Polycarbonate resin composition and molded article thereof

Abstract

To provide a polycarbonate resin composition excellent in impact resistance, light-shielding properties, heat resistance, and dry heat resistance.SOLUTION: The polycarbonate resin composition of the present disclosure contains: a polycarbonate resin (A) containing a structural unit represented by the following formula 1 as a repeating unit; and an impact resistance modifier (B). The impact resistance modifier (B) is contained in an amount of 1-20 pts.mass based on 100 pts.mass of the polycarbonate resin (A) and is an epoxy group-containing polyethylene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a polycarbonate resin composition and a molded article thereof. [Background technology]

[0002] Polycarbonate resins are typically polymers formed by linking aromatic or aliphatic diol compounds with carbonate esters. Among these, polycarbonate resins obtained from 2,2-bis(4-hydroxyphenyl)propane (sometimes called bisphenol A) are used in many fields due to their excellent transparency, heat resistance, and mechanical properties such as impact resistance.

[0003] Polycarbonate resins are generally produced using raw materials obtained from petroleum resources. However, in recent years, concerns have arisen about the depletion of petroleum resources, and polycarbonate resins using ether diols produced from carbohydrates of biological origin have been investigated.

[0004] For example, Patent Document 1 proposes a homopolycarbonate resin with a melting point of 203°C produced using a melt transesterification method. Patent Document 2 proposes a polycarbonate resin with a glass transition temperature of 170°C or higher produced using a tin catalyst. Patent Document 3 proposes a copolymer polycarbonate of isosorbide and a linear aliphatic diol. Patent Document 4 proposes a decorative sheet having a polycarbonate resin layer containing a plant-derived ether diol residue.

[0005] Patent Documents 5 to 7 disclose compositions in which various impact-modifying components are added to isosorbide polycarbonate resins for the purpose of improving impact resistance. Patent Document 8 discloses a polycarbonate resin composition with improved dry heat resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] GB Patent Application Publication No. 1079686 [Patent Document 2] International Publication No. 2007 / 013463 [Patent Document 3] International Publication No. 2004 / 111106 [Patent Document 4] International Publication No. 2011 / 021720 [Patent Document 5] International Publication No. 2012 / 008344 [Patent Document 6] International Publication No. 2014 / 021475 [Patent Document 7] Japanese Patent Application Laid-Open No. 2012-214692 [Patent Document 8] Japanese Patent Application Publication No. 2018-30908 Summary of the Invention [Problem to be solved by the invention]

[0007] For example, when considering the industrial application of polycarbonate resin prepared using plant-derived isosorbide, it is necessary to improve its impact resistance. For example, the notched Charpy impact strength according to ISO 179 of isosorbide homopolycarbonate resin with a specific viscosity of 0.33 is approximately 6 kJ / m 2 This value is insufficient for industrial applications, and further improvement is necessary.

[0008] Generally, impact resistance is highly dependent on the molecular weight, which contributes to the specific viscosity of the resin, and therefore, in order to improve impact resistance, it is necessary to increase the molecular weight of the resin. The isosorbide polycarbonate resins described in Patent Documents 1 and 2 have the problem that increasing the molecular weight makes the melt viscosity of the resin too high, making molding difficult. The polycarbonate resin described in Patent Document 3 also has a notched Charpy impact strength according to ISO 179 of a polycarbonate resin with a reduced viscosity of about 0.9, which corresponds to Example 6, for example, and is about 7 kJ / m 2 However, further improvement is required for industrial applications.

[0009] Patent Documents 5 to 7 disclose isosorbide polycarbonate resin compositions with improved impact resistance, but do not disclose any description of dry heat resistance, which is an important test item in actual environments. According to studies by the present inventors, it has been found that the impact modifiers used in the polycarbonate resin compositions described in Patent Documents 5 to 7 are inferior in dry heat resistance performance.

[0010] Furthermore, Patent Document 8 discloses a polycarbonate resin composition with improved dry heat resistance. However, due to its high transparency, it has poor light-blocking properties, which can cause problems when used in actual light-blocking applications. For example, it has been found to be unsuitable for use as a glass substitute for privacy glass in automobiles and smoked glass used in windows. Therefore, there has been a demand for a polycarbonate resin composition with excellent impact resistance, light-blocking properties, heat resistance, and dry heat resistance.

[0011] Therefore, an object of the present disclosure is to provide a polycarbonate resin composition that is excellent in impact resistance, light-shielding properties, heat resistance, and dry heat resistance. [Means for solving the problem]

[0012] <Aspect 1> A polycarbonate resin (A) containing a structural unit represented by the following formula 1 as a repeating unit, and Contains an impact modifier (B), A polycarbonate resin composition comprising the impact modifier (B) in an amount of 1 to 20 parts by mass relative to 100 parts by mass of the polycarbonate resin (A), and which is an epoxy group-containing polyethylene: [ka] <Aspect 2> Aspect 2. The composition according to aspect 1, wherein the polycarbonate resin (A) contains 30 mol % or more of the structural unit represented by Formula 1, relative to 100 mol % of all structural units derived from diol. <Aspect 3> 3. The composition of any one of the preceding aspects, wherein the impact modifier (B) is an ethylene-glycidyl (meth)acrylate copolymer. <Aspect 4> Aspect 4. The composition according to any one of Aspects 1 to 3, wherein the polycarbonate resin (A) further contains a structural unit derived from a diol compound other than that of Formula 1. <Aspect 5> Aspect 5. The composition according to any one of aspects 1 to 4, having a deflection temperature under load of 90° C. or higher under a pressure of 1.8 MPa. <Aspect 6> A composition according to any one of aspects 1 to 5, having a total light transmittance of 30% or less as measured using a molded plate having a thickness of 2 mm. <Aspect 7> A composition according to any one of aspects 1 to 6, having a haze of 50% or more as measured on a molded plate having a thickness of 2 mm. <Aspect 8> A polycarbonate resin molded article molded using the composition according to any one of aspects 1 to 7. [Effects of the Invention]

[0013] According to the present disclosure, it is possible to provide a polycarbonate resin composition having excellent impact resistance, light-shielding properties, heat resistance, and dry heat resistance.

[0014] Furthermore, the polycarbonate resin composition of the present disclosure having the above-described properties can be used in a wide variety of applications, including, for example, film or sheet materials, interior or exterior materials for electric or electronic devices, interior or exterior materials for various vehicles such as automobiles, various containers or packaging materials such as bottles, and interior or exterior materials for buildings. DETAILED DESCRIPTION OF THE INVENTION

[0015] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0016] A polycarbonate resin composition according to one embodiment of the present disclosure comprises a polycarbonate resin (A) containing a structural unit represented by the following formula 1 as a repeating unit, and an impact modifier (B), wherein the impact modifier (B) is contained in an amount of 1 to 20 parts by mass per 100 parts by mass of the polycarbonate resin (A), and the polycarbonate resin composition is an epoxy group-containing polyethylene: [ka]

[0017] The polycarbonate resin composition of the present disclosure has excellent impact resistance, light-shielding properties, heat resistance, and dry heat resistance. Without being limited by the theory, the action principle of the polycarbonate resin composition of the present disclosure is believed to be as follows.

