Antiviral polycarbonate resin composition and molded article made thereof

Abstract

The present invention provides an antiviral polycarbonate resin composition and molded articles made therefrom that offer excellent antiviral properties, thermal stability, color, and impact resistance. [Solution] A resin composition characterized by containing (A) 100 parts by weight of polycarbonate resin (component A), (B) 1 to 15 parts by weight of organic antiviral agent (component B), and (C) 0.1 to 20 parts by weight of surfactant (component C), wherein the antiviral activity value at 23°C, as measured by a test method based on ISO 21702, is 2.0 or higher.

Description

[Technical Field]

[0001] The present invention relates to an antiviral polycarbonate resin composition and a molded article made therefrom, which is excellent in antiviral properties, thermal stability, hue, and impact resistance. [Background technology]

[0002] Polycarbonate resin is an engineering plastic that generally possesses excellent transparency, impact resistance, dimensional stability, and flame retardancy, and is widely used in various fields such as electrical and electronics, automotive, and office equipment. In recent years, pandemics (infection outbreaks) caused by viruses spreading rapidly in a short period of time, resulting in the global spread of infectious diseases and a large number of infected people, have become a social problem. In particular, the spread of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and the emergence of its variants have become a global problem. In order to take measures against such pandemics, there is a demand for materials with antiviral properties for a wide variety of applications, including housing equipment and toiletries, home appliances such as televisions and air conditioners, medical equipment, ATMs (automated teller machines) installed in convenience stores, POS terminals, and mobile devices such as smartphones and tablets.

[0003] As a method for imparting antiviral performance to a polycarbonate resin, a method of adding an antiviral agent of an inorganic metal compound such as a silver compound or a copper compound (Patent Document 1) has been disclosed. However, in the case of a resin that requires a high processing temperature such as a polycarbonate resin, the thermal stability during molding is significantly reduced due to the catalytic action of the silver compound or the copper compound, and there are problems such as causing impact resistance, heat resistance, and discoloration. Further, a method of adding an antibacterial / antiviral agent of a quaternary ammonium salt or a pyridinium salt system to a transparent resin (Patent Document 2) has been disclosed. However, in the case of a resin having a carbonate bond such as a polycarbonate resin, ammonia or pyridine, which is a decomposition product of the quaternary ammonium salt or the pyridinium salt, decomposes the resin, and there is a problem that the impact resistance and transparency originally possessed by the resin are significantly reduced. Furthermore, a method of adding an antiviral composition composed of an inorganic filler and a sulfonic acid-based surfactant to a thermoplastic resin (Patent Document 3) has been disclosed, but there is no mention regarding the impact resistance of the resin composition.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In view of the above, an object of the present invention is to provide an antiviral polycarbonate resin composition excellent in antiviral properties, thermal stability, hue, and impact resistance, and a molded product made therefrom.

Means for Solving the Problems

[0006] As a result of intensive studies to solve such problems, the present inventors have found that by adding an organic antiviral agent and a surfactant to a polycarbonate resin, a polycarbonate resin composition excellent in antiviral properties, thermal stability, hue, and impact resistance can be obtained, and thus the present invention has been completed.

[0007] According to the present invention, the above problems are achieved by the following items 1 to 5. 1. A resin composition containing 1 to 15 parts by weight of an organic antiviral agent (component B) and 0.1 to 20 parts by weight of a surfactant (component C) with respect to 100 parts by weight of a polycarbonate resin (component A), and having an antiviral activity value at 23°C measured by a test method based on ISO21702 of 2.0 or more. 2. The resin composition according to item 1 above, wherein component B is an organic oxygen-based compound. 3. The resin composition according to item 1 or 2 above, wherein component C is an ionic surfactant. 4. The resin composition according to any one of items 1 to 3 above, having an antiviral activity value of 2.0 or more after wiping with water or alcohol. 5. A molded article made of the resin composition according to any one of items 1 to 4 above. Hereinafter, the present invention will be specifically described.

[0008] <Component A: Polycarbonate Resin> The polycarbonate resin used as component A of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of a carbonate prepolymer, and ring-opening polymerization of a cyclic carbonate compound.

[0009] Typical examples of divalent phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, and 4,4'-(p-phenyl Examples include bis(4-hydroxyphenyl)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred divalent phenols are bis(4-hydroxyphenyl)alkanes, among which bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0010] In this invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins manufactured using other divalent phenols as component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as some or all of the divalent phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly demanding. It is preferable that these divalent phenols other than BPA be used in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is especially preferable that component A constituting the polycarbonate resin composition be one of the copolymer polycarbonate resins (1) to (3) below. (1) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%) and BCF is 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0011] These special polycarbonate resins may be used individually or mixed in appropriate combinations of two or more types. They can also be mixed with commonly used bisphenol A type polycarbonate resins. The manufacturing methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Publication No. 6-172508, Japanese Patent Publication No. 8-27370, Japanese Patent Publication No. 2001-55435, and Japanese Patent Publication No. 2002-117580.

