Polycarbonate resin composition with excellent resistance to ionizing radiation and molded articles containing the same

Abstract

The present invention relates to a polycarbonate resin composition with excellent resistance to ionizing radiation and a molded article containing the same. More specifically, the present invention relates to a polycarbonate resin composition and a molded article containing the same, which, by containing a polycarbonate resin, a polyalkylene glycol adduct of anhydrous sugar alcohol, and a specific coloring agent component, exhibits significantly improved resistance to ionizing radiation compared to the prior art and has an excellent balance of mechanical properties, making it particularly suitable for use in medical supplies irradiated with gamma rays for sterilization.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition with excellent resistance to ionizing radiation and a molded article containing the same. More specifically, the present invention relates to a polycarbonate resin composition comprising a polyalkylene glycol adduct of anhydrous sugar alcohol and a specific coloring agent component, which exhibits significantly improved resistance to ionizing radiation compared to the prior art and also has an excellent balance of mechanical properties, making it particularly suitable for use in medical supplies irradiated with gamma rays for sterilization purposes, and a molded article containing the same. [Background technology]

[0002] Polycarbonate resin is a general-purpose thermoplastic engineering plastic with a glass transition temperature of around 150°C. It possesses excellent mechanical properties such as tensile strength and impact strength, as well as dimensional stability, heat resistance, and optical transparency. Due to these superior properties, it is widely used as a material for medical devices.

[0003] Due to the nature of their use, medical devices need to be sterilized before and after use, and gamma ray sterilization is the most commonly used sterilization method. However, irradiating polycarbonate materials with gamma rays, which are ionizing radiation, increases their yellowness index (YI) and degrades their appearance. Therefore, various attempts have been made to impart ionizing radiation resistance to polycarbonate resin compositions.

[0004] For example, Patent Document 1 discloses a composition comprising a polycarbonate resin and an anthraquinone-based colorant, which has resistance to ionizing radiation. In this prior art, the color of the test specimen after irradiation with ionizing radiation (gamma rays) is controlled using only the colorant, but there was a problem that after 7 days from irradiation with ionizing radiation (gamma rays), the Col-L (lightness) value of the 3 mm thick test specimen became dark, less than 85.

[0005] On the other hand, a technique has been proposed to reduce the degree of yellowing index (YI), which increases after gamma-ray irradiation, by introducing glycol-based additives into polycarbonate resin compositions. Examples of such commercially available products include INFINO® PC MR-1005 and INFINO® PC MR-1015 from Lotte Chemical Co., Ltd., and Makrolon Rx1805 and Makrolon Rx2430 from COVESTRO. All of the above products mainly consist of PC (polycarbonate resin) + PAG (polyalkylene glycol) + colorant, and their primary use is as transparent parts for ionizing radiation (gamma-ray) sterilization. However, such prior art, for example, the composition containing polycarbonate, polyalkylene glycol and organic / inorganic synthetic pigments disclosed in Patent Document 2, also had the problem of poor color recovery, as the L* (lightness) value of a 3 mm thick test piece became dark with a value of 85 or less after 7 days following ionizing radiation (gamma-ray) irradiation. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2012-207230 [Patent Document 2] South Korea JP Publication No. 10-2016-0122630 [Overview of the project] [Problems that the invention aims to solve]

[0007] The object of the present invention is to provide a polycarbonate resin composition and a molded article containing the same that has significantly improved ionizing radiation resistance compared to the prior art and has an excellent balance of mechanical properties. [Means for solving the problem]

[0008] To achieve the above objective, the present invention provides a polycarbonate resin composition resistant to ionizing radiation, comprising (A) a polycarbonate resin; (B) a polyalkylene glycol adduct of anhydrous sugar alcohol; and (C) a coloring agent component which is a blue pigment, a red pigment, or a combination thereof, wherein when a 3 mm thick test piece of the resin composition is irradiated with 25 kGy of gamma rays and measured according to ASTM D1925 7 days after irradiation, the change in yellowness index (△YI) value is 14.7 or less.