[0018] The polycarbonate resin composition of the present disclosure contains a specific polycarbonate resin and a specific impact modifier in specific proportions. It is believed that the structure of the impact modifier contributes to improving impact resistance without adversely affecting the heat resistance and dry heat resistance of the specific polycarbonate resin itself. Furthermore, neither the polycarbonate resin nor the impact modifier contains an unsaturated bond in its structure. Therefore, it is presumed that the generation of substances that cause coloration under heating conditions is suppressed, thereby reducing or preventing changes in hue.

[0019] Furthermore, it has been found that the incorporation of this specific impact modifier also contributes to light-blocking properties. Generally, the decrease in total light transmittance and increase in haze value associated with the incorporation of an impact modifier are often caused by a decrease in the dispersibility of the polycarbonate resin and the impact modifier. In this case, the decrease in the dispersibility of the impact modifier generally leads to a decrease in other performance properties, such as heat resistance, dry heat resistance, and impact resistance. However, it has been unexpectedly found that the specific impact modifier of the present disclosure can improve not only impact resistance but also light-blocking properties without adversely affecting the heat resistance and dry heat resistance of the specific polycarbonate resin itself. This is believed to be a previously unknown advantageous effect resulting from the selection of a specific polycarbonate resin and a specific impact modifier.

[0020] <Polycarbonate Resin Composition> From the viewpoint of impact resistance and light-blocking properties, the polycarbonate resin composition of the present disclosure preferably contains 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, or 5 parts by mass or more of an impact modifier (B) described below per 100 parts by mass of a polycarbonate resin (A) described below. There is no particular upper limit on the amount of impact modifier (B) added, but from the viewpoint of appearance performance such as in-plane unevenness of a molded article, it is preferable to add 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, or 10 parts by mass or less of impact modifier (B) per 100 parts by mass of the polycarbonate resin (A).

[0021] The polycarbonate resin composition of the present disclosure is excellent in various performances as shown below.

[0022] <Impact resistance> The polycarbonate resin composition of the present disclosure has excellent impact resistance. For example, a molded article obtained from the polycarbonate resin composition has a Charpy impact strength of 10 kJ / m 2 More than 15kJ / m 2 More than 20kJ / m 2 or more than 25kJ / m 2There is no particular upper limit to this value, but for example, 100 kJ / m 2 Below, 90kJ / m 2 or less, or 80kJ / m 2 It can be defined as follows:

[0023] <Shielding performance> (Total light transmittance) The polycarbonate resin composition of the present disclosure has excellent shielding properties. For example, when a 2 mm thick sheet obtained from the polycarbonate resin composition is used, the total light transmittance of the sheet can be 30% or less, 20% or less, 10% or less, 5% or less, or 1% or less. There is no particular restriction on the lower limit, but it can be specified as, for example, 0% or more, more than 0%, or 0.1% or more. Here, in the present disclosure, "total light transmittance" indicates the level of transparency and means the ratio of transmitted light to incident light according to method E308 of ASTM-D1003-61.

[0024] (Hayes) Light-blocking properties can be defined not only by total light transmittance but also by haze. For example, when a 2 mm thick sheet obtained from a polycarbonate resin composition is used, the haze of the sheet can be 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more. There is no particular upper limit, but it can be defined as, for example, 100% or less, less than 100%, or 99% or less. Here, in the present disclosure, "haze" indicates the level of transparency and means the percentage (%) of transmitted light that deviates from the incident light beam due to forward scattering when passing through a test piece according to ASTM-D1003-61.

[0025] <Heat resistance> The polycarbonate resin composition of the present disclosure has excellent heat resistance. Heat resistance refers to the degree to which a molded article undergoes minimal deformation at high temperatures, and can be evaluated, for example, by the deflection temperature under load test described below. Molded articles obtained from the polycarbonate resin composition can achieve a deflection temperature under load of 90°C or higher, 95°C or higher, or 100°C or higher. There is no particular upper limit, but the upper limit can be specified as 130°C or lower, 120°C or lower, or 110°C or lower, for example.

[0026] <Dry heat resistance> The polycarbonate resin composition of the present disclosure has excellent dry heat resistance. Dry heat resistance refers to the fact that the molded product undergoes little change in hue or deterioration when left at high temperatures for an extended period of time. For example, molded products obtained from the polycarbonate resin composition can achieve a yellowing index (ΔYI) of 10 or less, 8 or less, or 5 or less in the dry heat resistance test described below. There is no particular restriction on the lower limit, but it can be specified as, for example, 0.1 or more, 0.5 or more, or 1 or more.

[0027] <Polycarbonate resin (A)> The polycarbonate resin (A) of the present disclosure contains a structural unit represented by the following formula 1 as a repeating unit: [ka]

[0028] (Structural unit represented by formula 1) The proportion of the structural units represented by Formula 1 is not particularly limited, but from the viewpoint of substitution for petroleum resources and from the viewpoint of heat resistance and impact resistance, etc., it can be, for example, 30 mol% or more, preferably 40 mol% or more, more preferably 45 mol% or more, and particularly preferably 50 mol% or more, relative to 100 mol% of all structural units derived from diol. There is no particular limit to the upper limit of such structural units, but it can be specified, for example, as 100 mol% or less, 90 mol% or less, or 80 mol% or less. Here, the molar ratio of the structural units in the polycarbonate resin can be calculated, for example, by measurement using proton NMR on a JNM-AL400 manufactured by JEOL Ltd.

[0029] The structural unit of formula 1 can include structural units represented by the following formulae 1-1 to 1-3, which are in a stereoisomeric relationship: [ka] [ka] [ka]

[0030] These structural units are derived from carbohydrate-derived ether diols, which are substances obtained from natural sources such as biomass and are considered renewable resources.

[0031] The structural units represented by Formulas 1-1 to 1-3 are derived from substances called isosorbide, isomannide, and isoidide, respectively. For example, isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can also be obtained by similar reactions, excluding the starting material.

[0032] Among isosorbide, isomannide, and isoidide, isosorbide (1,4;3,6-dianhydro-D-sorbitol) is preferred. Polycarbonate resins containing structural units derived from isosorbide as repeating units are relatively easy to produce and have excellent heat resistance.

[0033] (Structural units other than Formula 1) The polycarbonate resin (A) may contain, as a repeating unit, structural units derived from various diol compounds other than the structural unit represented by Formula 1. Such diol compounds (diol monomers) may be any of aliphatic diol compounds, alicyclic diol compounds, and aromatic dihydroxy compounds, and examples thereof include the diol compounds described in Patent Documents 3 and 4, and oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. These may be used alone or in combination of two or more. Representative examples of diol compounds are shown below, but the present invention is not limited thereto.