[0012] Furthermore, among the various polycarbonate resins mentioned above, those whose copolymerization composition and other properties have been adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges exhibit excellent hydrolysis resistance of the polymer itself, as well as significantly superior low warping after molding. Therefore, they are particularly suitable for fields requiring morphological stability. (i) A polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0013] Here, the water absorption rate of the polycarbonate resin was measured using a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm, after immersion in water at 23°C for 24 hours in accordance with ISO 62-1980. The glass transition temperature (Tg) was determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0014] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0015] When producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, an end-terminating agent, an antioxidant to prevent oxidation of the divalent phenol, etc., may be used as needed. The polycarbonate resin of the present invention also includes a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with both such bifunctional carboxylic acid and bifunctional alcohol. Furthermore, a mixture of two or more of the obtained polycarbonate resins may also be used.

[0016] Branched polycarbonate resins can impart properties such as drip prevention to the polycarbonate resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0017] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be generated as a side reaction, but the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols. 1It can be calculated by 1H-NMR measurement.

[0018] Among aliphatic difunctional carboxylic acids, α,ω-dicarboxylic acids are preferred. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As for difunctional alcohols, alicyclic diols are more preferred, with examples including cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0019] The reaction methods used in the present invention for producing polycarbonate resin, such as interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well-known methods described in various literatures and patent publications.

[0020] In producing the polycarbonate resin composition of the present invention, the viscosity-average molecular weight of the polycarbonate resin is preferably 12,500 to 32,000, more preferably 16,000 to 28,000, and even more preferably 18,000 to 26,000. Polycarbonate resins with a viscosity-average molecular weight of less than 12,500 may not yield good mechanical properties. On the other hand, polycarbonate resin compositions obtained from polycarbonate resins with a viscosity-average molecular weight exceeding 32,000 may have poor moldability.

[0021] In this invention, the viscosity-average molecular weight is first calculated using the following formula: the specific viscosity (η SP The viscosity of the solution was 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 for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SPCalculate the viscosity-average molecular weight M from the following formula. η SP / c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23×10 -4 M 0.83 c = 0.7 In addition, the viscosity-average molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble components in the composition. Such soluble components are collected by filtration through Celite. Then, the solvent in the resulting solution is removed. The solid after solvent removal is thoroughly dried to obtain a solid of the components dissolved in methylene chloride. From a solution obtained by dissolving 0.7 g of such solid in 100 ml of methylene chloride, the specific viscosity at 20 °C is determined in the same manner as above, and the viscosity-average molecular weight M is calculated from the specific viscosity in the same manner as above.

[0022] The polycarbonate resin of the present invention can also use a polycarbonate resin containing 1 to 100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component A-1). By using a polycarbonate-polyorganosiloxane copolymer resin as component A, it may be possible to improve chemical resistance and impact resistance. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin composed of units derived from a divalent phenol represented by the following general formula (1) and units derived from a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0023]

Chemical formula

[0024] [In the above general formula (1), R 1 and R 2Each of the following groups independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. e and f are integers from 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the general formula (2) below.

[0025] [ka]

[0026] [In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 Each of these independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, R 19 and R 20 Each of these independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0027] [ka]

[0028] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 4 and 350. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0029] Examples of divalent phenols (I) represented by general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-H 1,1-bis(4-hydroxyphenyl)fluorene, 2,2-diphenylmethane, 3,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0030] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, with 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene being particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is the most suitable. These may be used individually or in combination of two or more.

[0031] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), the following compounds are preferably used, for example.

[0032] [ka]

[0033] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosiliculation reaction of olefinic unsaturated carbon-carbon bonded phenols, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol, to the ends of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, and (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxanes (II) preferably have a molecular weight distribution (Mw / Mn) of 3 or less. Furthermore, in order to exhibit excellent low outgassing and low-temperature impact resistance during high-temperature molding, such a molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this suitable range is exceeded, the amount of outgassing during high-temperature molding increases, and the low-temperature impact resistance may be poor.

[0034] Furthermore, in order to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane(II) is preferably 4 to 350, and more preferably 10 to 300. More preferably, the degree of diorganosiloxane polymerization (p+q) is 10 to 200, even more preferably 12 to 150, and particularly preferably 14 to 100. Below the lower limit of this range, the impact resistance characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, and above the upper limit of this range, appearance defects appear.

[0035] In the present invention, only one hydroxyaryl-terminated polydiorganosiloxane(II) may be used, or two or more may be used.

[0036] Furthermore, to the extent that it does not interfere with the present invention, other comonomers other than the divalent phenol (1) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of 10% by weight or less relative to the total weight of the copolymer.

[0037] In the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by the reaction of a divalent phenol (1) with a carbonate ester-forming compound in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution.

[0038] In producing the divalent phenol (1) oligomer, the entire amount of divalent phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a portion of it may be added as a reaction material to the subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to expedite the subsequent polycondensation reaction, and it is not necessary to add it if it is not needed. The method of this oligomer formation reaction is not particularly limited, but it is generally preferable to carry it out in a solvent in the presence of an acid binder.

[0039] The proportion of ester-forming compounds used can be adjusted as appropriate, taking into account the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using gaseous ester-forming compounds such as phosgene, a suitable method is to bubble them into the reaction system.

[0040] Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. The proportion of acid binder used should be determined appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder relative to the number of moles of divalent phenol (1) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0041] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0042] There are no particular restrictions on the reaction pressure for oligomer formation; it can be atmospheric pressure, pressurized pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization is often exothermic, water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out in 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as for known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0043] In this invention, a mixed solution containing an oligomer of divalent phenol (1) having terminal chloroformate groups is obtained, and while stirring the mixed solution, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, is added to the divalent phenol (1), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0044] [ka]

[0045] (In the above general formula (4), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 4 and 350. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0046] When carrying out an interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into consideration the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. Specifically, when adding a portion of the hydroxyaryl-terminated polydiorganosiloxane(II) or the divalent phenol(1) as described above as a post-added monomer to this reaction step, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the post-added divalent phenol(1) and hydroxyaryl-terminated polydiorganosiloxane(II) (usually 1 mole corresponds to 2 equivalents).