[0009] According to another aspect of the present invention, a molded article comprising the polycarbonate resin composition of the present invention is provided. In one embodiment, the molded product may be an ionizing radiation-resistant medical product. [Effects of the Invention]

[0010] The polycarbonate resin composition and molded articles containing the same according to the present invention exhibit remarkably little change in color and brightness even after irradiation with ionizing radiation (gamma rays) (i.e., show low ΔYI values ​​and high brightness values), have excellent color recovery over time after irradiation (i.e., a significant decrease in ΔYI over time after irradiation), and can maintain a good balance of mechanical properties. Therefore, they are extremely suitable for use in medical supplies irradiated with gamma rays for sterilization purposes. [Modes for carrying out the invention]

[0011] The present invention will be described in more detail below.

[0012] In this specification, the "change in yellowness index (ΔYI) value" refers to the difference between the yellowness index (YI) value of a test piece of the resin composition before gamma-ray irradiation and the yellowness index (YI) value of the yellowed test piece after irradiation. The radiation-resistant composition indicates that the ΔYI value decreases with time due to the resistance of the composition to color change after gamma-ray irradiation, which demonstrates the color recovery ability of the composition. Therefore, the ΔYI value data over time after gamma-ray irradiation serves as an indicator of the color recovery ability of the composition. The composition of the present invention is characterized by showing a significant decrease in ΔYI over time after gamma-ray irradiation, which means that the color recovery ability is extremely excellent.

[0013] The radiation-resistant polycarbonate resin composition of the present invention contains (A) polycarbonate (PC) resin; (B) a polyalkylene glycol adduct of a sugar alcohol; and (C) a colorant component containing a blue pigment. When a test piece with a thickness of 3 mm of the resin composition is irradiated with 25 kGy of gamma rays and the change in yellowness index (ΔYI) value measured according to ASTM D1925 7 days after irradiation (hereinafter, also referred to as "ΔYI value 7 days after gamma-ray irradiation") is 14.7 or less. More specifically, the ΔYI value 7 days after gamma-ray irradiation of the resin composition of the present invention may be 14.6 or less, 14.5 or less, 14.4 or less, 14.3 or less, 14.2 or less, 14.1 or less, or 14 or less. There are no specific restrictions on the lower limit value of the ΔYI value 7 days after gamma-ray irradiation. For example, it may be 9 or more, 9.5 or more, 10 or more, or 10.5 or more, but it is not limited thereto.

[0014] In one embodiment, when a test piece with a thickness of 3 mm of the resin composition of the present invention is irradiated with 25 kGy of gamma rays, the change in yellowness index (ΔYI) value measured according to ASTM D1925 1 day after irradiation (hereinafter, also referred to as "ΔYI value 1 day after gamma-ray irradiation") may be 25.5 or less, and more specifically, it may be 25.4 or less, 25 or less, 24.5 or less, or 24 or less. There are no particular restrictions on the lower limit value of the ΔYI value 1 day after gamma-ray irradiation. For example, it may be 17 or more, 17.5 or more, 18 or more, 18.5 or more, 19 or more, or 19.5 or more, but it is not limited thereto.

[0015] In one embodiment, a test piece with a thickness of 3 mm of the resin composition of the present invention is irradiated with 25 kGy of gamma rays, and the lightness (L) value measured in accordance with ASTM D2244 7 days after the irradiation (hereinafter, also referred to as "L value 7 days after gamma ray irradiation") may be 85.5 or more, more specifically, 85.6 or more, 86 or more, 86.5 or more, 87 or more, 87.5 or more, 88 or more, 88.5 or more, 89 or more, or 89.5 or more. There is no particular limitation on the upper limit of the L value 7 days after the gamma ray irradiation, and for example, it may be 95 or less, 94.5 or less, 94 or less, 93.5 or less, 93 or less, 92.5 or less, 92 or less, or 91.5 or less, but it is not limited thereto.