[0034] Examples of the aliphatic diol compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl- Examples include 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol.

[0035] Examples of alicyclic diol compounds include cyclohexanedimethanol, tricyclodecane dimethanol, adamantanediol, pentacyclopentadecanedimethanol, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2,4,4-tetramethylcyclobutanediol, 1,1'-spirobiindane-6,6'-diol, decalin-2,6-dimethanol, norbornane dimethanol, and cyclopentane-1,3-dimethanol.

[0036] Examples of aromatic dihydroxy compounds include α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (bisphenol M), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, bisphenol A, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3- Hexafluoropropane (bisphenol AF), biphenol, 1,1-bis(4-hydroxyphenyl)decane, bis(2-hydroxyethoxy)naphthalene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl) -1,8-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1,8-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-di Phenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-3,6-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-3,6-diphenylfluorene fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)- 4,5-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-4,5-Diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-diphenylfluorene, 2,2'-bis(2-hydroxyethoxy)-3,3'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-diphenyl-1 ,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-3,3'-dimethyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-dimethyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-7,7'-dimethyl-1,1'-binaphthyl, 1,1'-bi-2-naphthol, dihydroxynaphthalene, etc.

[0037] The proportion of structural units derived from diol compounds other than Formula 1 can be 70 mol% or less, 60 mol% or less, 55 mol% or less, or 50 mol% or less, relative to 100 mol% of all structural units derived from diols. There is no particular restriction on the lower limit of such structural units, but it can be specified, for example, as more than 0%, 10 mol% or more, or 20 mol% or more.

[0038] (Method for producing polycarbonate resin (A)) The method for producing the polycarbonate resin (A) is not particularly limited, and any known method for producing a typical polycarbonate resin can be used. For example, the polycarbonate resin (A) can be produced by reacting a diol component with a carbonate precursor such as a carbonic acid diester. Several embodiments of the method for producing the polycarbonate resin (A) are described below.

[0039] The transesterification reaction using a carbonate diester as a carbonate precursor is carried out by stirring a predetermined ratio of diol components with the carbonate diester under heating in an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is typically in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol. If necessary, a terminal capping agent, antioxidant, etc. may be used.

[0040] The carbonic acid diester used in the transesterification reaction is not particularly limited, and examples thereof include esters of an aryl group or aralkyl group having 6 to 12 carbon atoms, which may be substituted. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred.

[0041] The amount of the carbonate diester, particularly diphenyl carbonate, used is preferably in the range of 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the total amount of the dihydroxy compounds.

[0042] In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds. These compounds can be used alone or in combination of two or more. Among them, compounds such as organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, and quaternary ammonium hydroxides of alkali metals or alkaline earth metals are preferably used.

[0043] Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, and lithium salt of phenol.

[0044] Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, barium diacetate, and barium stearate.

[0045] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Other examples include tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Other examples include bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0046] Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0047] The amount of the polymerization catalyst used is preferably 1×10 -9 ~1×10 -2 equivalent, more preferably 1×10 -8 ~1×10 -5 equivalent, particularly preferably 1×10 -7 ~1×10 -3 It is equivalent.

[0048] A catalyst deactivator can also be added in the latter stage of the reaction. There are no particular restrictions on the catalyst deactivator used, but known catalyst deactivators are effectively used. Among these, ammonium salts of sulfonic acid, phosphonium salts of sulfonic acid, and sulfonic acid esters are preferred. These can be used alone or in combination of two or more.

[0049] Furthermore, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate, and salts of paratoluenesulfonic acid such as tetrabutylammonium paratoluenesulfonate are preferred.

[0050] Preferred examples of sulfonic acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, octyl paratoluenesulfonate, and phenyl paratoluenesulfonate. Among these, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used.

[0051] When at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds is used, the amount of these catalyst deactivators used is preferably 0.5 to 50 mol, more preferably 0.5 to 10 mol, and particularly preferably 0.8 to 5 mol, per mol of the catalyst.

[0052] The polycarbonate resin (A) of the present disclosure obtained in this manner can have the following properties.

[0053] (Specific viscosity:η SP ) The specific viscosity (η SP ) is preferably in the range of 0.2 to 1.5, more preferably in the range of 0.25 to 1.2, even more preferably in the range of 0.3 to 1.0, and particularly preferably in the range of 0.3 to 0.5, from the viewpoints of molding processability and the strength of the resulting molded product.

[0054] The specific viscosity can be determined from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C using an Ostwald viscometer according to the following equation 2: Specific viscosity (η SP )=(t-t0) / t0…Equation 2 Here, t0 is the number of seconds it takes for methylene chloride to fall, and t is the number of seconds it takes for the sample solution to fall.

[0055] More specifically, polycarbonate resin is dissolved in 20 to 30 times its weight of methylene chloride, and the methylene chloride soluble fraction is collected through Celite filtration. The methylene chloride is then thoroughly dried to remove the methylene chloride, and a solid polycarbonate resin is obtained from the methylene chloride soluble fraction. 0.7 g of the resulting solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined using an Ostwald viscometer.

[0056] (glass transition temperature: Tg) The glass transition temperature (Tg) of the polycarbonate resin (A) of the present disclosure is preferably in the range of 100 to 160°C, more preferably in the range of 110 to 150°C, and particularly preferably in the range of 120 to 140°C, from the viewpoints of heat resistance stability, moldability, and the like.

[0057] The glass transition temperature (Tg) can be measured, for example, using a 2910 DSC measuring device manufactured by TA Instruments Japan Co., Ltd. at a temperature rise rate of 20°C / min.

[0058] (5% weight loss temperature: Td) From the viewpoint of the decomposition resistance of the resin during molding, the 5% weight loss temperature (Td) of the polycarbonate resin (A) of the present disclosure is preferably 280° C. or higher, or 300° C. or higher, and is preferably 400° C. or lower, 390° C. or lower, or 380° C. or lower. The 5% weight loss temperature can be measured, for example, using a TGA measuring device (model TGA2950) manufactured by TA Instruments.

[0059] (melt viscosity) The polycarbonate resin (A) of the present disclosure has a melt viscosity measured with a capillary rheometer at 240°C and a shear rate of 6080 sec -1 Under the condition of 0.01×10 3 ~1.10×10 3 It is preferable that the range is Pa·s, and 0.05×10 3 ~1.0×10 3 It is more preferable that the range is Pa·s, and 0.1×10 3 ~0.8×10 3 It is more preferable that the melt viscosity is in the range of Pa·s. When the melt viscosity is in this range, the flowability is good, so that secondary processing such as injection molding can be performed at low temperatures, and heat-induced deterioration of the resin, such as deterioration in color and decrease in polymerization degree, can be reduced or prevented, so that the reject rate during molding can be reduced and molded products with sufficient mechanical strength can be obtained.