[0047] The polycondensation reaction between the divalent phenol (1) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0048] In such polymerization reactions, end-terminating agents or molecular weight modifiers are commonly used. Examples of end-terminating agents include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenols, p-tert-butylphenol, p-cumylphenol, and tribromophenol, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenylalkylates, and alkyl etherphenols. The amount used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all divalent phenolic compounds used, and it is naturally possible to use two or more compounds in combination.

[0049] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added. The reaction time for such polymerization is preferably 30 minutes or more, and more preferably 50 minutes or more. Optionally, a small amount of antioxidant such as sodium sulfite or hydrosulfide may be added.

[0050] Branching agents can be used in combination with the above-mentioned divalent phenolic compounds to form branched polycarbonate-polydiorganosiloxanes. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1 Examples include trisphenols such as 1-bis(4-hydroxyphenyl)ethyl]benzene-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The proportion of polyfunctional compounds in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, even more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%, of the total amount of the polycarbonate-polydiorganosiloxane copolymer resin.1 It can be calculated by 1H-NMR measurement.

[0051] The reaction pressure can be reduced, atmospheric, or pressurized, but it is usually preferable to use atmospheric pressure or the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization often generates heat, water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be specified in general terms, but it is usually carried out in 0.5 to 10 hours.

[0052] Depending on the circumstances, the obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking, partial decomposition, etc.) to obtain the desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of [c].

[0053] The resulting reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification) by various post-treatment methods, such as known separation and purification methods.

[0054] The average size of polydiorganosiloxane domains in polycarbonate-polydiorganosiloxane copolymer resin molded articles is preferably in the range of 1 to 40 nm. More preferably, this average size is 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, and above the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0055] The average domain size and normalized dispersion of polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product of this invention were evaluated by small-angle X-ray scattering (SAXS). Small-angle X-ray scattering is a method for measuring diffuse scattering and diffraction occurring in the small-angle region with a scattering angle (2θ) < 10° or less. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in size in the material, diffuse scattering of X-rays is measured due to the difference in electron density. The particle size of the object to be measured is determined based on this scattering angle and scattering intensity. In the case of polycarbonate-polydiorganosiloxane copolymer resin, which has an aggregated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I is measured at each scattering angle (2θ) in the range of less than 10° to obtain a small-angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical and that there is variability in the particle size distribution, a simulation is performed using commercially available analysis software with a hypothetical particle size and a hypothetical particle size distribution model to determine the average size and particle size distribution (normalized variance) of the polydiorganosiloxane domains. The small-angle X-ray scattering method allows for accurate, simple, and reproducible measurement of the average size and particle size distribution of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by transmission electron microscopy. The average domain size refers to the numerical average of the individual domain sizes. Normalized variance refers to a parameter that normalizes the spread of the particle size distribution by the average size. Specifically, it is the value obtained by normalizing the variance of the polydiorganosiloxane domain size by the average domain size, and is expressed by the following equation (1).

[0056]

number

[0057] The terms "average domain size" and "normalized dispersion" used in connection with the present invention refer to the measured values obtained by measuring the 1.0 mm thick portion of the three-layer plate prepared by the method described in the Examples by such small-angle X-ray scattering method. Further, analysis was performed using an isolated particle model that does not consider inter-particle interaction (inter-particle interference).

[0058] Furthermore, as the polycarbonate resin, it is also possible to use a polycarbonate resin regenerated from used products, that is, a recycled polycarbonate resin. Examples of used products preferably include various glazing materials typified by sound insulation walls, automobile windows, translucent roofing materials, and automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, light guide plates, spectacle lenses, and optical recording media. Also, crushed products obtained from defective products, sprues, runners, etc. of the product or pellets obtained by melting them can also be used.

[0059] <Component B: Organic antiviral agent> The antiviral agent used as component B in the polycarbonate resin composition of the present invention is an organic antiviral agent. If an antiviral agent other than an organic antiviral agent is used as the antiviral agent, the impact resistance, hue, and thermal stability deteriorate. Since the organic antiviral agent is added to the resin matrix component and subjected to injection molding or extrusion molding, its decomposition temperature is required to be higher than the melting temperature of the resin component, and is preferably 400 to 600°C. Among these, organophosphorus compounds, organosulfur compounds, and organic oxygen compounds that have antiviral activity against both enveloped viruses such as influenza virus and non-enveloped viruses such as feline calicivirus are examples, and organic oxygen compounds are preferred, wherein the constituent unit represented by the following formula (5) preferably accounts for at least 60 mol%, more preferably at least 80 mol%, of the total constituent units, and particularly preferably, an organic oxygen compound consisting substantially of the constituent unit represented by the following formula (5) is even more preferred.

[0060] [ka]

[0061] [In the above general formula (5), R 1 , R 2 and R 3 Each of these independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, R 4 represents a hydrogen atom or a methyl group. M represents an alkali metal atom, alkaline earth metal atom, silver atom, zinc atom, lanthanum atom, aluminum atom, cerium atom, ammonium, alkaline earth metal compound, zinc compound, lanthanum compound, or aluminum compound. n is an integer from 1 to 3.