[0016] In one embodiment, an impact strength test piece (thickness 1 / 8 inch, Izod with notch) of the resin composition of the present invention is irradiated with 25 kGy of gamma rays, and the impact strength retention rate (%) value measured in accordance with ASTM D256 1 day after the irradiation (hereinafter, also referred to as "impact strength retention rate value 1 day after gamma ray irradiation") may be 94.9% or more, more specifically, 95% or more, 95.5% or more, or 96% or more. The upper limit of the L value 1 day after the gamma ray irradiation is theoretically 100%, but in actuality, it may be larger (for example, 105%) due to measurement errors or the like.

[0017] As used herein, the "impact strength retention rate value" means the impact strength value of the test piece after irradiation, expressed as a relative percentage (%), when the impact strength value of the test piece before irradiation is taken as 100%, when the test piece of the resin composition is irradiated with gamma rays.

[0018] (A) Polycarbonate (PC) resin As the polycarbonate resin that can be contained in the resin composition of the present invention, an aromatic polycarbonate resin is preferable, but there is no particular limitation on the type as long as the technical idea of the present invention can be realized, and any thermoplastic aromatic polycarbonate resin conventionally used in this field can be used. In one embodiment, the aromatic polycarbonate resin can be produced from a divalent phenol, a carbonate precursor, and a molecular weight modifier. The divalent phenol is one of the monomers constituting the aromatic polycarbonate resin, and is given by the following formula (1) [ka] (In the formula, X represents a linear, branched, or cyclic alkylene group without functional groups; or a linear, branched, or cyclic alkylene group containing one or more functional groups selected from the group consisting of sulfides, ethers, sulfoxides, sulfones, ketones, naphthyl, or isobutylphenyl; more specifically, X may be a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 6 carbon atoms.) R1 and R2 each independently represent a halogen atom or an alkyl group, for example, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms). n and m each independently represent integers from 0 to 4. The compound may also be represented by ).

[0019] Non-restrictive examples of the aforementioned divalent phenols include bisphenol (more specifically, 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A)), hydroquinone, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ether, and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane Examples include halogenated bisphenols such as bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis(4-hydroxyphenyl)decane, and 2-methyl-1,1-bis(4-hydroxyphenyl)propane, with bisphenol A being preferred.

[0020] The carbonate precursor is another monomer that constitutes the aromatic polycarbonate resin, and non-limiting examples include carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate, and dimethyl carbonate, but carbonyl chloride (phosgene) is preferred.

[0021] As the molecular weight modifier, conventionally known compounds, i.e., monofunctional substances similar to monomers used in the production of thermoplastic aromatic polycarbonate resins, can be used. Non-limiting examples of the molecular weight modifier include phenolic derivatives (e.g., p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, p-isononylphenol, etc.) and aliphatic alcohols, with p-tert-butylphenol (PTBP) being preferred.

[0022] Aromatic polycarbonate resins produced from such divalent phenols, carbonate precursors, and molecular weight modifiers can be, for example, linear polycarbonate resins, branched polycarbonate resins, copolymer resins, polyester carbonate resins, and silicone copolymer polycarbonates, either individually or in combination of two or more.

[0023] The aromatic polycarbonate resin preferably has a viscosity-average molecular weight (Mv, measured in a methylene chloride solution at 25°C) (g / mol) of 15,000 to 40,000, more preferably 17,000 to 30,000, and most preferably 20,000 to 30,000. If the viscosity-average molecular weight of the aromatic polycarbonate resin is less than 15,000, mechanical properties such as impact strength and tensile strength may decrease, while if it exceeds 40,000, the melt viscosity increases, which may hinder the processing of the resin.

[0024] (B) Polyalkylene glycol adduct of anhydrous sugar alcohol The polyalkylene glycol adduct of anhydrous sugar alcohol contained in the resin composition of the present invention is a compound in which a polyalkylene glycol substituent is bonded to the terminal hydroxyl group of anhydrous sugar alcohol.