[0060] <Impact modifier (B)> The polycarbonate resin composition of the present disclosure contains an impact modifier (B). The impact modifier (B) is not particularly limited as long as it is an epoxy group-containing polyethylene, i.e., a polyethylene having epoxy groups, and may be, for example, a copolymer of ethylene and a compound having epoxy groups, or polyethylene graft-modified with a compound having epoxy groups.

[0061] As a compound having an epoxy group used in producing the epoxy group-containing polyethylene, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity. Therefore, an ethylene-glycidyl (meth)acrylate copolymer is particularly preferably used as the impact modifier (B). Here, in the present disclosure, (meth)acrylate means acrylate or methacrylate.

[0062] The content of epoxy groups in the epoxy group-containing polyethylene is preferably 1% by mass or more, 2% by mass or more, or 3% by mass or more from the viewpoints of impact resistance, light-shielding properties, etc., and is preferably 20% by mass or less, 15% by mass or less, or 10% by mass from the viewpoints of ease of production of the epoxy group-containing polyethylene, etc.

[0063] The epoxy group-containing polyethylene may contain, in addition to ethylene, a copolymerization component having an ethylenic double bond. Examples of such copolymerization components include alkyl (meth)acrylate, acrylonitrile, α-olefin, conjugated diene, etc. Among these, from the viewpoint of good polymerization reactivity as a raw material monomer for the epoxy group-containing polyethylene, at least one selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, ethyl (meth)acrylate, vinyl acetate, styrene, butadiene, acrylonitrile, and propylene is preferred, and methyl acrylate and / or vinyl acetate is more preferred.

[0064] The impact modifier (B) of the present disclosure can be obtained as a commercially available product. Examples of commercially available products include "BONDFAST" manufactured by Sumitomo Chemical Co., Ltd., which is an ethylene-glycidyl methacrylate (GMA) copolymer, and "LOTADER" manufactured by Arkema.

[0065] The epoxy group-containing polyethylene may be used alone, or two or more kinds of polyethylenes having different ethylene unit contents, copolymerization components, physical properties, etc. may be mixed and used.

[0066] The average particle size of the impact modifier (B) is not particularly limited, but is preferably 10 nm or more, 15 nm or more, or 20 nm or more, and is preferably 1000 nm or less, 900 nm or less, or 800 nm or less, from the viewpoint of impact resistance, light blocking properties, etc. Here, the average particle size of the impact modifier (B) can be measured, for example, by dynamic light scattering.

[0067] <Optional ingredients> The polycarbonate resin composition of the present disclosure may optionally contain additives such as heat stabilizers, mold release agents, UV absorbers, light stabilizers, bluing agents, dyes, fluorescent dyes, fillers, pigments, polycarbonate plasticizers, flame retardants, lubricants, antibacterial agents, surfactants, and antistatic agents, as well as other resin components other than the polycarbonate resin (A). These optional components may be used alone or in combination of two or more. Some of these additives are described in more detail below.

[0068] The method for mixing the polycarbonate resin (A) with the various optional components is not particularly limited, and any commonly used polymer blending method may be used, such as a method using a tumbler, V-type blender, super mixer, Nauta mixer, Banbury mixer, kneading roll, or extruder, or a solution blending method in which the optional components are mixed in a state of being dissolved in a common good solvent such as methylene chloride.

[0069] The polycarbonate resin composition of the present disclosure can exhibit light-blocking properties by using a polycarbonate resin (A) in combination with an impact modifier (B). Therefore, it is not necessary to incorporate inorganic pigments, which have traditionally been incorporated to impart light-blocking properties, into the composition. Therefore, the polycarbonate resin composition of the present disclosure can be lighter than conventional light-blocking polycarbonate resin materials that contain inorganic pigments. When incorporating an inorganic pigment into the polycarbonate resin composition of the present disclosure, the amount of inorganic pigment incorporated can be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less per 100 parts by mass of the polycarbonate resin (A).

[0070] Furthermore, the impact modifiers used in the polycarbonate resin compositions described in Patent Documents 5 to 7 are composed of rubber or elastomer containing an acrylic component, a butadiene component, a styrene component, etc., and the inventors have found that such impact modifiers reduce dry heat resistance. Therefore, from the viewpoint of dry heat resistance, it is preferable that the polycarbonate resin composition of the present disclosure does not contain an impact modifier composed of rubber or elastomer, particularly an impact modifier composed of rubber or elastomer containing an acrylic component, a butadiene component, a styrene component, etc., and if such an impact modifier is blended, it is preferable that the amount thereof is 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less per 100 parts by mass of the polycarbonate resin (A).

[0071] (heat stabilizer) The polycarbonate resin (A) preferably contains a heat stabilizer to prevent a decrease in molecular weight and deterioration in color during various molding processes such as extrusion. In particular, the ether diol residue of the structural unit represented by the above formula 1 is susceptible to deterioration and coloration due to heat and oxygen, so it is preferable to contain a phosphorus-based heat stabilizer. Furthermore, it is more preferable to blend a pentaerythritol-type phosphite compound or a phosphite compound having a cyclic structure that reacts with a dihydric phenol as the phosphorus-based heat stabilizer.

[0072] Examples of pentaerythritol phosphite compounds include 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, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite. Of these, distearyl pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are preferred.

[0073] Examples of phosphite compounds that react with dihydric phenols and have a cyclic structure 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, and 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite. phosphite, 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylene-bis-(4,6-di-t-butylphenyl)octylphosphite, 6-tert-butyl-4-[3-[(2,4,8,10)-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol, and the like.

[0074] Other phosphorus-based heat stabilizers include various phosphite compounds, phosphate compounds, phosphonite compounds, and phosphonate compounds other than those mentioned above.

[0075] Examples of the phosphite compound 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-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, and tris(2,6-di-tert-butylphenyl)phosphite.

[0076] Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

[0077] Examples of the phosphonite compound include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, Examples of suitable phosphonite compounds include 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)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. These phosphonite compounds are preferred because they can be used in combination with the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups.

[0078] Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0079] The above phosphorus-based heat stabilizers can be used alone or in combination of two or more kinds, but it is preferable to blend an effective amount of at least a pentaerythritol-type phosphite compound or a phosphite compound that reacts with a dihydric phenol and has a cyclic structure.

[0080] The amount of the phosphorus-based heat stabilizer added is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 parts by mass, and even more preferably 0.01 to 0.3 parts by mass per 100 parts by mass of the polycarbonate resin (A).

[0081] For the purpose of suppressing a decrease in molecular weight and deterioration in color during molding such as extrusion of the polycarbonate resin (A), a hindered phenol-based heat stabilizer can be added in combination with a phosphorus-based heat stabilizer as a heat stabilizer.