[0062] The content of component B is 1 to 15 parts by weight per 100 parts by weight of component A, preferably 1.5 to 12 parts by weight, and more preferably 2 to 10 parts by weight. If the amount of component B is less than 1 part by weight, sufficient antiviral activity cannot be obtained, and if it exceeds 15 parts by weight, the hue, impact resistance and thermal stability deteriorate.

[0063] <Component C: Surfactant> The antiviral polycarbonate resin composition of the present invention contains a surfactant as Component C. Such surfactants include ionic surfactants (anionic surfactants and cationic surfactants), non-ionic surfactants, and amphoteric surfactants. To exhibit antiviral properties, ionic surfactants are preferred, and anionic surfactants are more preferred. Examples of anionic surfactants include sodium alkyl sulfonate, sodium alkyl benzene sulfonate, and alkyl phosphate. To exhibit antiviral properties, sodium linear alkyl sulfonate having 4 to 20 carbon atoms is more preferred.

[0064] The content of Component C is 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of Component A. If the content of Component C is less than 0.1 part by weight, the antiviral property deteriorates, and if it exceeds 20 parts by weight, the impact resistance deteriorates.

[0065] <Other Components> (i) Anti-drip agent The antiviral polycarbonate resin composition of the present invention can contain an anti-drip agent. When such an anti-drip agent is contained, good flame retardancy can be achieved without impairing the physical properties of the molded product.

[0066] Examples of the anti-drip agent include fluorine-containing polymers having fibril-forming ability. Such polymers include polytetrafluoroethylene, tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in U.S. Patent No. 4379910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0067] PTFE with fibril-forming ability has an extremely high molecular weight and tends to bond with other PTFE materials to form fibers under external forces such as shear force. Its molecular weight, calculated from the standard specific gravity, is 1 million to 10 million, preferably 2 million to 9 million. Such PTFE can be used in solid form as well as aqueous dispersion form. Furthermore, to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties, it is also possible to use PTFE mixtures in mixed form with other resins.

[0068] Examples of commercially available PTFE products possessing such fibril-forming ability include Daikin Industries, Ltd.'s "Polyflon MPA FA series (FA-500H and FA-5601, etc.)". Representative examples of commercially available aqueous dispersions of PTFE include Daikin Industries, Ltd.'s "Polyflon PTFE D series (D-111 and D-210C, etc.)".

[0069] As for PTFE in mixed form, (1) a method of mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-aggregated mixture (methods described in Japanese Patent Publication No. 60-258263, Japanese Patent Publication No. 63-154744, etc.), (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Publication No. 4-272957), (3) a method of uniformly mixing an aqueous dispersion of PTFE with an organic polymer particle solution and separating each medium from the mixture. (1) A method of removing the organic polymer in an aqueous dispersion of PTFE (as described in Japanese Patent Publication No. 06-220210, Japanese Patent Publication No. 08-188653, etc.), (2) a method of polymerizing monomers that form an organic polymer in an aqueous dispersion of PTFE (as described in Japanese Patent Publication No. 9-95583), and (3) a method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, further polymerizing vinyl monomers in the mixed dispersion, and then obtaining a mixture (as described in Japanese Patent Publication No. 11-29679, etc.) can be used. Examples of commercially available PTFE in these mixed forms include "Metablen A series (A-3750 and A-3800)" manufactured by Mitsubishi Chemical Corporation.

[0070] In the mixed form, the proportion of PTFE is preferably 1 to 60% by weight, and more preferably 5 to 55% by weight, of 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE can sometimes be achieved.

[0071] Furthermore, examples of styrene monomers used in the organic polymers used in the polytetrafluoroethylene-based mixtures of the present invention include, but are not limited to, styrenes that may be substituted with one or more groups selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogens, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethylstyrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, and vinylnaphthalene. The styrene monomers can be used individually or in combination of two or more types.

[0072] The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene mixture in the present invention includes a substituted (meth)acrylate derivative. Specifically, the acrylic monomer may be a (meth)acrylate derivative substituted with one or more groups selected from the group consisting of C1-C20 alkyl groups, C3-C8 cycloalkyl groups, aryl groups, and glycidyl groups, for example, (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl ( Examples of acrylic monomers include, but are not limited to, meth)acrylate, cyclohexyl(meth)acrylate, octyl(meth)acrylate, dodecyl(meth)acrylate, phenyl(meth)acrylate, benzyl(meth)acrylate, and glycidyl(meth)acrylate, maleimides which may be substituted with C1-C6 alkyl groups or aryl groups, such as maleimide, N-methyl-maleimide, and N-phenyl-maleimide, maleic acid, phthalic acid, and itaconic acid. The acrylic monomers can be used individually or in combination of two or more types. Among these, (meth)acrylonitrile is preferred.

[0073] The amount of acrylic monomer-derived units in the organic polymer used in the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, and even more preferably 8 to 9 parts by weight, per 100 parts by weight of styrene monomer-derived units. If the amount of acrylic monomer-derived units is less than 8 parts by weight, the coating strength may decrease, and if it is more than 11 parts by weight, the surface appearance of the molded product may deteriorate.

[0074] The polytetrafluoroethylene-based mixture in the present invention preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, and even more preferably 0.1 to 0.3% by weight. A residual moisture content greater than 0.5% by weight may adversely affect flame retardancy.