[0025] The aforementioned anhydrous sugar alcohol can be produced by the dehydration reaction of naturally derived hydrides. Hydrides (also called "sugar alcohols") refer to compounds obtained by adding hydrogen to the reducing terminal group of a sugar, and are generally HOCH2(CHOH) n It is represented as CH2OH (where n is an integer from 2 to 5). Hydrogenated sugars are classified according to the number of carbon atoms into tetriitol, pentitol, hexitol, and heptitol (with 4, 5, 6, and 7 carbon atoms, respectively). Of these, hexitol, which has 6 carbon atoms, includes sorbitol, mannitol, iditol, and galactitol, with sorbitol and mannitol being particularly useful substances.

[0026] The anhydrous sugar alcohol may be a monoanhydrous sugar alcohol, a dianhydrous sugar alcohol, or a mixture thereof, and is not particularly limited, but a dianhydrous sugar alcohol can be used.

[0027] Monoanhydrosucrose alcohols are anhydrous sugar alcohols formed by removing one water molecule from within a hydride sugar, and have a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of monoanhydrosucrose alcohol is not particularly limited, but it is preferably monoanhydrosucrose hexitol, and more specifically, it may be 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more of these.

[0028] Dihydrous sugar alcohols are anhydrous sugar alcohols formed by removing two water molecules from within a hydride sugar. They have a diol form with two hydroxyl groups in the molecule and can be produced using hexitol derived from starch. Because dihydrous sugar alcohols are environmentally friendly substances derived from renewable natural resources, they have attracted considerable interest for many years, and research into their production continues to this day. Among these dihydrous sugar alcohols, isosorbide, produced from sorbitol, currently has the greatest potential for industrial application.

[0029] The type of dianhydrosodium alcohol is not particularly limited, but is preferably dianhydrosodium hexitol, and more specifically 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more of these. In a preferred embodiment of the present invention, the anhydrous sugar alcohol may be isosorbide.

[0030] In one embodiment, the polyalkylene glycol may be polyethylene glycol, polypropylene glycol, polybutylene glycol, or a combination thereof.

[0031] In one embodiment, the molecular weight (weight-average molecular weight) of the polyalkylene glycol may be 500 to 5000 g / mol, and more specifically, 1000 to 4000 g / mol, but is not limited thereto.

[0032] In one embodiment, the polyalkylene glycol adduct of the anhydrous sugar alcohol is given by the following formula (2) [ka] (In the formula, [OAO] is the part derived from anhydrous sugar alcohol obtained by removing hydrogen atoms from both terminal hydroxyl groups of anhydrous sugar alcohol, H-[X] p It is independently H-[O-alkylene] p And, [X'] q -H is independently [alkylene-O] q -H is, p and q each independently represent integers between 2 and 15. (This is shown by ). More specifically, the anhydro sugar alcohol may be isosorbide; the alkylene may be a linear alkylene having 2 to 8 carbon atoms or a branched alkylene having 3 to 8 carbon atoms, and more specifically, may be ethylene, propylene, butylene or a combination thereof; p and q may each independently represent an integer of 2 to 12.

[0033] In one embodiment, the polyalkylene glycol adduct of the anhydro sugar alcohol is represented by the following formula (3)

Chemical formula

[0034] In one embodiment, the polyalkylene glycol adduct of the anhydro sugar alcohol is obtained, for example, as shown in the following reaction formula, by reacting the hydroxy groups at both ends or one end (preferably both ends) of the anhydro sugar alcohol with an alkylene oxide in the presence of a catalyst (for example, a base catalyst), so that the hydrogen of the hydroxy groups at both ends or one end (preferably both ends) of the anhydro sugar alcohol is substituted with a hydroxyalkyl group which is an open-ring form of the alkylene oxide.

Chemical formula

[0035] In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, it may be ethylene oxide, propylene oxide, butylene oxide, or a combination thereof.