[0082] The hindered phenol-based heat stabilizer is not particularly limited as long as it has an antioxidant function, and examples thereof include n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, tetrakis{methylene-3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate}methane, distearyl(4-hydroxy-3-methyl-5-t-butylbenzyl)malonate, triethyleneglycol-bis{3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate}, 1,6-hexanediol-bis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, pentaerythrityl-tetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2- Thiodiethylene bis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2-thiobis(4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4-bis{(octyl thio)methyl}-o-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, and the like.

[0083] Among these, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, pentaerythrityl-tetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol, 2,2-thiodiethylenebis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, and the like are preferred.

[0084] These hindered phenol-based heat stabilizers may be used alone or in combination of two or more.

[0085] The amount of the hindered phenol-based heat stabilizer added is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.5 parts by mass, and even more preferably 0.01 to 0.3 parts by mass per 100 parts by mass of the polycarbonate resin (A).

[0086] (mold release agent) In order to further improve the releasability from the mold during melt molding, a mold release agent may be blended into the polycarbonate resin (A) within a range that does not impair the object of the present invention.

[0087] Examples of such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin-based waxes, olefin-based waxes containing a carboxy group and / or a carboxylic acid anhydride group, silicone oils, and organopolysiloxanes.

[0088] Preferred examples of higher fatty acid esters include partial or full esters of monohydric or polyhydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms. Examples of such partial or full esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearate monosorbitate, stearyl stearate, behenic acid monoglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, and 2-ethylhexyl stearate.

[0089] Among these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

[0090] The higher fatty acid is preferably a saturated fatty acid having a carbon number of 10 to 30. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

[0091] These release agents may be used alone or in combination of two or more. The amount of such release agent added is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

[0092] (UV absorbers, light stabilizers) The polycarbonate resin composition of the present invention may contain an ultraviolet absorber or a light stabilizer, provided that the object of the present invention is not impaired. The ultraviolet absorber and light stabilizer may be used alone or in combination of two or more kinds.

[0093] Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane. Examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenylbenzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], methyl-3-[3-tert-butyl-5-(2H-benzotriazole ... Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, such as a condensation product of 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-4-hydroxyphenylpropionate and polyethylene glycol.Further examples of the ultraviolet absorber include hydroxyphenyltriazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol.

[0094] Examples of light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate. Examples of suitable light stabilizers include hindered amine light stabilizers, such as poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidyl)imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]}, and polymethylpropyl 3-oxy-[4-(2,2,6,6-tetramethyl)piperidinyl]siloxane. When used in combination with the ultraviolet absorbers and various antioxidants, these light stabilizers can exhibit better performance in terms of weather resistance and the like.

[0095] The blending amount of such ultraviolet absorber and light stabilizer is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of the polycarbonate resin (A).

[0096] (Bluing agent) The composition of the present disclosure may contain a bluing agent to counteract the yellowish color of the molded article due to the polycarbonate resin or ultraviolet absorber. The bluing agent is not particularly limited as long as it is used for polycarbonate resins. Generally, anthraquinone dyes are preferred because they are readily available.

[0097] Representative examples of specific bluing agents include those with the generic name Solvent Violet 13 (CA No. (Color Index No.) 60725), those with the generic name Solvent Violet 31 (CA No. 68210), those with the generic name Solvent Violet 33 (CA No. 60725), those with the generic name Solvent Blue 94 (CA No. 61500), those with the generic name Solvent Violet 36 (CA No. 68210), those with the generic name Solvent Blue 97 (Macrolex Violet RR, manufactured by Bayer AG), and those with the generic name Solvent Blue 45 (CA No. 61110).

[0098] These bluing agents may be used alone or in combination of two or more. These bluing agents are usually used in an amount of preferably 0.1 × 10 based on 100 parts by mass of the polycarbonate resin (A). -4 ~2×10 -4 It is blended in a ratio of parts by mass.

[0099] (fluorescent dyes, dyes) The composition of the present disclosure may contain fluorescent dyes and other dyes as long as the purpose of the present invention is not impaired.

[0100] The fluorescent dye is not particularly limited as long as it can be used in thermoplastic resins, and examples thereof include xanthene-based, thiazole-based, thiazine-based, perylene-based, coumarin-based, and diaminostilbene-based fluorescent dyes. Perylene-based and coumarin-based fluorescent dyes are particularly preferred. Such fluorescent dyes are commercially available and can be easily obtained, for example, as Lumogen Color manufactured by BASF, Fluoresent manufactured by Arimoto Chemical Industry, and Macrolex manufactured by Baycr.

[0101] Taking into consideration the fluorescence and discoloration resistance, the fluorescent dye is preferably blended in an amount of 0.001 to 5 parts by mass, more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the polycarbonate resin (A).

[0102] (filler) The composition of the present disclosure may contain a filler as long as it does not impair the object of the present invention. Examples of such fillers include inorganic fillers and organic fillers. The filler may be in any form, such as particulate, fibrous, or plate-like. The fillers may be used alone or in combination of two or more.

[0103] Examples of inorganic fillers include glass fibers, milled glass fibers, glass flakes, glass beads, silica particles, alumina particles, titanium oxide particles, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate particles, talc, mica, calcium silicates such as wollastonite; carbon fibers, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide particles, silicon carbide fibers, silicon nitride particles, silicon nitride fibers, brass fibers, stainless steel fibers, potassium titanate fibers, and whiskers thereof. Among these, glass fibrous fillers, glass powder fillers, glass flake fillers; various whiskers, mica, and talc are preferred. Glass fibers, glass flakes, milled glass fibers, wollastonite, mica, and talc are more preferred, and glass fibers and / or talc are particularly preferred.

[0104] Any glass fiber or milled glass fiber that is used in thermoplastic resins can be used, but those made of alkali-free glass (E glass) are particularly preferred.

[0105] The diameter of the glass fiber is preferably 6 μm to 20 μm, more preferably 9 μm to 14 μm, taking into consideration the balance between the reinforcing effect and the appearance of the molded product.

[0106] As the glass fiber, chopped strands cut to a length of 1 mm to 6 mm, milled glass fiber pulverized to a length of 0.01 mm to 0.5 mm, and the like can also be suitably used.

[0107] The glass fibers may be surface-treated with a silane coupling agent such as aminosilane or epoxysilane to improve adhesion to the polycarbonate resin (A), or may be bundled with an acrylic resin, a urethane resin, or the like to improve handleability.

[0108] The glass beads may be any type used in thermoplastic resins. Among them, those made of alkali-free glass (E glass) are preferred. The glass beads are preferably spherical and have an average particle size of 10 μm to 50 μm.