[0075] The manufacturing process for the polytetrafluoroethylene mixture in the present invention includes a step of forming a coating layer on the outside of branched polytetrafluoroethylene containing one or more monomers selected from the group consisting of styrene monomers and acrylic monomers in the presence of an initiator. Furthermore, it is preferable to include a step of drying after the coating layer formation step so that the residual moisture content is 0.5% by weight or less, preferably 0.2 to 0.4% by weight, and more preferably 0.1 to 0.3% by weight. The drying step can be carried out using, for example, an art-known method such as hot air drying or vacuum drying.

[0076] The initiator used in the polytetrafluoroethylene mixture of the present invention can be any initiator used in polymerization reactions of styrene-based and / or acrylic monomers without limitation. Examples of such initiators include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. One or more of the above initiators can be used in the polytetrafluoroethylene mixture of the present invention depending on the reaction conditions. The amount of the initiator can be freely selected within a range that takes into account the amount of polytetrafluoroethylene and the type / amount of monomers, and it is preferable to use 0.15 to 0.25 parts by weight based on the amount of the total composition.

[0077] The polytetrafluoroethylene-based mixture used in this invention was produced by suspension polymerization according to the following procedure. First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15-0.3 μm) were added to a reactor. Acrylic monomer, styrene monomer, and cumene hydroperoxide as a water-soluble initiator were added while stirring, and the reaction was carried out at 80-90°C for 9 hours. After the reaction was complete, water was removed by centrifugation for 30 minutes to obtain a paste-like product. The paste was then dried in a hot air dryer at 80-100°C for 8 hours. The dried product was then pulverized to obtain the polytetrafluoroethylene-based mixture of the present invention.

[0078] This suspension polymerization method does not require the emulsion dispersion polymerization step exemplified in emulsion polymerization methods such as Patent No. 3469391, and therefore does not require emulsifiers or electrolyte salts for coagulating and precipitating the polymerized latex. Furthermore, in polytetrafluoroethylene mixtures produced by emulsion polymerization, emulsifiers and electrolyte salts tend to be mixed in the mixture and are difficult to remove, making it difficult to reduce the sodium and potassium ions derived from such emulsifiers and electrolyte salts. Since the polytetrafluoroethylene mixture used in the present invention is produced by suspension polymerization, such emulsifiers and electrolyte salts are not used, thus reducing the sodium and potassium ion content in the mixture and improving thermal stability and hydrolysis resistance.

[0079] Furthermore, in the present invention, coated branched PTFE can be used as a drip-preventing agent. Coated branched PTFE is a polytetrafluoroethylene mixture consisting of branched polytetrafluoroethylene particles and an organic polymer, and has a coating layer on the outside of the branched polytetrafluoroethylene consisting of an organic polymer, preferably a polymer containing styrene monomer-derived units and / or acrylic monomer-derived units. The coating layer is formed on the surface of the branched polytetrafluoroethylene. It is also preferable that the coating layer contains a copolymer of styrene monomers and acrylic monomers.

[0080] The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the anti-dropping effect will be insufficient when the amount of polytetrafluoroethylene added is small. Branched polytetrafluoroethylene is particulate and preferably has a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene with a particle size smaller than 0.1 μm. Also, when the particle size is larger than 0.6 μm, the surface appearance of the molded product may be poor. The number average molecular weight of the polytetrafluoroethylene used in this invention is 1 × 10⁻⁶ 4 ~1 × 10 7 Preferably, 2 × 10 6 ~9×10 6 Generally, polytetrafluoroethylenes with higher molecular weights are more preferable in terms of stability. They can be used in either powder or dispersion form. The branched polytetrafluoroethylene content in coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, even more preferably 47 to 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight, per 100 parts by weight of the total weight of coated branched PTFE. When the proportion of branched polytetrafluoroethylene is within this range, good dispersibility of the branched polytetrafluoroethylene can sometimes be achieved.

[0081] The amount of drip inhibitor is preferably 0.1 to 2 parts by weight, and more preferably 0.2 to 1.5 parts by weight, per 100 parts by weight of component A. If the amount is less than 0.1 parts by weight, sufficient flame retardancy may not be achieved, and if it exceeds 2 parts by weight, impact resistance may decrease. Note that the amount of drip inhibitor refers to the net amount of drip inhibitor, and in the case of PTFE in mixed form, it refers to the net amount of PTFE.

[0082] (ii) Phosphate stabilizers The antiviral polycarbonate resin composition of the present invention may contain a phosphorus-based stabilizer. The inclusion of such a phosphorus-based stabilizer suppresses thermal decomposition during molding and is effective in maintaining good impact resistance and flame retardancy.

[0083] Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and their esters, as well as tertiary phosphines. Specifically, examples of phosphite compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl) phosphite, tris(di-iso-propylphenyl) phosphite, and tris(di-n-butylphenyl) phosphite. Examples include tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

[0084] Furthermore, other phosphite compounds that react with divalent phenols to form cyclic structures can also be used. Examples include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite, and 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite.

[0085] Examples of phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and octadecyl phosphate. Octadecyl phosphate, triphenyl phosphate, and trimethyl phosphate are preferred.

[0086] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2 Examples include ,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Among these, tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such phosphonite compounds can be used in combination with phosphite compounds having aryl groups substituted with two or more alkyl groups, and this is preferable.

