Polycarbonate resin composition and molded article

Abstract

To provide a polycarbonate resin composition that enables the production of a molding with excellent appearance and wear resistance, and a molding thereof.SOLUTION: The present invention provides a polycarbonate resin composition that contains polycarbonate resin (A) and fatty acid amide (B), and a molding thereof. The polycarbonate resin (A) includes a structural unit derived from a dihydroxy compound represented by the formula (1). The fatty acid amide (B) includes an alkyl end with 19 or more carbon atoms and one or more amide groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a molded article containing a polycarbonate resin having structural units derived from a specific dihydroxy compound. [Background technology]

[0002] Due to their excellent physical properties, polycarbonate resins are used as engineering plastics in a variety of applications. In particular, polycarbonate resins using isosorbide as a monomer exhibit superior performance that differs from conventional aromatic polycarbonate resins, and are therefore being investigated for a variety of applications. For example, Patent Document 1 describes a resin composition containing a polycarbonate resin having structural units derived from a specific dihydroxy compound such as isosorbide and a specific fatty acid bisamide, and describes that such a resin composition exhibits high abrasion resistance while maintaining transparency and surface hydrophilicity. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-131661 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, molded articles using polycarbonate resins having structural units derived from isosorbide have been considered for use in interior and exterior parts of vehicles such as automobiles. Such molded articles are required to have improved abrasion resistance in order to prevent scratches that occur during use while maintaining a good appearance. However, the polycarbonate resin composition of Patent Document 1 has insufficient abrasion resistance, and there is still room for improvement.

[0005] The present invention has been made in view of the above background, and aims to provide a polycarbonate resin composition that enables the production of molded articles that combine excellent appearance and abrasion resistance, and a molded article made thereof. [Means for solving the problem]

[0006] As a result of investigations, the present inventors have found that a polycarbonate resin composition containing a polycarbonate resin (A) having structural units derived from a specific dihydroxy compound and a specific fatty acid amide (B) enables the production of molded articles that combine excellent appearance and abrasion resistance, and have thus completed the present invention.

[0007] That is, the present invention is summarized as follows. [1] A polycarbonate resin (A) having a structural unit derived from a dihydroxy compound represented by the following formula (1): and a fatty acid amide (B) having an alkyl terminal with 19 or more carbon atoms and one or more amide groups.

[0008] [ka]

[0009] [2] The polycarbonate resin composition according to [1], wherein the polycarbonate resin (A) has structural units derived from at least one dihydroxy compound selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1), aliphatic dihydroxy compounds, and alicyclic dihydroxy compounds, and structural units derived from the dihydroxy compound represented by formula (1). [3] The polycarbonate resin composition according to [1] or [2], wherein the fatty acid amide (B) has a melting point of 90°C or higher. [4] The polycarbonate resin composition according to any one of [1] to [3], wherein the content of the fatty acid amide (B) per 100 parts by mass of the polycarbonate resin (A) is 0.001 parts by mass or more and 5 parts by mass or less.

[0010] [5] The polycarbonate resin composition according to any one of [1] to [4], further comprising an elastomer (C) having a core-shell structure. [6] The polycarbonate resin composition according to [5], wherein the content of the elastomer (C) having a core-shell structure is 0.1 to 20 parts by mass per 100 parts by mass of the polycarbonate resin composition.

[0011] [7] A molded article formed from the polycarbonate resin composition according to any one of [1] to [6]. [8] The molded article according to [7], which is an automotive part. [Effects of the Invention]

[0012] The polycarbonate resin composition can provide molded articles that have excellent appearance and excellent abrasion resistance. That is, the polycarbonate resin composition can provide molded articles that combine excellent appearance and abrasion resistance. Furthermore, the polycarbonate resin composition can reduce appearance defects during injection molding, making it suitable for injection molding. Therefore, the polycarbonate resin composition is expected to be applied in a wide range of fields, such as the injection molding fields of electric and electronic parts, automotive parts, etc., the film and sheet fields, and building materials fields. DETAILED DESCRIPTION OF THE INVENTION

[0013] The following describes embodiments of the present invention in detail. However, the following description of the configuration is merely an example (i.e., a representative example) of an embodiment of the present invention, and the present invention is not limited to the following content as long as it does not depart from the gist of the present invention. In this specification, the term "structural unit" refers to a partial structure constituting a resin, specifically a specific partial structure contained in a repeating structural unit. Specifically, the term "structural unit" refers to a partial structure sandwiched between adjacent linking groups in a polymer constituting a resin, and a partial structure sandwiched between a polymerizable reactive group present at the terminal portion of the polymer and a linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is the linking group, and a partial structure sandwiched between adjacent carbonyl groups is referred to as a structural unit. In addition, when the expression "to" is used in this specification, it is intended to include the numerical or physical values ​​written before and after it. Furthermore, numerical values ​​or physical values ​​written as upper and lower limits are intended to include the values ​​themselves. Furthermore, "parts by weight" and "parts by mass," "% by weight" and "% by mass" are essentially synonymous.

[0014] The polycarbonate resin composition contains a polycarbonate resin (A) having a structural unit derived from a dihydroxy compound represented by the following formula (1), and a fatty acid amide (B) having an alkyl terminal with 19 or more carbon atoms and one or more amide groups. [ka]

[0015] The reason why the present invention exhibits the above-mentioned effects is not yet clear, but is presumed to be as follows: When a polycarbonate resin composition contains a fatty acid amide having a short alkyl group terminal (for example, an alkyl group terminal having 18 or fewer carbon atoms), the fatty acid amide gasifies during molding and does not remain on the surface of the molded article, resulting in insufficient abrasion resistance of the molded article. In addition, this can cause problems such as the occurrence of silver streaks and mold contamination, which can deteriorate the appearance of the molded article. In contrast, when the polycarbonate resin composition contains a fatty acid amide having a long alkyl group terminal (e.g., an alkyl group terminal having 19 or more carbon atoms), the fatty acid amide forms a crystalline film on the surface of the molded article, improving the abrasion resistance of the molded article. Furthermore, the interaction between the crystalline film and the surface of the molded article due to intermolecular forces makes the abrasion resistance less likely to deteriorate, thereby maintaining excellent abrasion resistance. This is because the fatty acid amide (B) that constitutes the crystalline film has a functional group (specifically, one or more amide groups), and the polycarbonate resin (A) that constitutes the molded article has a structural unit derived from the dihydroxy compound represented by the aforementioned formula (1), which is a polar molecule. Furthermore, when the fatty acid amide has an alkyl group terminal having 19 or more carbon atoms, gasification of the fatty acid amide during molding is suppressed, thereby preventing poor appearance of the molded article.

[0016] [Polycarbonate resin (A)] The polycarbonate resin composition contains a polycarbonate resin (A). The polycarbonate resin (A) has at least a structural unit derived from a dihydroxy compound represented by the following formula (1) (hereinafter, this will be referred to as "structural unit (a1)" as appropriate). The polycarbonate resin (A) may be a homopolymer of the structural unit (a1), or may be a copolymer containing the structural unit (a1) and a structural unit (a2) other than the structural unit (a1). From the viewpoints of increasing the molecular weight and further improving impact resistance, the polycarbonate resin (A) is preferably a copolymer.