[0036] In one embodiment, the anhydrous sugar alcohol may be treated with an acid component before reacting with the alkylene oxide. The reaction between the acid-treated anhydrous sugar alcohol and the alkylene oxide may be carried out, for example, in a pressurized (e.g., pressurized to 3 MPa or higher) high-pressure reactor at a high temperature (e.g., 100°C to 180°C or 120°C to 160°C) in the presence of a base catalyst (e.g., alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, or alkaline earth metal hydroxides such as calcium hydroxide) for, for, for, 1 to 8 hours or 2 to 4 hours, but is not limited to these. The reaction molar ratio of the anhydrous sugar alcohol to the alkylene oxide may be, for example, 1 mole or more, 2 moles or more, or 3 moles or more of alkylene oxide per mole of anhydrous sugar alcohol, or 30 moles or less, 20 moles or less, 15 moles or less, or 12 moles or less, for example, 1 mole to 30 moles, preferably 2 to 20 moles, more preferably 3 to 15 moles, but is not limited to these.

[0037] In one embodiment, the amount of the polyalkylene glycol adduct of anhydrous sugar alcohol contained in the resin composition of the present invention may be more than 0.1 parts by weight and less than 5 parts by weight per 100 parts by weight of the polycarbonate resin. If the content of the polyalkylene glycol adduct of anhydrous sugar alcohol in the resin composition is outside the above range, the ionizing radiation resistance of the resin composition decreases, the change in color and brightness after gamma ray irradiation becomes significant, the color recovery over time is poor, and the impact strength retention rate may also be poor.

[0038] In one embodiment, the content of the polyalkylene glycol adduct of the anhydrous sugar alcohol in the resin composition of the present invention is, for example, more than 0.1 parts by weight, 0.11 parts by weight or more, 0.15 parts by weight or more, 0.2 parts by weight or more, 0.25 parts by weight or more, 0.3 parts by weight or more, 0.35 parts by weight or more, 0.4 parts by weight or more, 0.45 parts by weight or more, 0.5 parts by weight or more, or 0.55 parts by weight or less, relative to 100 parts by weight of the polycarbonate resin. The above amounts may be 0.6 parts by weight or more, 0.65 parts by weight or more, 0.7 parts by weight or more, 0.75 parts by weight or more, or 0.8 parts by weight or more, and may also be less than 5 parts by weight, 4.9 parts by weight or less, 4.5 parts by weight or less, 4 parts by weight or less, 3.5 parts by weight or less, 3 parts by weight or less, 2.5 parts by weight or less, 2 parts by weight or less, 1.5 parts by weight or less, 1.4 parts by weight or less, 1.3 parts by weight or less, or 1.2 parts by weight or less, but are not particularly limited to these.

[0039] (C) Coloring agent ingredients The coloring agent component contained in the resin composition of the present invention is a blue pigment, a red pigment, or a combination thereof.

[0040] In one embodiment, the coloring agent component is a blue pigment; or a blue pigment and a red pigment. (Alternatively, the coloring agent component is also called a blue-violet pigment.) In one embodiment, the blue pigment may be an anthraquinone-based blue pigment, a phthalocyanine-based blue pigment, or a combination thereof. In one embodiment, examples of the anthraquinone-based blue pigment include Solusis VIOLET B and Solusis SLS VT 13, and examples of the phthalocyanine-based blue pigment include Chemizone and BLUE K6907, but the invention is not limited to these.

[0041] In one embodiment, the red pigment may be an anthraquinone-based red pigment. In one embodiment, examples of the anthraquinone-based red pigment include, but are not limited to, Solusis VIOLETE 3R, MJ Finechem VIOLET 3R, and UNI VIOLET S-BR.

[0042] In one embodiment, when the coloring agent component is a combination of a blue pigment and a red pigment, the combination ratio may be 1 to 3 (blue pigment): 1 (red pigment) as the weight ratio of blue to red pigment, more specifically 1.5 to 2.5 (blue pigment): 1 (red pigment), for example, 2:1.

[0043] In one embodiment, the amount of the coloring agent component contained in the resin composition of the present invention may be 0.0001 parts by weight to 0.001 parts by weight per 100 parts by weight of the polycarbonate resin. If the content of the coloring agent component in the resin composition is less than the above range, the ionizing radiation resistance of the resin composition will decrease, the change in color and brightness after gamma ray irradiation will be significant, and the ability to recover color over time may be poor. Conversely, if it exceeds the above range, the change in brightness after gamma ray irradiation may be significant.