[0087] Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0088] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0089] The phosphorus-based stabilizers described above may be a mixture of two or more types, not just one. Among the phosphorus-based stabilizers, combination use with phosphite compounds and phosphonite compounds is preferred.

[0090] The phosphorus-based stabilizer content is preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.9 parts by weight, per 100 parts by weight of component A. If the content is less than 0.01 parts by weight, the suppression of thermal decomposition during molding may be insufficient, and the effect on maintaining impact resistance may not be observed. If it exceeds 1 part by weight, thermal decomposition during molding may be promoted, and impact resistance may decrease.

[0091] (iii) Phenolic stabilizers The antiviral polycarbonate resin composition of the present invention may contain a phenolic stabilizer. Examples of phenolic stabilizers include hindered phenols, semi-hindered phenols, and less-hindered phenol compounds, but hindered phenol compounds are particularly preferred from the viewpoint of providing a heat-stable formulation to resins containing polycarbonate resins and styrene-based resins.

[0092] Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di-tert-butyl-4-hydroxybenzylphosphonatediethyl Luester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl-6-tert-butylphenol 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxyphenyl] [C-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1, 3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3 (3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert- Examples include tetraxyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate.

[0093] Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used. The above-mentioned phenolic stabilizers can be used individually or in combination of two or more types.

[0094] The content of the phenolic stabilizer is preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.9 parts by weight, per 100 parts by weight of component A. If the content is less than 0.01 parts by weight, the suppression of thermal decomposition during molding may not be sufficient, and the effect on maintaining impact resistance may not be observed. If it exceeds 1 part by weight, it may promote thermal decomposition during molding, and impact resistance may decrease.

[0095] (iv) Release agent The antiviral polycarbonate resin composition of the present invention may contain a release agent to the extent that it exhibits the effects of the present invention, such as improving mold release properties during molding and reducing distortion of molded products.

[0096] Known release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc., those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds (silicone oils, organosiloxanes, etc.), fluorine compounds (fluorine oils represented by polyfluoroalkyl ethers, etc.), paraffin wax, beeswax, etc. Among these, fatty acid esters are preferred as release agents.

[0097] Such fatty acid esters are esters of an aliphatic alcohol and an aliphatic carboxylic acid. Such aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol with two or more carbon atoms, preferably in the range of 3 to 32 carbon atoms, and more preferably in the range of 5 to 30 carbon atoms. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid esters of the present invention, polyhydric alcohols are more preferred.

[0098] On the other hand, aliphatic carboxylic acids are preferably those having 3 to 32 carbon atoms, and particularly preferably those having 10 to 22 carbon atoms. Examples of such aliphatic carboxylic acids include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, eicosanic acid, and docosanic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Saturated aliphatic carboxylic acids are more preferred among these. Stearic acid and palmitic acid are particularly preferred.

[0099] The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural oils and fats, such as animal fats and fats, represented by beef tallow and lard, and vegetable oils, represented by palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Accordingly, in the production of fatty acid esters of the present invention, aliphatic carboxylic acids produced from such natural oils and fats, and in the form of mixtures containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used.

[0100] The above fatty acid ester may be either a partial ester or a full ester. However, since partial esters usually have a high hydroxyl value and tend to induce decomposition of resins at high temperatures, full esters are more preferable. From the viewpoint of thermal stability, the acid value of such fatty acid esters is preferably 20 or less, more preferably 4 to 20, and even more preferably 4 to 12. Note that the acid value can be substantially 0. In addition, the hydroxyl value of such fatty acid esters is preferably 0.1 to 30, and the iodine value of such fatty acid esters is preferably 10 or less. Note that the iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070.

[0101] The above-mentioned release agent may be a mixture of two or more types, not just one. The release agent content is preferably 0.01 to 2 parts by weight, and more preferably 0.02 to 1 part by weight, per 100 parts by weight of component A. If the content is less than 0.01 parts by weight, good release properties may not be achieved, and if it exceeds 2 parts by weight, impact resistance may decrease.

[0102] (v) UV absorbers The antiviral polycarbonate resin composition of the present invention may contain an ultraviolet absorber for the purpose of imparting light resistance. Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Among these, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers are preferred.

[0103] Benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl) Examples include (nyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole. Examples of polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton include copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer.

[0104] Suitable examples of triazine-based UV absorbers include hydroxyphenyltriazine compounds such as 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butyloxyphenol. Furthermore, compounds in which the phenyl group of the above-exemplified hydroxyphenyltriazine compounds has been replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol, are also exemplified. The above ultraviolet absorbers may be used individually or as a mixture of two or more.

[0105] (vi) dyes and pigments The antiviral polycarbonate resin composition of the present invention contains various dyes and pigments, and can provide molded articles that exhibit diverse design properties. By incorporating fluorescent whitening agents or other fluorescent dyes that emit light, even better design effects can be imparted by utilizing the luminescent color. Furthermore, a resin composition that can be colored with a minute amount of dye and pigment and exhibits vivid color development can also be provided.

[0106] Examples of fluorescent dyes (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiaidine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and do not degrade much during the molding process of polycarbonate resin.

[0107] Other dyes besides the fluorescent dyes mentioned above include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can also be blended with metallic pigments to obtain good metallic colors. Suitable metallic pigments include those having a metal coating or metal oxide coating on various plate-shaped fillers.