[0017] [ka]

[0018] Examples of the dihydroxy compound represented by the above formula (1) (hereinafter referred to as "compound (1)") include isosorbide, isomannide, and isoidet, which are stereoisomers. These may be used alone or in combination of two or more. Among these, isosorbide, which is obtained by dehydration condensation of sorbitol, which is produced from various starches that are abundant and easily available as plant-derived resources, is most preferred in terms of availability and ease of production, moldability, and properties of the resulting molded products (for example, heat resistance, impact resistance, surface hardness, and carbon neutrality).

[0019] The dihydroxy compound represented by formula (1) is easily oxidized gradually by oxygen. Therefore, during storage or handling during production, it is preferable to avoid moisture contamination and to use an oxygen scavenger or store under a nitrogen atmosphere to prevent decomposition by oxygen. For example, when isosorbide is oxidized, decomposition products such as formic acid may be generated. If isosorbide containing these decomposition products is used as a raw material for producing polycarbonate resin (A), coloration of polycarbonate resin (A) and the polycarbonate resin composition may occur. Furthermore, not only may physical properties be significantly deteriorated, but the polymerization reaction may be affected, making it impossible to obtain a high-molecular-weight polymer.

[0020] The polycarbonate resin (A) is preferably a copolymer having, as the structural unit (a2), a structural unit (a2-1) derived from at least one dihydroxy compound (hereinafter, these may be referred to as "compound 2") selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1), aliphatic dihydroxy compounds, and alicyclic dihydroxy compounds. That is, the polycarbonate resin (A) is preferably a copolymer having the structural unit (a1) and the structural unit (a2-1). In this case, the impact resistance of the polycarbonate resin (A) can be improved.

[0021] Examples of aliphatic hydrocarbon dihydroxy compounds that can be used include the following: straight-chain aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; and branched-chain aliphatic dihydroxy compounds such as 1,2-propanediol, 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

[0022] Examples of dihydroxy compounds of alicyclic hydrocarbons that can be used include the following dihydroxy compounds: dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons, exemplified by dihydroxy compounds derived from terpene compounds such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and limonene; and dihydroxy compounds which are secondary or tertiary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0023] Examples of the ether group-containing dihydroxy compound include oxyalkylene glycols and dihydroxy compounds containing an acetal ring. As the oxyalkylene glycol, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, etc. can be used.

[0024] As the dihydroxy compound containing an acetal ring, for example, spiro glycol represented by the following formula (2) or dioxane glycol represented by the following formula (3) can be used.

[0025] [ka]

[0026] [ka]

[0027] The polycarbonate resin (A) may further contain structural units other than the structural unit (a1) and the structural unit (a2-1). Examples of other dihydroxy compounds that serve as such structural units include dihydroxy compounds containing aromatic groups. However, if the polycarbonate resin (A) contains a large number of structural units derived from dihydroxy compounds containing aromatic groups, it may not be possible to obtain a polycarbonate resin (A) with a high molecular weight, and the effect of improving impact resistance may be reduced. Furthermore, as described below, in the case of a polycarbonate resin (A) that contains a large number of structural units derived from dihydroxy compounds containing aromatic groups as structural units of the polycarbonate resin (A), the addition of an amine compound may cause decomposition, resulting in a decrease in the impact resistance and color tone of the polycarbonate resin composition. Therefore, from the viewpoint of further improving impact resistance and color tone, the content of structural units derived from dihydroxy compounds containing aromatic groups is preferably less than 50 mol%, more preferably 10 mol% or less, and even more preferably 5 mol% or less, relative to 100 mol% of all structural units derived from dihydroxy compounds, and it is most preferable that the polycarbonate resin (A) does not contain structural units derived from dihydroxy compounds containing aromatic groups.

[0028] As the dihydroxy compound containing an aromatic group, for example, the following dihydroxy compounds can be used, but dihydroxy compounds other than these can also be used: 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4- 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)methane bis(4-hydroxyphenyl)pentane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxy Aromatic bisphenol compounds such as diphenyl ether and 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; dihydroxy compounds having an ether group bonded to an aromatic group such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone;9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene Dihydroxy compounds having a fluorene ring, such as 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene;

[0029] The other dihydroxy compounds can be appropriately selected depending on the properties required for the polycarbonate resin (A). One or more types of the other dihydroxy compounds may be used. By using the other dihydroxy compounds in combination with the compound (1), it is possible to obtain an effect of improving the flexibility and mechanical properties of the polycarbonate resin (A), an effect of improving the moldability, and the like.

[0030] The dihydroxy compound used as a raw material for polycarbonate resin (A) may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, or heat stabilizer. Compound (1) in particular has the property of being easily degraded under acidic conditions. Therefore, the use of a basic stabilizer in the synthesis process of polycarbonate resin (A) can suppress the degradation of compound (1). This can further improve the quality of the resulting polycarbonate resin composition.

[0031] Examples of the basic stabilizer that can be used include the following compounds: hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates, and fatty acid salts of metals of Group 1 or 2 of the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005); tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, and methyltriphenylammonium hydroxide. basic ammonium compounds such as diethylamine, dibutylamine, triethylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, 3-amino-1-propanol, ethylenediamine, N-methyldiethanolamine, diethylethanolamine, diethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline; and hindered amine compounds such as di-(tert-butyl)amine and 2,2,6,6-tetramethylpiperidine.

[0032] There are no particular limitations on the content of the basic stabilizer in the dihydroxy compound. However, since compound (1) is unstable under acidic conditions, it is preferable to set the content of the basic stabilizer so that the pH of an aqueous solution of the dihydroxy compound containing the basic stabilizer is around 7.

[0033] The content of the basic stabilizer in compound (1) (specifically, the content of the basic stabilizer relative to 100% by weight of the total of compound (1) and the basic stabilizer) is preferably 0.0001 to 1% by weight. In this case, the effect of preventing the deterioration of compound (1) is sufficiently obtained. From the viewpoint of further enhancing this effect, the content of the basic stabilizer is more preferably 0.001 to 0.1% by weight.

[0034] The polycarbonate resin (a) is obtained by using a dihydroxy compound and a carbonic acid diester as raw materials and polycondensing these raw materials, for example, by an ester exchange reaction. As the carbonic acid diester, a compound represented by the following formula (4) is usually used. These carbonic acid diesters may be used alone or in combination of two or more.

[0035] [ka]

[0036] In the above formula (4), A 1 and A 2 are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A 1 and A 2 A may be the same or different. 1 and A 2 is preferably a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted aromatic hydrocarbon group.