[0109] The glass flakes include, for example, scaly glass flakes. The maximum diameter of the glass flakes after being blended into the polycarbonate resin composition is preferably 1000 μm or less, more preferably in the range of 1 μm to 500 μm. The aspect ratio of the glass flakes (ratio of maximum diameter to thickness) is preferably 5 or more, 10 or more, or 30 or more. There is no particular restriction on the upper limit of the aspect ratio, and it can be, for example, 10,000 or less, and is preferably 200 or less. The aspect ratio of the glass flakes is the value in the resin composition.

[0110] The carbon fiber is not particularly limited, and examples thereof include those produced by burning raw materials such as acrylic fiber, petroleum or carbon-based special pitch, cellulose fiber, or lignin, and include various types such as flame-resistant, carbonaceous, or graphite fibers.

[0111] Considering the conductivity, strength, rigidity, etc. of the polycarbonate resin composition, the diameter of the carbon fibers is preferably 3 μm to 15 μm, and the average aspect ratio (fiber length / fiber diameter) of the carbon fibers is preferably 10 or more, 30 or more, or 50 or more. There is no particular upper limit to the aspect ratio, and it can be, for example, 10,000 or less, and is preferably 200 or less. The aspect ratio of the carbon fibers is the value in the resin composition.

[0112] The carbon fibers may be subjected to a surface treatment such as an epoxy treatment, a urethane treatment, or an oxidation treatment in order to improve their affinity with the polycarbonate resin, as long as the properties of the polycarbonate resin composition of the present disclosure are not impaired.

[0113] Examples of organic fillers include powdered organic fillers such as wood flour, bamboo flour, palm starch, curcuma flour, and pulp flour; bulging and spherical organic fillers such as cross-linked polyester, polystyrene, styrene-acrylic copolymer, and urea resin; and fibrous organic fillers such as synthetic fibers and natural fibers.

[0114] The amount of filler to be blended is preferably 1 part by mass or more, 2 parts by mass or more, or 5 parts by mass or more per 100 parts by mass of polycarbonate resin, taking into consideration the balance between the reinforcing effect and the appearance of the molded article, and is preferably 100 parts by mass or less, 70 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, or 35 parts by mass or less.

[0115] <Method for producing polycarbonate resin composition> There are no particular limitations on the method for producing the polycarbonate resin composition of the present disclosure. For example, the polycarbonate resin composition can be produced by premixing the polycarbonate resin (A), the impact modifier (B), and optional components (hereinafter, these may be collectively referred to as "each component"), followed by melt-kneading and pelletizing.

[0116] Examples of means for premixing include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc. In premixing, granulation can also be carried out using an extrusion granulator or a briquetting machine.

[0117] After premixing, the mixture is melt-kneaded in a melt mixer, typically a vented twin-screw extruder, and pelletized using equipment such as a pelletizer. Other examples of melt mixers include a Banbury mixer, a kneading roll, and a thermostatically controlled stirring vessel, with a vented twin-screw extruder being preferred. Alternatively, each component may be independently fed to a melt mixer, typically a twin-screw extruder, without premixing. The cylinder temperature during melt mixing is preferably 180 to 270°C, more preferably 190 to 260°C, and even more preferably 200 to 250°C, taking into consideration factors such as thermal decomposition of the polycarbonate resin.

[0118] The polycarbonate resin composition of the present disclosure is preferably produced by melt-kneading the components using an extruder. A twin-screw extruder is particularly suitable as the extruder, and one having a vent capable of degassing moisture in the raw materials and volatile gases generated from the melt-kneaded resin is preferably used. The vent is preferably equipped with a vacuum pump for efficiently discharging the generated moisture and volatile gases to the outside of the extruder.

[0119] It is also possible to remove foreign matter from the polycarbonate resin composition by installing a screen in a zone before the die of the extruder to remove foreign matter mixed in the extrusion raw materials. Examples of such a screen include a wire mesh, a screen changer, and a sintered metal plate (e.g., a disk filter).

[0120] The method for feeding the impact modifier (B) and optional components (hereinafter, these may be collectively referred to as "additives") to the extruder is not particularly limited, and the following methods (i) to (iv) are representative examples: (i) A method in which the additives are fed into the extruder independently of the polycarbonate resin (A). (ii) A method in which the resin powder of the polycarbonate resin (A) and the additives are premixed using a mixer such as a super mixer, and then the premixed mixture is fed into an extruder. (iii) A method in which the additive and the polycarbonate resin (A) are melt-kneaded in advance to form master pellets. (iv) Another premixing method involves preparing a solution in which the polycarbonate resin (A) and the additives are uniformly dispersed in a solvent, and then removing the solvent.

[0121] The polycarbonate resin composition extruded from the extruder can be directly cut and pelletized, or can be formed into strands, which can then be cut and pelletized with a pelletizer. When it is necessary to reduce the influence of external dust, etc., it is preferable to purify the atmosphere around the extruder.

[0122] In addition, in the production of pellets, it is preferable to appropriately narrow the shape distribution of the pellets, reduce miscuts, reduce fine powder generated during transportation and handling, and reduce bubbles (vacuum bubbles) generated inside the strands and pellets using methods already proposed for polycarbonate resins for optical disks and cyclic polyolefin resins for optical use. These formulations can achieve high-cycle molding and reduce the rate of defects such as silver.

[0123] The pellets may be in the form of a cylinder, a rectangular pillar, a sphere, or any other common shape, but are preferably cylinders. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm. The length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 3.5 mm.

[0124] <Molded products> The polycarbonate resin composition of the present disclosure has excellent impact resistance, light-shielding properties, heat resistance, and dry heat resistance. Therefore, molded articles formed using polycarbonate resin compositions having such properties can be used in a wide variety of applications, including interior or exterior components for electric or electronic devices, interior or exterior components for various vehicles such as automobiles, various containers or packaging materials such as bottles, and interior or exterior components for buildings. Specifically, such molded articles can be used, for example, as substitutes for flat or curved glass, such as smoked glass or privacy glass, or as smoked films or privacy films to be attached to glass or the like.

[0125] The shape of the molded product is not particularly limited, and various shapes can be adopted, such as flat shapes such as films, sheets, or plates, curved shapes, and three-dimensional shapes.

[0126] <Method for manufacturing molded products> Molded articles obtained from the polycarbonate resin composition of the present disclosure can be produced by known methods such as injection molding and extrusion molding.

[0127] When forming by injection molding, the cylinder temperature is preferably in the range of 180 to 270°C, more preferably in the range of 190 to 260°C, in order to suppress coloration and molecular weight reduction due to polymer decomposition. The mold temperature can be in the range of 40 to 140°C, but from the viewpoint of shortening the molding cycle and the molten resin residence time, it is preferably in the range of 40 to 120°C, more preferably in the range of 40 to 100°C.

[0128] Injection molding can be performed not only by the usual cold runner method but also by the hot runner method. Injection molding is not limited to the usual injection molding method, but also by injection compression molding, injection press molding, gas-assisted injection molding, foam molding, insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding, depending on the purpose. Here, foam molding also includes foam molding by injecting a supercritical fluid.