[0108] (vii) Other resins and elastomers The antiviral polycarbonate resin composition of the present invention may also contain other resins or elastomers in small proportions, as long as they do not exert the effects of the present invention.

[0109] Other resins include, for example, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, and epoxy resins.

[0110] Examples of such elastomers include silicone rubber / isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, and polyamide elastomers.

[0111] (viii) Other additives In addition, antiviral polycarbonate resin compositions may contain small amounts of well-known additives to impart various functions or improve the properties of molded articles. These additives are added in normal amounts, as long as they do not impair the objectives of the present invention.

[0112] Examples of such additives include lubricants (e.g., PTFE particles), colorants (e.g., pigments and dyes other than the above-mentioned dyes, such as carbon black), light diffusing agents (e.g., acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, etc.), inorganic phosphors (e.g., phosphors with aluminate as the matrix crystal), nucleating agents, radical generators, infrared absorbers (heat absorbers), and photochromic agents.

[0113] <Manufacturing of antiviral polycarbonate resin composition> Any method can be used to produce the antiviral polycarbonate resin composition according to the present invention. For example, components A to C, and optionally other additives, can be thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, and extruder mixer, respectively. Then, if necessary, the premix can be granulated using an extruder granulator and briquetting machine, and subsequently melt-kneaded in a melt-kneader such as a vented twin-screw extruder, and then pelletized using equipment such as a pelletizer.

[0114] <Manufacturing of molded articles made from antiviral polycarbonate resin compositions> The antiviral polycarbonate resin composition of the present invention can be used to produce various molded products by injection molding pellets obtained by the method described above. In such injection molding, it is possible to manufacture not only the product using the conventional cold runner method, but also using a hot runner that enables runnerless molding. Furthermore, in injection molding, not only conventional molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (including those using supercritical fluids), rapid heating and cooling mold molding, in-mold remelting molding, and molding methods consisting of combinations thereof can be used.

[0115] Furthermore, the resin composition of the present invention can be used in the form of various irregularly shaped extruded products, sheets, films, etc., 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 as a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be molded into products by rotational molding or blow molding.

[0116] Furthermore, molded products formed from resin compositions can be subjected to various surface treatments. These surface treatments include decorative coatings, hard coatings, water-repellent / oil-repellent coatings, hydrophilic coatings, UV-absorbing coatings, infrared-absorbing coatings, electromagnetic wave-absorbing coatings, heat-generating coatings, antistatic coatings, antistatic coatings, conductive coatings, and metallizing (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.).

[0117] <Antiviral> The antiviral activity value of the antiviral polycarbonate resin composition of the present invention, as measured by the test method based on ISO 21702, must be 2.0 or higher, and preferably 3.0 or higher. While there is no particular upper limit to the antiviral activity value, 4.0 is sufficient.

[0118] Furthermore, the antiviral activity value of the antiviral polycarbonate resin composition of the present invention after wiping with water or alcohol is preferably 2.0 or higher, and more preferably 3.0 or higher. While there is no particular upper limit to this antiviral activity value, 4.0 is sufficient.

[0119] <Impact Resistance> The notched Charpy impact strength of a test specimen made from the antiviral polycarbonate resin composition of the present invention, conditioned at 23°C in accordance with ISO 179, was 20 kJ / m². 2 The above is preferable, with a 30 kJ / m³ 2 The above is more preferable: 40 kJ / m 2The above is even more preferable. Below this preferable range, it is difficult to apply to various applications, and in particular, it is difficult to apply to housings and other applications where strength is required. The upper limit of the measured value of the notched Charpy impact strength is not particularly limited except for the limitations of the detection limit of the measuring instrument, but 100 kJ / m 2 It performs optimally in the following situations. [Effects of the Invention]

[0120] The antiviral polycarbonate resin composition of the present invention is excellent in antiviral properties, thermal stability, color, and impact resistance, making it useful for plastic parts related to toilets and washbasins, exteriors of tablets, laptops, smartphones, digital cameras, medical monitors, POS systems, office equipment, printers, televisions, etc., which may be used and touched by an unspecified number of people, as well as irons, hair dryers, rice cookers, microwave ovens, air conditioners, air purifiers, negative ion generators, various buttons and switches, doorknobs, plastic parts related to amusement and various plastic parts related to mobility. Therefore, the industrial effects achieved by the present invention are exceptional. [Modes for carrying out the invention]

[0121] The present inventors consider the best possible form of the present invention to be a combination of the preferred ranges of the above requirements, and a representative example is described in the following embodiments. Of course, the present invention is not limited to these forms. [Examples]

[0122] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the present invention. Unless otherwise specified, parts in the examples are parts by weight, and % are weight percent. The evaluation was carried out according to the following method.

[0123] (Evaluation of antiviral polycarbonate resin compositions) (1) Antiviral activity (without pretreatment, antiviral activity value) Using a test specimen (width 50 mm, length 50 mm, thickness 2 mm) obtained by cutting a rectangular plate molded product (width 150 mm, length 150 mm, thickness 2 mm) prepared by the method described below, a test was conducted under the following conditions in accordance with ISO 21702. *Test virus solution concentration: 1.8 × 10 7 PFL / mL *Test solution inoculation volume: 0.4 mL (covering film: surface area 16 cm²) 2 (Polyethylene film) *Test environment: 25℃ × 24 hours *Test virus: Influenza virus (H3N2) *Wash solution: SCDLP medium The antiviral activity was evaluated based on the following criteria. Antiviral activity value = log 10 (Virus count in unprocessed test specimens after 24 hours) - log 10 (Number of viruses after 24 hours on antiviral treated test specimens) ○: Antiviral activity value of 3.0 or higher △: Antiviral activity value is 2.0 or higher but less than 3.0 ×: Antiviral activity value less than 2.0 Antiviral-treated test specimens refer to test specimens made of a resin composition containing an antiviral agent (the resin compositions listed in the Examples and Comparative Examples below). On the other hand, untreated test specimens refer to test specimens made of polycarbonate resin alone.