[0037] Examples of the carbonate diester represented by formula (4) include diphenyl carbonate (i.e., DPC) and substituted diphenyl carbonates such as ditolyl carbonate. Further, examples of the carbonate diester represented by formula (4) include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, and the like. Among these carbonate diesters, it is preferable to use diphenyl carbonate or a substituted diphenyl carbonate, and it is more preferable to use diphenyl carbonate. Carbonate diesters may contain impurities such as chloride ions, which may inhibit the polycondensation reaction or deteriorate the color tone of the resulting polycarbonate resin (A). Therefore, it is preferable to use a diester purified by distillation or the like, as necessary.

[0038] [Method for producing polycarbonate resin (A)] The polycarbonate resin (A) can be synthesized by polycondensing the dihydroxy compound and the carbonic acid diester through a transesterification reaction. More specifically, the polycarbonate resin (A) can be obtained by removing the monohydroxy compound and other by-products produced in the transesterification reaction from the system during the polycondensation.

[0039] The transesterification reaction proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst will be referred to as a "polymerization catalyst.") By selecting the type of polymerization catalyst, the reaction rate of the transesterification reaction and the quality of the resulting polycarbonate resin (A) can be appropriately adjusted.

[0040] The polymerization catalyst is not limited as long as it can provide the resulting polycarbonate resin (A) with satisfactory transparency, color tone, heat resistance, weather resistance, mechanical strength, etc. Examples of polymerization catalysts that can be used include basic compounds such as metal compounds of Group I or Group II (hereinafter simply referred to as "Group 1" and "Group 2") in the long periodic table, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds, and among these, Group 1 metal compounds and / or Group 2 metal compounds are preferred.

[0041] Examples of Group 1 metal compounds that can be used include the following: sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborohydride, and boron phenylide. Potassium, lithium phenylborate, cesium phenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, sodium, potassium, lithium, and cesium alcoholates and phenolates, disodium, dipotassium, dilithium, and dicesium salts of bisphenol A, etc. As the Group 1 metal compound, a lithium compound is preferred from the viewpoint of polymerization activity and the color tone of the resulting polycarbonate resin (A).

[0042] Examples of the Group 2 metal compound that can be used include the following compounds: calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. As the Group 2 metal compound, a magnesium compound, a calcium compound, or a barium compound is preferred, and from the viewpoints of polymerization activity and the color tone of the resulting polycarbonate resin (A), a magnesium compound and / or a calcium compound is more preferred, and a calcium compound is most preferred.

[0043] It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with the above-mentioned Group 1 metal compound and / or Group 2 metal compound as an auxiliary compound, but it is particularly preferable to use only the Group 1 metal compound and / or Group 2 metal compound.

[0044] As the basic phosphorus compound, for example, the following compounds can be used: triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salts, etc.

[0045] Examples of the basic ammonium compound that can be used include the following compounds: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0046] Examples of the amine compound that can be used include the following compounds: 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, and guanidine.

[0047] The amount of the polymerization catalyst used is preferably 0.1 to 300 μmol, more preferably 0.5 to 100 μmol, and particularly preferably 1 to 50 μmol per mol of the total dihydroxy compounds used in the reaction.

[0048] When a compound containing at least one metal selected from the group consisting of Group 2 metals in the long periodic table and lithium is used as the polymerization catalyst, particularly when a magnesium compound and / or a calcium compound is used, the amount of the polymerization catalyst used is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more, in terms of the metal atomic weight of the compound containing the metal, per mol of the total dihydroxy compounds used in the reaction. The upper limit is preferably 10 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less.

[0049] By adjusting the amount of polymerization catalyst used within the above range, the polymerization rate can be increased, making it possible to obtain a polycarbonate resin (A) with the desired molecular weight without necessarily increasing the polymerization temperature. This can suppress deterioration in the color tone of the polycarbonate resin (A). Furthermore, it can prevent unreacted raw materials from volatilizing during polymerization, which would disrupt the molar ratio of the dihydroxy compound to the carbonate diester, thereby more reliably obtaining a polycarbonate resin (A) with the desired molecular weight. Furthermore, it can suppress the occurrence of side reactions, which can further prevent deterioration in the color tone of the polycarbonate resin (A) or discoloration during molding.

[0050] Considering the adverse effects of sodium, potassium, or cesium, among the Group 1 metals, on the color tone of the polycarbonate resin (A), and the adverse effects of iron on the color tone of the polycarbonate resin (A), the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is preferably 1 ppm by weight or less. In this case, deterioration of the color tone of the polycarbonate resin (A) can be further prevented, and the color tone of the polycarbonate resin (A) can be further improved. From the same perspective, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is more preferably 0.5 ppm by weight or less. Note that these metals may be mixed in not only from the catalyst used but also from raw materials or the reaction equipment. Regardless of their origin, the total amount of compounds of these metals in the polycarbonate resin (A) is preferably within the above-mentioned range as the total content of sodium, potassium, cesium, and iron.

[0051] The polycarbonate resin composition may contain one type of resin alone as the polycarbonate resin (A), or may contain a mixture of two or more resins that differ in the type of structural unit (a2) derived from compound 2, copolymerization ratio, physical properties, etc.

[0052] [Synthesis of polycarbonate resin (A)] The polycarbonate resin (A) can be obtained, for example, by polycondensing a dihydroxy compound such as compound (1) with a carbonic acid diester through an ester exchange reaction in the presence of a polymerization catalyst.

[0053] The dihydroxy compound and the carbonate diester are preferably mixed uniformly before the transesterification reaction. The mixing temperature is usually 80°C or higher, preferably 90°C or higher, and usually 250°C or lower, preferably 200°C or lower, and more preferably 150°C or lower, with 100°C or higher and 120°C or lower being most preferred. In this case, the dissolution rate can be increased, the solubility can be sufficiently improved, and problems such as solidification can be sufficiently avoided. Furthermore, in this case, the thermal degradation of the dihydroxy compound can be sufficiently suppressed, resulting in a further improvement in the color tone of the polycarbonate resin (A) and improved weather resistance.

[0054] The operation of mixing the dihydroxy compound and the carbonic acid diester is usually carried out in an atmosphere with an oxygen concentration of 10 vol% or less, preferably 0.0001 to 10 vol%, more preferably 0.0001 to 5 vol%, and even more preferably 0.0001 to 1 vol%, which can improve the color tone and increase the reactivity.

[0055] To obtain polycarbonate resin (A), it is preferable to use a carbonic acid diester in a molar ratio of 0.90 to 1.20 relative to the total dihydroxy compounds used in the reaction. In this case, an increase in the number of terminal hydroxy groups in polycarbonate resin (A) can be suppressed, thereby improving the thermal stability of the polymer. This can further prevent coloration during molding and increase the rate of the transesterification reaction. It also makes it possible to more reliably obtain a desired high molecular weight polymer. Furthermore, by adjusting the amount of carbonic acid diester used within the above range, a decrease in the rate of the transesterification reaction can be suppressed, enabling more reliable production of polycarbonate resin (A) with the desired molecular weight. Furthermore, this can suppress an increase in thermal history during the reaction, thereby further improving the color tone and weather resistance of polycarbonate resin (A). Furthermore, this can reduce the amount of residual carbonic acid diester in polycarbonate resin (A), thereby avoiding or mitigating stains and odors during molding. From the same viewpoint as above, the amount of carbonic acid diester used relative to the total amount of dihydroxy compounds is more preferably 0.95 to 1.10 in terms of molar ratio.