[0129] The polycarbonate resin composition of the present disclosure can also be extruded to form extrusion molded articles such as tubes or various other shapes, or sheets and films. For forming sheets and films, methods such as inflation, calendering, and casting can be used. Furthermore, the composition can be molded into heat-shrinkable tubes by a specific stretching operation. Furthermore, molded articles can also be obtained using methods such as rotational molding and blow molding. [Example]

[0130] The present disclosure will be explained in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0131] Examples 1 to 2 and Comparative Examples 1 to 8 The polycarbonate resins and compositions containing the resins obtained by the methods shown in Synthesis Examples 1 and 2 below were evaluated as follows, and the results are shown in Tables 1 and 2. Here, the values for the polycarbonate resin and impact modifier in Table 2 are all in parts by mass.

[0132] <Evaluation of Polycarbonate Resin> (Specific viscosity (η sp )) The pellets obtained in each synthesis example were dissolved in methylene chloride to a polycarbonate resin concentration of approximately 0.7 g / dL. At a temperature of 20°C, the specific viscosity (η sp ) was obtained: η sp =t / t o -1...Formula 3 where t is the flow time of the sample solution, and t o is the solvent-only flow time.

[0133] (melt viscosity) Using a capillary rheometer (Capillograph Model 1D) manufactured by Toyo Seiki Co., Ltd., the shear rate / viscosity curve was obtained by varying the measurement speed at a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 240°C. ー1 The melt viscosity was read at 100°C.

[0134] (glass transition temperature (Tg)) Using a DSC measuring device (model DSC2910) manufactured by TA Instruments, about 10 mg of the pellets obtained in each synthesis example were heated at a temperature increase rate of 20°C / min to measure the glass transition temperature.

[0135] (5% weight loss temperature) Using a TGA measuring device (model TGA2950) manufactured by TA Instruments, about 10 mg of the pellets obtained in each synthesis example was heated at a temperature increase rate of 20°C / min, and the 5% weight loss temperature was measured.

[0136] <Evaluation of Polycarbonate Resin> (Charpy impact strength (impact resistance)) Pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110°C for 12 hours, and then molded into test specimens at a cylinder temperature of 240°C and a mold temperature of 90°C using a JSWJ-75EIII manufactured by The Japan Steel Works, Ltd. The obtained test specimens were subjected to a notched Charpy impact test in accordance with ISO179 to measure the Charpy impact strength.

[0137] (heat deflection temperature) Pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110°C for 12 hours, and then molded into test specimens using a JSWJ-75EIII manufactured by The Japan Steel Works, Ltd. at a cylinder temperature of 240°C and a mold temperature of 90°C. The deflection temperature under load of the obtained test specimens under a high load (1.8 MPa) was measured in accordance with ISO75.

[0138] (Total light transmittance) The pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110 ° C for 12 hours, and then molded using an injection molding machine (manufactured by The Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 240 ° C, a mold temperature of 80 ° C, and a molding cycle of 50 seconds to form a three-level plate having a width of 50 mm, a length of 90 mm, and thicknesses of 3.0 mm (20 mm), 2.0 mm (45 mm), and 1.0 mm (25 mm) from the gate side, and an arithmetic mean roughness (Ra) of 0.03 μm. The total light transmittance of the three-level plate at a thickness of 2.0 mm was measured using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with ISO 13468.

[0139] (Hayes) The pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110 ° C for 12 hours, and then molded using an injection molding machine (manufactured by The Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 240 ° C, a mold temperature of 80 ° C, and a molding cycle of 50 seconds to form a three-stage plate having a width of 50 mm, a length of 90 mm, and thicknesses of 3.0 mm (20 mm), 2.0 mm (45 mm), and 1.0 mm (25 mm) from the gate side, with an arithmetic mean roughness (Ra) of 0.03 μm. The haze of the 2.0 mm thick portion of the three-stage plate was measured using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with ISO 17482.

[0140] (Dry heat resistance test) The pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110 ° C for 12 hours, and then an injection molding machine (manufactured by Japan Steel Works, Ltd., JSW J-75EIII) was used to mold the polycarbonate resin composition at a molding temperature of 240 ° C, a mold temperature of 80 ° C, and a molding cycle of 50 seconds. A three-level plate having a width of 50 mm, a length of 90 mm, and thicknesses of 3.0 mm (20 mm), 2.0 mm (45 mm), and 1.0 mm (25 mm) from the gate side was molded, and the arithmetic mean roughness (Ra) was 0.03 μm. A 2 mm portion of the three-level plate was cut into a 50 mm x 45 mm piece to prepare a molded plate. This molded plate was then placed in a Tokyo Rikakikai Co., Ltd. vacuum oven VOS-301SD for 300 hours at 110 ° C without vacuum treatment.

[0141] The yellowing index (ΔYI) of the molded plate before and after static treatment was measured using a Macbeth CE-7000 colorimeter under illuminant C in accordance with JIS K7136 (2000). In this evaluation, the smaller the ΔYI value, the smaller the color change when used for a long period in a high-temperature, dry environment, indicating excellent dry heat resistance.

[0142] (Appearance evaluation of molded products) The pellets of the polycarbonate resin composition obtained in each example were dried at 80 to 110 ° C for 12 hours, and then molded using an injection molding machine (manufactured by The Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 240 ° C, a mold temperature of 80 ° C, and a molding cycle of 50 seconds to form a three-tiered plate with a width of 50 mm, a length of 90 mm, and thicknesses of 3.0 mm (20 mm), 2.0 mm (45 mm), and 1.0 mm (25 mm) from the gate side, and an arithmetic mean roughness (Ra) of 0.03 μm. The appearance of the three-tiered plate was visually observed. Plates with a uniform appearance without molding irregularities were evaluated as "○", and plates with appearance irregularities were evaluated as "×".

[0143] <Synthesis of Polycarbonate Resin> (Synthesis Example 1: Production of Copolymer Polycarbonate Resin (PC-1)) 441.29 parts by mass of isosorbide (hereinafter abbreviated as ISS), 65.99 parts by mass of 1,9-nonanediol (hereinafter abbreviated as ND), 749.77 parts by mass of diphenyl carbonate (hereinafter abbreviated as DPC), and 3.0 × 10 tetramethylammonium hydroxide as a catalyst. -2 parts by mass and sodium hydroxide 2.0 x 10 -3 The mass parts were mixed and melted by heating to 170°C under a nitrogen atmosphere.

[0144] After melting, the transesterification reaction process was initiated. After the start of depressurization, the pressure was reduced over 70 minutes while adjusting the final vacuum level to 13.4 kPa, and after reaching 13.4 kPa, this vacuum level was maintained. Simultaneously with the start of depressurization, the temperature was raised at a rate of 10°C / hour until the final resin temperature reached 190°C. After reaching 190°C, the pressure was maintained at 13.4 kPa and the resin temperature at 190°C for 10 minutes until 80% of the theoretical amount of phenol had been distilled off.