[0044] In one embodiment, the content of the coloring agent component in the resin composition of the present invention may be, for example, 0.0001 parts by weight or more, 0.0005 parts by weight or more, or 0.0006 parts by weight or more, or 0.001 parts by weight or less, 0.0009 parts by weight or less, 0.0008 parts by weight or less, 0.0007 parts by weight or less, or 0.0006 parts by weight or less, but is not particularly limited to these.

[0045] The resin composition of the present invention may further contain a phosphorus-based stabilizer in addition to the above-mentioned components. The phosphorus-based stabilizer can be one of the conventionally known substances, specifically, for example, phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphate, and other phosphorus oxoacids; acidic pyrophosphate metal salts such as sodium acidic pyrophosphate, potassium acidic pyrophosphate, and calcium acidic pyrophosphate; phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; phosphate compounds, phosphite compounds, and phosphonitrite compounds. Phosphite compounds are preferred due to their resistance to discoloration and continuous productivity, but the invention is not limited to these.

[0046] In one embodiment, the phosphite compound may be a trivalent phosphorus compound represented by formula: P(OR)3, where R represents a monovalent or divalent organic group. More specifically, the phosphite compound may be, for example, triphenyl phosphite, tris(mononylphenyl) phosphite, tris(mononyl / dinonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, distearylpentaerythritol diphosphite, bis(2,4-di-tert Examples include, but are not limited to, butyl-4-methylphenyl)pentaerythritol phosphite, bis(2,6-di-tert-butylphenyl)octyl phosphate, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphite, and 6-[3-(3-tert-butyl-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]-dioxaphosfepine. The phosphorus-based stabilizer may be used alone or in combination of two or more types.

[0047] In one embodiment, if the resin composition of the present invention contains the phosphorus-based stabilizer, its content may be 0.05 parts by weight to 1 part by weight per 100 parts by weight of the polycarbonate resin, more specifically 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more, or 0.9 parts by weight or less, 0.8 parts by weight or less, 0.7 parts by weight or less, 0.6 parts by weight or less, or 0.5 parts by weight or less, but is not particularly limited to these.

[0048] The resin composition of the present invention may further contain a phenolic stabilizer in addition to the above-mentioned components.

[0049] The phenolic stabilizer can be one of conventionally known types, and its content may be 0.05 parts by weight to 1 part by weight per 100 parts by weight of the polycarbonate resin, more specifically 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more, or 0.9 parts by weight or less, 0.8 parts by weight or less, 0.7 parts by weight or less, 0.6 parts by weight or less, or 0.5 parts by weight or less, but is not limited to these.

[0050] The resin composition of the present invention may further contain a lubricant in addition to the above-mentioned components.

[0051] Specifically, the lubricant may be a polyethylene compound, an ethylene-ester compound, an ethylene glycol-glyceric acid ester compound, a montan compound, an ethylene glycol-glycerin montan acid ester compound, or a mixture of two or more of these. Its content may be 0.05 to 1 part by weight per 100 parts by weight of the polycarbonate resin, more specifically 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more, or 0.9 parts by weight or less, 0.8 parts by weight or less, 0.7 parts by weight or less, 0.6 parts by weight or less, or 0.5 parts by weight or less, but is not limited to these. In addition to the components described above, the resin composition of the present invention may optionally contain one or more further additives, to the extent that the objectives of the present invention can be achieved. If other additives are present, their amount may be, for example, 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight, per 100 parts by weight of the polycarbonate resin.

[0052] According to another aspect of the present invention, a molded article comprising the polycarbonate resin composition of the present invention is provided. The molded articles of the present invention are manufactured by extrusion molding, casting, blow molding, or injection molding of a molten polycarbonate resin composition of the present invention.

[0053] In one embodiment, the molded article of the present invention is a medical product resistant to ionizing radiation.