[0056] The polycondensation of a dihydroxy compound and a carbonate diester is carried out in multiple stages using multiple reactors in the presence of the above-mentioned catalyst. The reaction may be carried out in a batchwise manner, a continuous manner, or a combination of a batchwise manner and a continuous manner. However, it is preferable to adopt a continuous manner from the viewpoint of obtaining a polycarbonate resin (A) with less thermal history and excellent productivity.

[0057] From the viewpoint of controlling the polymerization rate and the quality of the resulting polycarbonate resin (A), it is preferable to appropriately select the jacket temperature, internal temperature, and pressure in the reaction system depending on the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stage of the polycondensation reaction, and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the later stage of the reaction. In this case, distillation of unreacted monomers is suppressed, and it becomes easier to adjust the molar ratio of the dihydroxy compound to the carbonate diester to the desired ratio. As a result, a decrease in the polymerization rate can be suppressed. Furthermore, it becomes possible to more reliably obtain a polymer with the desired molecular weight and terminal groups.

[0058] Furthermore, the polymerization rate in a polycondensation reaction is controlled by the balance between hydroxyl and carbonate terminal groups. Therefore, if the balance of terminal groups fluctuates due to the distillation of unreacted monomers, it becomes difficult to maintain a constant polymerization rate, which can lead to significant fluctuations in the molecular weight of the resulting resin. Because the molecular weight of a resin correlates with its melt viscosity, fluctuations in melt viscosity can occur during melt processing of the resulting resin, making it difficult to maintain consistent molded product quality. This problem is particularly likely to occur when polycondensation reactions are performed continuously.

[0059] The use of a reflux condenser in a polymerization reactor is effective in suppressing the amount of unreacted monomer distilled off, and is particularly effective in the early stages of the reaction when a large amount of unreacted monomer is present. The temperature of the refrigerant introduced into the reflux condenser can be selected appropriately depending on the monomer used. Typically, the temperature of the refrigerant introduced into the reflux condenser at the inlet of the reflux condenser is 45 to 180°C, preferably 80 to 150°C, and particularly preferably 100 to 130°C. By adjusting the refrigerant temperature within these ranges, the reflux amount can be sufficiently increased, its effects can be fully achieved, and the efficiency of distillation of the monohydroxy compound to be distilled off can be sufficiently improved. As a result, a decrease in the reaction rate can be prevented, and discoloration of the resulting resin can be further prevented. Examples of refrigerants that can be used include hot water, steam, and heat transfer oil, with steam and heat transfer oil being preferred.

[0060] In order to maintain an appropriate polymerization rate, suppress distillation of monomers, and improve the color tone of the resulting polycarbonate resin (A), it is preferable to select the type and amount of the polymerization catalyst described above.

[0061] The polycarbonate resin (A) is usually produced through two or more steps using a polymerization catalyst. The polycondensation reaction may be carried out in two or more steps using one polycondensation reactor, with conditions sequentially changed, but from the viewpoint of production efficiency, it is preferable to carry out the reaction in multiple steps using multiple reactors, with conditions changed for each step.

[0062] From the viewpoint of efficiently carrying out the polycondensation reaction, in the early stage of the reaction when the reaction solution contains a large amount of monomer, it is preferable to maintain the required polymerization rate while suppressing the evaporation of the monomer. Furthermore, in the later stage of the reaction, it is preferable to shift the equilibrium toward the polycondensation reaction by sufficiently distilling off the by-product monohydroxy compound. Therefore, the reaction conditions suitable for the early stage of the reaction are usually different from the reaction conditions suitable for the later stage of the reaction. Therefore, by using multiple reactors arranged in series, the respective conditions can be easily changed, thereby improving production efficiency.

[0063] As described above, the number of polymerization reactors used in the production of the polycarbonate resin (A) may be at least two, but from the viewpoint of production efficiency, the number is three or more, preferably 3 to 5, and particularly preferably 4. When there are two or more polymerization reactors, a plurality of reaction stages under different conditions may be carried out in each polymerization reactor, or the temperature and pressure may be changed continuously.

[0064] The polymerization catalyst can be added to a raw material preparation tank or a raw material storage tank, or can be added directly to a polymerization reactor. From the viewpoint of supply stability and control of the polycondensation reaction, it is preferable to install a catalyst supply line in the raw material line before supplying the raw materials to the polymerization reactor, and supply the polymerization catalyst in the form of an aqueous solution.

[0065] Adjusting the temperature of the polycondensation reaction can improve productivity and prevent the product from being subjected to increased heat history. Furthermore, it is possible to further prevent volatilization of the monomer and decomposition or discoloration of the polycarbonate resin (A). Specifically, the following reaction conditions can be adopted for the first-stage reaction. The maximum internal temperature of the polymerization reactor is set within the range of usually 150 to 250°C, preferably 160 to 240°C, and more preferably 170 to 230°C. The pressure of the polymerization reactor (hereinafter, "pressure" refers to absolute pressure) is set within the range of usually 1 to 110 kPa, preferably 5 to 70 kPa, and more preferably 7 to 30 kPa. The reaction time is set within the range of usually 0.1 to 10 hours, preferably 0.5 to 3 hours. The first-stage reaction is preferably carried out while distilling off the generated monohydroxy compound from the reaction system.

[0066] From the second stage onwards, it is preferable to gradually reduce the pressure of the reaction system from the pressure of the first stage, and ultimately reduce the pressure (absolute pressure) of the reaction system to 1 kPa or less while continuously removing the generated monohydroxy compound from the reaction system. The maximum internal temperature of the polymerization reactor is usually set in the range of 200 to 260°C, preferably 210 to 250°C. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.3 to 6 hours, and particularly preferably 0.5 to 3 hours.

[0067] From the viewpoint of further suppressing discoloration and thermal degradation of the polycarbonate resin (A) and obtaining a polycarbonate resin (A) with a better color tone, it is preferable to set the maximum internal temperature of the polymerization reactor in all reaction stages to 210 to 240° C. Furthermore, in order to prevent a decrease in the polymerization rate in the latter half of the reaction and to minimize deterioration due to thermal history, it is preferable to use a horizontal reactor with excellent plug flow properties and interface renewal properties in the final stage of the polycondensation reaction.

[0068] In continuous polymerization, in order to control the molecular weight of the polycarbonate resin (A) finally obtained at a constant level, it is preferable to adjust the polymerization rate as necessary. In this case, a method with good operability is to adjust the pressure in the polymerization reactor in the final stage.

