or less by weight of the constituent unit represented by formula (1) based on 100% by weight of all constituent units.

3. The molded article for use against influenza viruses according to claim 1 or 2, wherein the polycarbonate resin has a specific viscosity of 0.15 or more and 1.5 or less.

4. A molded article for use against influenza viruses according to any one of claims 1 to 3, wherein the water contact angle is 60° or less.

5. The molded article for use against influenza viruses according to any one of claims 1 to 4, wherein the constituent unit represented by formula (1) is the constituent unit represented by the following formula (3). 【Transformation 3】 (In equation (3), R ３ (where n represents a hydrogen atom or a methyl group; n is between 2 and 150.)

6. The anti-influenza virus molded article is an antiviral molded article 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 / household goods, clothing, or vehicles, as described in any one of claims 1 to 5.

7. The molded article for use against influenza viruses according to any one of claims 1 to 6, wherein the shape of the components constituting the molded article for use against influenza viruses is a porous body, fiber, nonwoven fabric, particle, film, sheet, tube, or powder.

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