[0054] The present invention will be described in more detail through the following examples and comparative examples. However, the scope of the present invention is not limited in any way by these examples. [Examples]

[0055] The components used in the examples and comparative examples of the present invention are described below, and the amounts of each component are shown in Table 1. (A) Polycarbonate resin: (A-1) TRIREX 3022PJ with viscosity-average molecular weight of 23,000 (A-2) TRIREX 3030PJ with viscosity-average molecular weight of 30,000 (A-3) TRIREX 3020PJ with viscosity-average molecular weight of 19,000 (B) Alkylene glycol adducts of isosorbide: (B-1) ISB-PPG: PI-1000 (Polypropylene glycol adduct, Molecular weight: 1000 g / mol) (B-2) ISB-PPG: PI-2000 (Polypropylene glycol adduct, Molecular weight: 2000 g / mol) (B-3) ISB-PEG:EI-2000 (Polyethylene glycol adduct, Molecular weight: 2000 g / mol) (B-4) ISB-PBG: BI-2000 (Polybutylene glycol adduct, Molecular weight: 2000 g / mol) (C) Polypropylene glycol (PPG): PPG-2000 (molecular weight: 2000g / mol) (D) Polyethylene glycol (PEG): PEG-2000 (molecular weight: 2000g / mol) (E) Phosphorus stabilizers: (E-1) Tris-(2,4-di-tert-butylphenyl)-phosphite (Songnox 1076) (E-2) Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (ALK240) (F) Lubricant: Fatty acid methyl ester lubricant (PETS-AHS) (G) Coloring agent ingredients: (G-1) Anthraquinone-based blue pigment (blue-violet oil-based solvent dye Violet 13, Solusis SLS VT 13) (G-2) Anthraquinone-based red pigment (reddish-purple transparent oil-based solvent dye Violet 36, UNI VIOLET S-BR) (G-3) Phthalocyanine-based blue pigment (blue pigment 15:1, Chemizone, BLUE K6907)

[0056] Examples 1-20 and Comparative Examples 1-14 The resin composition was prepared by mixing the components in the composition ratios shown in Table 1 below, and extruded using a twin-screw molten metal extruder with L / D=48 and Φ=25mm under the conditions of a melting temperature of 280-300°C, a screw rotation speed of 150 rpm, a first vent pressure of approximately -600 mmHg, and a self-feeding rate of 15 kg / h. After cooling the extruded strands in water, they were cut with a rotary cutter to produce pellets. The prepared pellets were dried with hot air at 100°C to 120°C for 4 hours, and then test specimens were prepared by injection molding at a cylinder temperature of 280°C to 300°C and a molding temperature of 80°C. The physical properties of each prepared test specimen were measured using the method described below, and the results are shown in Table 2.

[0057] - Melt Index (MI): Measured at 300°C and 1.2 kgf load based on ASTM D1238. -Tensile strength (MPa): Evaluated based on ASTM D638 - Bending strength (MPa) and flexural modulus (MPa): Evaluated according to ASTM D790 - Impact strength (J / m): Evaluated based on ASTM D256 (1 / 8 inch thickness, notched Izod). - Heat distortion temperature (HDT, °C): 18.6 kg / cm² based on ASTM D648. 2 Evaluated under load - Yellowness Index (YI): The YI value of a square test specimen (50 × 80 × 3.0 mm) was measured using an X-rite CI 7800SE spectrophotometer, based on ASTM D1925. - Brightness (L): The L value of a square test specimen (50 × 80 × 3.0 mm) was measured using an X-rite CI7800SE spectrophotometer, based on ASTM D2244. - △YI value 1 day after gamma ray irradiation (△YI 1d ): For the square test piece of the resin composition, the YI value before gamma ray irradiation (YI0) and the YI value one day after irradiation with 25 kGy of gamma rays (YI 1d ) is measured, and the ΔYI value (ΔYI) after 1 day of gamma ray irradiation is measured according to the following formula. 1d ) was calculated. △YI 1d =YI 1d -YI0 -△YI value 7 days after gamma ray irradiation (△YI 7d ): For the square test piece of the resin composition, the YI value before gamma ray irradiation (YI0) and the YI value 7 days after irradiation with 25 kGy of gamma rays (YI 7d After measuring the ΔYI value 7 days after gamma ray irradiation, the following formula is used to determine the ΔYI value (ΔYI 7d ) was calculated. △YI 7d =YI 7d -Y I0 - Impact strength retention rate value (impact strength %) one day after gamma ray irradiation 1dFor test specimens used to measure the impact strength of resin compositions, the impact strength before gamma ray irradiation and the impact strength one day after 25 kGy of gamma ray irradiation were measured. The impact strength of the test specimen after gamma ray irradiation was expressed as a relative percentage (%), with the impact strength of the test specimen before gamma ray irradiation set to 100%. - L value 7 days after gamma ray irradiation (L 7d ): For the square test piece of the resin composition, the L value (L) after 7 days of gamma ray irradiation with 25 kGy 7d ) was calculated.