[0069] Furthermore, as mentioned above, the polymerization rate varies depending on the ratio of hydroxyl group terminals to carbonate group terminals. Therefore, by deliberately reducing one of the terminal groups to suppress the polymerization rate and maintaining a high vacuum in the final-stage polymerization reactor, the amount of remaining low-molecular-weight components in the resin, including monohydroxy compounds, can be reduced. However, in this case, if the amount of one terminal group is too small, even a slight change in the terminal group balance can drastically reduce the reactivity, and the molecular weight of the resulting polycarbonate resin (A) may fall short of the desired molecular weight. To avoid this problem, it is preferable that the polycarbonate resin (A) obtained in the final-stage polymerization reactor contain at least 10 mol / ton of both hydroxyl group terminals and carbonate group terminals. On the other hand, if both terminal groups are too large, the polymerization rate will be too fast and the molecular weight will be too high, so it is preferable that the amount of one terminal group be 60 mol / ton or less.

[0070] In this way, by adjusting the amount of terminal groups and the pressure of the final-stage polymerization reactor within preferred ranges, the amount of monohydroxy compounds remaining in the resin at the outlet of the polymerization reactor can be reduced. The amount of monohydroxy compounds remaining in the resin at the outlet of the polymerization reactor is preferably 2000 ppm by weight or less, more preferably 1500 ppm by weight or less, and even more preferably 1000 ppm by weight or less. By reducing the content of monohydroxy compounds at the outlet of the polymerization reactor in this way, volatilization of monohydroxy compounds and the like can be easily carried out in a subsequent step.

[0071] Although it is preferable that the residual amount of the monohydroxy compound is small, in order to reduce it to less than 100 ppm by weight, it is necessary to extremely reduce the amount of one of the terminal groups and adopt operating conditions such as maintaining the pressure of the polymerization reactor at a high vacuum. In this case, as mentioned above, it becomes difficult to maintain the molecular weight of the obtained polycarbonate resin (A) at a constant level, so the amount is usually 100 ppm by weight or more, preferably 150 ppm by weight or more.

[0072] From the viewpoint of effective resource utilization, it is preferable to reuse the by-produced monohydroxy compound as a raw material for other compounds after purifying it as necessary. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A, etc.

[0073] The polycarbonate resin (A) preferably contains a catalyst deactivator. The catalyst deactivator is not particularly limited as long as it is an acidic substance that has the function of deactivating the polymerization catalyst, but examples thereof include phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, phosphonium salts such as octylsulfonate tetrabutylphosphonium salt, benzenesulfonate tetramethylphosphonium salt, benzenesulfonate tetrabutylphosphonium salt, dodecylbenzenesulfonate tetrabutylphosphonium salt, and p-toluenesulfonate tetrabutylphosphonium salt; ammonium salts such as decylsulfonate tetramethylammonium salt, and dodecylbenzenesulfonate tetrabutylammonium salt; and alkyl esters such as methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, and ethyl hexadecylsulfonate.

[0074] The catalyst deactivator preferably contains a phosphorus-based compound (hereinafter referred to as the "specific phosphorus-based compound") containing either the partial structure represented by the following formula (5) or (6). The specific phosphorus-based compound can be added after the polycondensation reaction is completed, i.e., during the kneading process, pelletization process, or the like, to deactivate the polymerization catalyst described below and inhibit the subsequent unnecessary progression of the polycondensation reaction. As a result, the progression of polycondensation when the polycarbonate resin (A) is heated in a molding process or the like can be inhibited, and thus the elimination of the monohydroxy compound can be inhibited. Furthermore, by deactivating the polymerization catalyst, discoloration of the polycarbonate resin (A) at high temperatures can be further inhibited.

[0075] [ka]

[0076] [ka]

[0077] The specific phosphorus-based compound containing the partial structure represented by the above formula (5) or (6) may be phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonate ester, acidic phosphate ester, etc. Among the specific phosphorus-based compounds, phosphorous acid, phosphonic acid, and phosphonate ester are more effective in deactivating the catalyst and inhibiting coloration, and phosphorous acid is particularly preferred.

[0078] As the phosphonic acid, for example, the following compounds can be used: phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrilotris(methylenephosphonic acid), propylphosphonic anhydride, etc.

[0079] As the phosphonate ester, for example, the following compounds can be used: dimethyl phosphonate, diethyl phosphonate, bis(2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl ethylphosphonate, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl)phosphonate, diethyl vinylphosphonate, hydroxymethyl phosphonate, diethyl phosphonate, dimethyl (2-hydroxyethyl)phosphonate, diethyl p-methylbenzylphosphonate, diethyl phosphonoacetic acid, ethyl diethylphosphonoacetate, tert-butyl diethylphosphonoacetate, diethyl 4-chlorobenzylphosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl phosphonoacetaldehyde diethyl acetal, diethyl (methylthiomethyl)phosphonate and the like.

[0080] Examples of acidic phosphate esters that can be used include the following compounds: phosphate diesters such as dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis(butoxyethyl) phosphate, bis(2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl phosphate, distearyl phosphate, diphenyl phosphate, and dibenzyl phosphate, or mixtures of diesters and monoesters, diethyl chlorophosphate, and zinc stearyl phosphate.

[0081] The specific phosphorus compounds may be used singly or in combination of two or more in any ratio.

[0082] The content of the specific phosphorus compound in the polycarbonate resin (A) is preferably 0.1 ppm by weight or more and 5 ppm by weight or less in terms of phosphorus atoms. In this case, the specific phosphorus compound can sufficiently suppress catalyst deactivation and coloration. In addition, in this case, coloration of the polycarbonate resin (A) can be further prevented, particularly in durability tests under high temperature and high humidity.

[0083] Furthermore, by adjusting the content of the specific phosphorus-based compound according to the amount of the polymerization catalyst, the effect of suppressing catalyst deactivation and coloration can be more reliably obtained. The content of the specific phosphorus-based compound is preferably 0.5 to 5 times the molar amount of phosphorus atoms per 1 mol of metal atoms in the polymerization catalyst, more preferably 0.7 to 4 times the molar amount, and particularly preferably 0.8 to 3 times the molar amount of phosphorus atoms per 1 mol of metal atoms in the polymerization catalyst.

[0084] [Physical properties of polycarbonate resin (A)] The preferred physical properties of the polycarbonate resin (A) are shown below.

[0085] <Glass transition temperature> The glass transition temperature (Tg) of the polycarbonate resin (A) is lower than 145°C. In this case, coloration is easily suppressed and impact strength can be more easily improved. In addition, in this case, the mold temperature can be lowered when transferring the shape of the mold surface to the molded product during molding. This increases the number of temperature regulators available and improves mold surface transferability.