[0145] After 80% was distilled off, the temperature was increased at a rate of 0.5° C. / min so that the final resin temperature became 220° C. In parallel with the temperature increase, the pressure was reduced over 60 minutes so that the final reduced pressure became 3 kPa.

[0146] Subsequently, the temperature was increased at a rate of 1°C / min until the final resin temperature reached 240°C. In parallel with the temperature increase, the pressure was reduced over 20 minutes until the final vacuum reached 134 Pa. The reaction was terminated when a predetermined stirring power value was reached, and dodecylbenzenesulfonic acid tetrabutylphosphonium salt was added in an amount twice the moles of the catalyst to deactivate the catalyst. The polycarbonate resin was then discharged from the bottom of the reaction vessel under nitrogen pressure, cooled in a water bath, and cut into pellets using a pelletizer. The evaluation results of the pellets are shown in Table 1.

[0147] (Synthesis Example 2: Production of Copolymer Polycarbonate Resin (PC-2)) Pellets were obtained in the same manner as in Synthesis Example 1, except that 375.74 parts of ISS, 101.23 parts of 1,6-hexanediol (hereinafter abbreviated as HD), and 749.70 parts of DPC were used. The evaluation results of the pellets are shown in Table 1.

[0148] [Table 1]

[0149] Example 1 The polycarbonate resin (A-1) and the impact modifier (B-1) were weighed and mixed uniformly in the proportions shown in Table 2 below, and the resulting mixture was fed into an extruder to prepare pellets of the polycarbonate resin composition. The pellets were dried at 90°C for 12 hours and then evaluated for various physical properties. The results are shown in Table 2.

[0150] The extruder used here was a vented twin-screw extruder with a diameter of 15 mm (KZW15-25MG manufactured by Technovel Co., Ltd.) The extrusion conditions were a discharge rate of 8.4 kg / hour, a screw rotation speed of 250 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 240°C from the first feed port to the die.

[0151] (Example 2 and Comparative Examples 1 to 8) The same operations as in Example 1 were carried out except that the polycarbonate resin and impact modifier were used in the proportions shown in Table 2. The evaluation results are shown in Table 2. The polycarbonate resin and impact modifier corresponding to each symbol in Table 2 are shown below.

[0152] (Component A: Polycarbonate resin) A-1 is a pellet of the copolymer polycarbonate resin (PC-1) produced in Synthesis Example 1.

[0153] A-2 is a pellet of the copolymer polycarbonate resin (PC-2) produced in Synthesis Example 2.

[0154] (Component B: Impact modifier) B-1 is an impact modifier composed of an ethylene-glycidyl methacrylate-methyl acrylate copolymer (BONDFAST (trademark) 7M manufactured by Sumitomo Chemical Co., Ltd.). The content of glycidyl methacrylate units in this copolymer is 3% by mass, and the content of methyl acrylate units is 27% by mass.

[0155] B-2 is an impact modifier composed of a core-shell rubber polymer in which the core is a rubber polymer made of butadiene and butyl acrylate and the shell is methyl methacrylate.

[0156] B-3 is an impact modifier composed of a core-shell rubber polymer in which the core is a rubber polymer made of butyl acrylate and the shell is made of methyl methacrylate.

[0157] [Table 2]

[0158] <result> As can be seen from the results in Table 2, the polycarbonate resin compositions of Examples 1 and 2, which contained predetermined amounts of a specific polycarbonate resin and a specific impact modifier, exhibited excellent results in all evaluation items, including impact resistance, light blocking properties, molded product appearance, heat resistance, and dry heat resistance.

[0159] The results show that the polycarbonate resin composition of the present disclosure can provide a polycarbonate resin composition and a molded article thereof that have improved impact resistance and dry heat resistance while maintaining heat resistance.

[0160] Furthermore, the polycarbonate resin composition of the present disclosure is lighter than glass, has high impact resistance, and also has excellent light-blocking properties, and therefore is particularly suitable for use as a replacement for glass, for example, in applications that require a material with low total light transmittance while still requiring impact resistance, such as privacy glass for automobiles, etc., or smoked glass for window construction materials. Alternatively, it is also suitable for applications such as smoke films used on window glass, etc. [Industrial Applicability]

[0161] The polycarbonate resin composition of the present disclosure has excellent impact resistance, light-shielding properties, heat resistance, and dry heat resistance. Therefore, molded articles formed using the polycarbonate resin composition having such properties can be used in a wide variety of applications, including, for example, film or sheet members, interior or exterior members for electric or electronic devices, interior or exterior members for various vehicles such as automobiles, various containers or packaging members such as bottles, and interior or exterior members for buildings.

Claims

1. A polycarbonate resin (A) containing a structural unit represented by the following formula 1 as a repeating unit, and Contains an impact modifier (B), the impact resistance modifier (B) is contained in an amount of 1 to 20 parts by mass relative to 100 parts by mass of the polycarbonate resin (A), and is an ethylene-glycidyl methacrylate-methyl acrylate copolymer; the blending amount of the inorganic pigment is 40 parts by mass or less per 100 parts by mass of the polycarbonate resin (A), the blending amount of the impact modifier composed of a rubber or elastomer containing an acrylic component, a butadiene component, or a styrene component is 40 parts by mass or less per 100 parts by mass of the polycarbonate resin (A); The Charpy impact strength of the test piece measured in accordance with ISO 179 is 10 kJ / m ２ More than 100kJ / m ２ is as follows: The total light transmittance measured in accordance with ISO 13468 using a molded plate having a thickness of 2 mm is 30% or less, or the haze measured in accordance with ISO 17482 using a molded plate having a thickness of 2 mm is 50% or more, or the total light transmittance measured in accordance with ISO 13468 using a molded plate having a thickness of 2 mm is 30% or less and the haze measured in accordance with ISO 17482 using a molded plate having a thickness of 2 mm is 50% or more, The deflection temperature under load of the test piece measured in accordance with ISO 75 under a condition of 1.8 MPa is 90°C or higher and 130°C or lower, and The yellowing index (ΔYI) of a 2 mm thick molded plate that has been left to stand in a vacuum oven for 300 hours at 110°C without reducing pressure, as measured in accordance with JIS K7136 (2000), is 0.1 or more and 10 or less before and after the standing treatment. Polycarbonate resin composition: 【Chemical 1】

2. The composition according to claim 1, wherein the polycarbonate resin (A) contains 30 mol% or more of the structural unit represented by formula 1 relative to 100 mol% of all structural units derived from diol.

3. The composition according to claim 1 or 2, wherein the polycarbonate resin (A) further contains a structural unit derived from a diol compound other than that represented by formula 1.

4. A polycarbonate resin molded article molded using the composition according to any one of claims 1 to 3.

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