[0058] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4]

[0059] As shown in Table 2 above, all compositions of Examples 1 to 20 exhibited superior mechanical properties compared to the comparative examples, as well as remarkably superior resistance to ionizing radiation (i.e., even after irradiation with ionizing radiation (gamma rays), the change in yellow index was small, the impact strength retention rate was high, and the brightness (L) was also excellent). In particular, compositions of Examples 1 to 20 showed a ΔYI value (ΔYI) after 1 day of gamma ray irradiation. 1dThe ΔYI value (ΔYI) after 7 days of gamma ray irradiation was significantly lower than that of Comparative Examples 1-14, which means that the discoloration resistance is significantly better than that of the comparative examples. 7d The value is significantly lower compared to the comparative example, which means that the color recovery power is significantly superior to that of the comparative example.

Claims

1. A radiation-resistant polycarbonate resin composition, (A) Polycarbonate resin; (B) Polyalkylene glycol adducts of anhydrous sugar alcohols; and (C) Colorant components that are blue pigments, red pigments, or combinations thereof; Includes, A polycarbonate resin composition in which, when a 3 mm thick test piece of the resin composition is irradiated with 25 kGy of gamma rays and measured according to ASTM D1925 7 days after irradiation, the change in yellowness index (△YI) value is 14.7 or less.

2. The polycarbonate resin composition according to claim 1, wherein when a 3 mm thick test piece of the resin composition is irradiated with 25 kGy of gamma rays and measured according to ASTM D1925 one day after irradiation, the change in yellowness index (△YI) value is 25.5 or less.

3. The polycarbonate resin composition according to claim 1, wherein when a 3 mm thick test piece of the resin composition is irradiated with 25 kGy of gamma rays and measured according to ASTM D2244 7 days after irradiation, the lightness value is 85.5 or higher.

4. The polycarbonate resin composition according to claim 1, wherein when an impact strength test specimen (1 / 8 inch thick, notched Izod) of the resin composition is irradiated with 25 kGy of gamma rays and measured according to ASTM D256 one day after irradiation, the impact strength retention rate is 94.9% or more.

5. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate resin.

6. The polyalkylene glycol adduct of the anhydrous sugar alcohol is given by the following formula (2) 【Chemistry 1】 (In the formula, [O-A-O] is the part derived from anhydrous sugar alcohol obtained by removing hydrogen atoms from both terminal hydroxyl groups of anhydrous sugar alcohol, H-[X] p It is independently H-[O-alkylene] p And, [X'] q -H is independently [alkylene-O] ｑ -H, The polycarbonate resin composition according to claim 1, where p and q each independently represent an integer from 2 to 15.

7. The polycarbonate resin composition according to claim 1, wherein the coloring agent component is solely a blue pigment.

8. The polycarbonate resin composition according to claim 1, wherein the coloring agent component is a combination of a blue pigment and a red pigment.

9. The polycarbonate resin composition according to claim 1, further comprising a phosphorus-based stabilizer.

10. The polycarbonate resin composition according to claim 1, further comprising a lubricant.

11. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 10.

12. The molded article according to claim 11, which is a medical product having resistance to ionizing radiation.

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