[0124] (2) Sustained antiviral activity (water wiping treatment, antiviral activity value) A test specimen (50 mm wide, 50 mm long, 2 mm thick) obtained by cutting a rectangular plate molded product (150 mm wide, 150 mm long, 2 mm thick) prepared by the method described below was sprayed with pure water five times using a spray bottle, and then wiped three times with a dry cloth. After the test specimen wiped with the obtained water was left to stand for 24 hours, the test was carried out in accordance with ISO 21702 under the same conditions as "(1) Antiviral activity (no pretreatment, antiviral activity value)" above, and evaluated using the same criteria.

[0125] (3) Impact resistance (Charpy impact strength with notch) The notched Charpy impact strength of test specimens (width 10 mm, length 80 mm, thickness 4.0 mm) prepared using the method described below was measured in accordance with ISO 179.

[0126] (4) Hue (YI value) The YI values ​​of plate-shaped test specimens (50 mm wide, 50 mm long, 2.0 mm thick) prepared using the method described below were measured with an X-Rite Ci7800 spectrophotometer (D65 light source, 10° field of view) and evaluated as follows. ○: YI value is less than 5.0 △: YI value is 5.0 or higher and less than 25.0 ×: YI value is 25.0 or higher

[0127] (5) Thermal stability (surface appearance) The surface appearance of five 50mm x 50mm x 2mm thick plate-shaped test specimens, prepared using the method described below, was visually observed and evaluated as follows. Injection molding defects include silvering, flow marks, and surface roughness. ○: No cosmetic defects were found in any of the test specimens. △: Some test pieces show slight surface defects caused by injection molding. ×: There are test specimens in which surface defects caused by injection molding are observed.

[0128] [Examples 1-9, Comparative Examples 1-6] The compositions of components A to C and other components shown in Tables 1 and 2 were uniformly mixed using a blender, and then melt-kneaded using a vented twin-screw extruder to obtain pellets. For each of these components, a premix was prepared with the main component A powder at a concentration of approximately 10 to 100 times the amount of each component, and then the entire mixture was mixed using a blender. A Kobe Steel, Ltd. KTX-30 (30 mm diameter) vented twin-screw extruder was used. The extrusion conditions were cylinder and die temperatures of 280°C, screw rotation speed of 200 rpm, discharge rate of 20 kg / h, and vent suction of 3 kPa. After extruding the strands and cooling them in a water bath, the strands were cut with a pelletizer to form pellets. The obtained pellets were dried in a hot air circulation dryer at 120°C for 5 hours, and then molded products for various evaluations were produced using an injection molding machine (Nissei Plastic Industrial Co., Ltd.; NEX140IV) at a cylinder temperature of 280°C and a mold temperature of 80°C.

[0129] The results of various evaluations are shown in Tables 1 and 2. The components represented by the symbols in Tables 1 and 2 are as follows: (Component A) A-1: Aromatic polycarbonate resin [Manufactured by Teijin Limited; Panlite L-1225WP (product name), a linear aromatic polycarbonate resin powder with a viscosity-average molecular weight of 22,400, based on a repeating 2,2-bis(4-hydroxyphenyl)propane backbone] (B component) B-1: Organic antiviral agent (manufactured by Sumika Environmental Science Co., Ltd.; ES2799, organic oxygen compound) B-2 (Comparative Example): Metal-based antiviral agent (manufactured by Toagosei Co., Ltd.; Novalon IV4000) (C component) C-1: Ionic surfactant (Kao Corporation; K-3000), anionic surfactant) (Other ingredients) S-1: Hindered phenol-based antioxidant (Manufactured by ADEKA Corporation; ADEKA Stab AO-50) S-2: Phosphate-based antioxidant (Manufactured by ADEKA Corporation; ADEKA Stab 2112) L-1: Fatty acid ester-based release agent (manufactured by NOF Corporation; Unistar H-476-S)

[0130] [Table 1]

[0131] [Table 2]

[0132] Tables 1 and 2 show that by adding organic antiviral agents and surfactants to polycarbonate resin in specific amounts, an antiviral polycarbonate resin composition with excellent antiviral properties, thermal stability, color, and impact resistance can be obtained.

Claims

1. A resin composition characterized by containing (A) 100 parts by weight of polycarbonate resin (component A), (B) 1 to 15 parts by weight of organic antiviral agent (component B), and (C) 0.1 to 20 parts by weight of surfactant (component C), wherein the antiviral activity value at 23°C, as measured by a test method based on ISO 21702, is 2.0 or higher.

2. The resin composition according to claim 1, characterized in that component B is an organic oxygen compound.

3. The resin composition according to claim 1 or 2, characterized in that component C is an ionic surfactant.

4. The resin composition according to claim 1 or 2, characterized in that the antiviral activity value after wiping with water or alcohol is 2.0 or higher.

5. A molded article comprising the resin composition described in claim 1 or 2.

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