[0086] The glass transition temperature (Tg) of the polycarbonate resin (A) is more preferably lower than 140° C., and even more preferably lower than 135° C. The glass transition temperature of the polycarbonate resin (A) of the present invention is usually 90° C. or higher, and preferably 95° C. or higher. Methods for setting the glass transition temperature of polycarbonate resin (A) below 145°C include reducing the proportion of structural unit (a1) in polycarbonate resin (A), selecting a cyclic dihydroxy compound with low heat resistance as the dihydroxy compound used in producing polycarbonate resin (A), and reducing the proportion of structural units derived from aromatic dihydroxy compounds such as bisphenol compounds in polycarbonate resin (A). The glass transition temperature (Tg) of polycarbonate resin (A) is measured using a differential scanning calorimeter (DSC6220, manufactured by SII NanoTechnology Inc.) in accordance with JIS K7121 (1987).

[0087] <Reduced viscosity> The molecular weight of polycarbonate resin (A) can be expressed by reduced viscosity, and the higher the reduced viscosity, the higher the molecular weight. The reduced viscosity of polycarbonate resin (A) is measured using an Ubbelohde viscometer at a temperature of 20.0°C ± 0.1°C, with the polycarbonate resin concentration precisely adjusted to 0.6 g / dL using methylene chloride as a solvent.

[0088] From the viewpoints of improving fluidity during molding, thereby improving the molding cycle in, for example, injection molding, and also of reducing distortion of molded articles and preventing thermal deformation, the reduced viscosity of the polycarbonate resin (A) is preferably 2.0 dL / g or less, more preferably 1.7 dL / g or less, and even more preferably 1.4 dL / g or less. On the other hand, from the viewpoint of further improving mechanical strength, the reduced viscosity of the polycarbonate resin (A) is preferably 0.25 dL / g or more, more preferably 0.30 dL / g or more, and even more preferably 0.35 dL / g or more.

[0089] [Fatty acid amide (B)] The polycarbonate resin composition contains a fatty acid amide (B), which has an alkyl terminal having 19 or more carbon atoms and one or more amide groups.

[0090] The fatty acid amide is preferably at least one selected from the group consisting of compounds represented by the following formulas (7) and (8): Such fatty acid amide (B) forms a crystalline film on the surface of the molded article as described above, thereby improving the abrasion resistance.

[0091] Formula (7) represents a fatty acid amide having one amide group. 1 is an alkyl group having 19 or more carbon atoms. 2 , R 3 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms and an ester bond. Examples of the substituent include an alkyl group, a hydroxy group, a carbonyl group, a carboxy group, an aldehyde group, and a silanol group. The number of carbon atoms in the substituent is 30 or less. Formula (8) represents a fatty acid amide having two amide groups. 4 and R 6 is an alkyl group having 19 or more carbon atoms. 5 are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms and an ester bond. Examples of the substituent include an alkyl group, a hydroxy group, a carbonyl group, a carboxy group, an aldehyde group, and a silanol group. The number of carbon atoms in the substituent is 30 or less.

[0092] [ka]

[0093] [ka]

[0094] When the fatty acid amide (B) has one or more amide groups, such as those represented by formula (7) or (8), the abrasion resistance of the molded article is improved, and the amount of gas generated during molding is reduced, preventing the molded article from becoming hazy. The term "haze" refers to a cloudy white portion that may occur at the end of a molded article during molding, and the occurrence of the haze impairs the appearance of the molded article. From the viewpoint of improving abrasion resistance, the number of amide groups is preferably one or more and two or less.

[0095] From the viewpoint of improving wear resistance, in the fatty acid amide (B) represented by the above formula (7), R 1 The number of carbon atoms in R is 19 or more, preferably 20 or more, more preferably 21 or more, and even more preferably 22 or more. On the other hand, from the viewpoint of achieving a good balance between the hydrophobicity and hydrophilicity of the hydrocarbon chain, R 1 The number of carbon atoms is preferably 30 or less, more preferably 29 or less, even more preferably 28 or less, and most preferably 27 or less.

[0096] In equation (7), R 2 , R 3 are each independently preferably a hydrogen atom, in which case the abrasion resistance of the molded article can be further improved.

[0097] In equation (8), R 4 and R 6 are alkyl groups, each independently having 19 or more carbon atoms, more preferably 20 or more, even more preferably 21 or more, and most preferably 22 or more. On the other hand, from the viewpoint of achieving a good balance between the hydrophobicity and hydrophilicity of the hydrocarbon chain, the number of carbon atoms is preferably 30 or less, more preferably 29 or less, even more preferably 28 or less, and most preferably 27 or less.

[0098] In the above formula (8), R 5is preferably a hydrocarbon chain linking group (e.g., an alkylene group) having 2 to 10 carbon atoms. In other words, the divalent hydrocarbon group between the two amide groups in formula (8) preferably has 2 to 10 carbon atoms. In this case, the abrasion resistance of the molded article can be further improved.

[0099] In the above formula (8), R 5 may be either linear or branched. It may also contain a hydrocarbon group having a monocyclic or polycyclic aliphatic ring or an aromatic ring. It may also contain a hydrocarbon group having a linear or branched alkyl group as a substituent on the ring.

[0100] Specific examples of the fatty acid amide (B) include behenic acid amide (for example, BNT-22H manufactured by Nippon Fine Chemical Co., Ltd.), ethylene bisbehenic acid amide (for example, Slipax B manufactured by Mitsubishi Chemical Corporation), and the like.

[0101] From the viewpoint of suppressing the occurrence of haze on the molded article, the melting point of the fatty acid amide (B) is preferably 80° C. or higher, more preferably 90° C. or higher, and even more preferably 100° C. or higher. On the other hand, from the viewpoint of further improving the abrasion resistance of the surface of the molded article, the melting point of the fatty acid amide (B) is preferably 165° C. or lower, more preferably 155° C. or lower, even more preferably 150° C. or lower, and even more preferably 145° C. or lower.

[0102] From the viewpoint of improving abrasion resistance and suppressing haze due to gas generation, the content of fatty acid amide (B) per 100 parts by mass of polycarbonate resin (A) is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, and is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0103] The polycarbonate resin composition may also contain an elastomer component. Specifically, the polycarbonate resin composition may contain, for example, an elastomer (C) having a core-shell structure. The elastomer component (C) having a core-shell structure is an optional component. When the polycarbonate resin composition contains the elastomer component (C) having a core-shell structure, the impact resistance is improved.

[0104] [Elastomer (C)] From the viewpoint of further suppressing appearance defects and deterioration of heat resistance of molded articles, the content of the elastomer (C) having a core-shell structure is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and particularly preferably 20 parts by mass or less, per 100 parts by mass of the total amount of the polycarbonate resin (A), the fatty acid amide (B), and the elastomer (C). On the other hand, from the viewpoint of fully exhibiting the effects of improving surface impact resistance and impact resistance, the content of the elastomer (C) having a core-shell structure is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 5 parts by mass or more, per 100 parts by mass of the total amount of the polycarbonate resin (A), the fatty acid amide (B), and the elastomer (C).

[0105] Elastomers with a core-shell structure consist of a core (core layer) and one or more covering layers (shell layers). Elastomers with a core-shell structure are core-shell graft copolymers in which copolymerizable monomer components are graft copolymerized onto the core layer to form the shell layer.

[0106] The elastomer (C) having a core-shell structure is preferably a core-shell type graft copolymer in which a polymer component called a rubber component forms the core layer and a monomer component copolymerizable with the core component forms the shell layer through graft copolymerization. The core-shell graft copolymer may be produced by any of the following methods: bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The copolymerization method may be either single-stage or multi-stage grafting. However, commercially available core-shell elastomers can usually be used. Examples of commercially available core-shell elastomers are listed below.

[0107] The elastomer (C) having a core-shell structure is not particularly limited, but is preferably an acrylic-styrene rubber having a core-shell structure, which provides a molded article of the polycarbonate resin composition with a good balance of heat aging resistance, chemical resistance, moldability, molded article appearance, and heat resistance.

[0108] The glass transition temperature of the polymer component forming the core layer is usually 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower. Specific examples of the polymer component forming the core layer include polybutadiene, polyisoprene, polyalkyl acrylates such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone rubbers such as polyorganosiloxane rubber, butadiene-acrylic composites, IPN (Interpenetrating Polymer Network) composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene copolymers, ethylene-α-olefin copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-acrylic copolymers, and fluororubbers. These may be used alone or in combination. Among these, polybutadiene, polyalkyl acrylate, polyorganosiloxane, a composite of polyorganosiloxane and polyalkyl acrylate, and butadiene-styrene copolymer are preferred in terms of mechanical properties and surface appearance.

[0109] Specific examples of the monomer component constituting the shell layer and capable of graft copolymerization with the polymer component of the core layer include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and anhydrides thereof (e.g., maleic anhydride). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferred in terms of mechanical properties and surface appearance, and (meth)acrylic acid ester compounds are more preferred. Specific examples of the (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate. Among these, methyl (meth)acrylate and ethyl (meth)acrylate, which are relatively easily available, are preferred, and methyl (meth)acrylate is more preferred. Here, "(meth)acrylic" collectively refers to "acrylic" and "methacrylic."

[0110] The core-shell elastomer (C) is preferably a core-shell graft copolymer, which comprises a core layer made of at least one polymer component selected from polybutadiene-containing rubber, polybutylacrylate-containing rubber, polyorganosiloxane rubber, and an IPN composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, and a shell layer formed by graft copolymerization of a (meth)acrylic acid ester around the core layer. The core-shell graft copolymer preferably contains 40% by weight or more of the polymer component of the core layer, more preferably 60% by weight or more. The shell layer preferably contains 10% by weight or more of the (meth)acrylic acid ester component.

[0111] Preferred specific examples of these core-shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (i.e., MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (i.e., MABS), methyl methacrylate-butadiene copolymer (i.e., MB), methyl methacrylate-acrylic rubber copolymer (i.e., MA), methyl methacrylate-acrylic rubber-styrene copolymer (i.e., MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate-(acrylic-silicone complex) copolymer, etc.

[0112] Examples of such core-shell type graft copolymers include "Paraloid (registered trademark) EXL2602", "Paraloid (registered trademark) EXL2603", "Paraloid (registered trademark) EXL2655", "Paraloid (registered trademark) EXL2311", "Paraloid (registered trademark) EXL2313", "Paraloid (registered trademark) EXL2315", "Paraloid (registered trademark) KM330", "Paraloid (registered trademark) KM336P", and "Paraloid (registered trademark) KM336P", all manufactured by Rohm and Haas Japan. ) KCZ201" manufactured by Mitsubishi Rayon Co., Ltd., "Metablen (registered trademark) C-223A," "Metablen (registered trademark) E-901," "Metablen (registered trademark) S-2001," "Metablen (registered trademark) W-450A," and "Metablen (registered trademark) SRK-200" manufactured by Kaneka Corporation, and "Kane Ace (registered trademark) M-511," "Kane Ace (registered trademark) M-600," "Kane Ace (registered trademark) M-400," "Kane Ace (registered trademark) M-580," and "Kane Ace (registered trademark) MR-01" manufactured by Kaneka Corporation.

[0113] The impact strength modifiers having a core-shell structure, such as these core-shell type graft copolymers, may be used singly or in combination of two or more kinds.

[0114] [Additives] Various well-known additives can be added to the polycarbonate resin composition of the present invention within the scope of not impairing the object of the present invention, such as antioxidants, light stabilizers, ultraviolet absorbers, heat stabilizers, fillers and other fillers, neutralizing agents, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, crosslinking agents, crosslinking aids, metal deactivators, molecular weight modifiers, antibacterial agents, antifungal agents, fluorescent brighteners, and light diffusing agents such as organic diffusing agents and inorganic diffusing agents.

[0115] [Antioxidants] As the antioxidant, a general antioxidant used in resins can be used. From the viewpoints of oxidation stability, thermal stability, and good jet black coloring, phosphite-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants are preferred. As the antioxidant, one type of compound may be used, or two or more types of compounds may be used in combination.

[0116] <Phosphite-based antioxidant> Examples of the phosphite antioxidant include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)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, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite. Among these, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are preferably used.

[0117] <Sulfur-based antioxidant> Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl]sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, and 1,1'-thiobis(2-naphthol). Among these, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred.

[0118] <Phenol-based antioxidant> Examples of phenolic antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzyl. Examples of compounds include 2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, 2,6-di-tert-butyl-p-cresol, and 2,6-di-tert-butyl-4-ethylphenol.

[0119] [Light stabilizer] Light stabilizers include 2,2,6,6-tetramethyl-4-piperidinol, tetrakis(2,2,6,6-tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), tetrakis(2,2,6,6-tetramethyl-4-piperidyl-butane-1,2,3,4-tetracarboxylate, bis(1,2,3,6,6-pentamethyl-4-piperidyl)[[ 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, a condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane-diethanol, and a mixed ester of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0120] [UV absorber] The polycarbonate resin composition may contain an ultraviolet absorber (i.e., UVA) within the scope of the present invention. Examples of ultraviolet absorbers include 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 2,2'-p-phenylenebis(1,3-benzoxazin-4-one).

[0121] [Physical properties of polycarbonate resin composition] <Appearance> The appearance of the polycarbonate resin composition can be evaluated, for example, by the evaluation method described in detail in the Examples below.

[0122] <Wear resistance test> The abrasion performance of the polycarbonate resin composition can be evaluated, for example, by an abrasion resistance test described in detail in the Examples below. The color change in the abrasion resistance test is preferably 5 or less. In this case, the polycarbonate resin composition has excellent abrasion performance.

[0123] <Impact strength> The impact strength of the polycarbonate resin composition can be evaluated, for example, by a notched Charpy impact strength test, which will be described in detail in the Examples below. The notched Charpy impact strength (notch tip radius R: 0.25 mm) is preferably 40 kJ / m 2 In this case, the polycarbonate resin composition has excellent impact strength.

[0124] [Blending method] In the polycarbonate resin composition, examples of the method for blending the polycarbonate resin composition with the various additives and the like include a method of mixing and kneading using a tumbler, V-type blender, super mixer, Nauta mixer, Banbury mixer, kneading roll, extruder, or the like, or a solution blending method in which the additives are dissolved in a common good solvent such as methylene chloride and mixed, but the method is not particularly limited, and any commonly used blending method may be used.

[0125] There is no limitation on the timing of blending the polycarbonate resin composition with the various additives, etc. For example, various additives, etc. may be blended after multiple polycarbonate resin compositions with different compositions are mixed and pelletized, various additives, etc. may be blended with each of multiple polycarbonate resin compositions with different compositions to form composition pellets and then mixed, or various additives, etc. may be blended simultaneously with mixing multiple polycarbonate resin compositions with different compositions.

[0126] [Method for producing polycarbonate resin composition] The polycarbonate resin composition of the present invention can be produced, for example, by mechanically melt-kneading the above-mentioned components. Examples of melt-kneading machines that can be used here include single-screw extruders, twin-screw extruders, Brabender mixers, Banbury mixers, kneader blenders, and roll mills. Among these, twin-screw extruders are preferred, and the kneading is preferably carried out under reduced pressure in order to remove residual phenol by distillation. The lower limit of the kneading temperature is usually 100°C or higher, preferably 145°C or higher, and more preferably 160°C or higher. The upper limit of the kneading temperature is usually 350°C, preferably 300°C, and more preferably 250°C. During kneading, the components may be kneaded all at once, or a multi-stage division kneading method may be used in which any component is kneaded and then the remaining components are added and kneaded. The extruded mixture is preferably pelletized using a strand cutter or the like and then appropriately dried before use.

[0127] [Method for molding polycarbonate resin composition] The polycarbonate resin composition of the present invention can be processed into various molded articles by molding methods such as injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, etc.), extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding. The shape of the molded article is not particularly limited, and examples include sheets, films, plates, particles, lumps, fibers, rods, porous bodies, and foams, with sheets, films, and plates being preferred. The molded film can also be uniaxially or biaxially stretched. Examples of stretching methods include the roll method, tenter method, and tubular method. Furthermore, surface treatments commonly used in industry, such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, can also be applied.

[0128] [Application] The uses of the molded article obtained by molding the polycarbonate resin composition of the present invention are not particularly limited, but examples thereof include the following uses. In the field of electrical and electronic components, these include covering materials for electric wires, cords, and wire harnesses, insulating sheets, displays and touch panels for office automation equipment, membrane switches, photo covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, FDD collets, and floppy hubs. In the field of optical components, these include optical disc substrates, optical disc pickup lenses, optical lenses, LCD substrates, PDP substrates, television screens for projection televisions, phase difference films, fog lamp lenses, illuminated switch lenses, sensor switch lenses, Fresnel lenses, protective glasses, projection lenses, camera lenses, sunglasses, light guide plates, camera strobe reflectors, and LED reflectors. In the field of automotive components, these include headlamp lenses, turn signal lamp lenses, tail lamp lenses, plastic window glass, meter covers, outer panels, door handles, rear panels, wheel caps, visors, roof rails, sunroofs, instrument panels, panels, control cable covering materials, airbag covers, mudguards, bumpers, boots, and air hoses. Cases, lamp packings, gaskets, various moldings such as window moldings, sight shields, weather strips, glass run channels, grommets, vibration control and sound insulation materials, joint materials in the building materials field, handrails, windows, table edge materials, sashes, bathtubs, window frames, signs, lighting covers, water tanks, staircase skirting, carports, highway sound insulation walls, multi-wall sheets, steel wire coating materials, lighting globes, switch breakers, protective covers for machine tools, industrial deep-drawn vacuum formed containers, pump housings, home appliances, various packings in the low-voltage field Grips, belts, rubber feet, rollers, protectors, suction cups, gaskets for refrigerators, switches, connector covers, game machine covers, pachinko machines, OA housings, notebook PC housings, HDD head trays, instrument windows, transparent housings, OA gear rollers, switch case sliders, gas cock knobs, watch frames, watch gear train center pieces, amber caps, various rolls for OA equipment, tubular molded products such as hoses and tubes, irregular extrusion products, leather-like products, interlocking devices, toys such as soft-touch dolls,Examples of applications include pen grips, straps, suction cups, watches, umbrella bones, cosmetic cases, toothbrush handles and other general goods, housewares, Tupperware and other containers, cable ties, blow-molded infusion bottles, food bottles, water bottles, various bottles for personal care such as cosmetic bottles, catheters in medical parts, syringes, syringe gaskets, drip tubes, tubes, ports, caps, rubber stoppers, dialyzers, blood connectors, dentures, disposable containers, and the like, and foam molding applications are also possible. Among the above, in particular, the material is suitable for tubes for medical use, which can prevent the adsorption of medicinal components, and in the case of multi-layer tubes, it is most suitable for the inner layer material or the intermediate layer material. Molded articles made of polycarbonate resin compositions are particularly preferably used for automobile parts, and more preferably used for automobile interior parts. [Example]

[0129] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In the following, the physical properties and characteristics of polycarbonate resin compositions, molded articles, etc. were evaluated by the following methods.

[0130] [Test specimen preparation method and various evaluations] (1) How to prepare the test specimen First, pellets of the polycarbonate resin composition were dried using a hot air dryer at 90°C for 6 hours or more. Next, the pellets were fed into an injection molding machine (J85AD manufactured by The Japan Steel Works, Ltd.) and injection-molded plates (100 mm wide x 100 mm long x 2 mm thick) were molded under conditions of a resin temperature of 240°C and a mold temperature of 60°C. This injection-molded plate was used as a test piece.

[0131] (2) Appearance evaluation The test pieces obtained by the above (1) test piece preparation method were evaluated by visual observation. Test pieces with poor appearance such as surface turbidity or silver streaks were evaluated as "×", and those without poor appearance were evaluated as "◯".

[0132] (3) Abrasion resistance test The abrasion resistance test was carried out using a reciprocating abrasion tester (manufactured by Shinto Scientific Co., Ltd., model: TYPE30S). First, Kanakin No. 3 (JIS L 0803-compliant test attachment white cotton cloth) was cut to a width of 15 mm, and the resulting cut piece was attached to a Shinto Scientific 30 mm flat indenter measurement jig. Next, the cut piece (i.e., Kanakin No. 3) attached to the 30 mm flat indenter measurement jig was reciprocated 100 times on the surface of the test piece obtained by the above (1) test piece preparation method. The reciprocating motion was carried out under the conditions of a load of 1 kgf, a stroke of 50 mm, and a speed of 6000 mm / min. After that, a spectrophotometer (CM-M6 manufactured by Konica Minolta Inc.) was used to measure the color difference (ΔL * ) and calculate the color difference (ΔL * ) and the degree of scratches on the test piece surface was evaluated. In this example, when the difference in the surface roughness of the test piece was 5 or less, it was evaluated as "Good", and when it was more than 5, it was evaluated as "Poor".

[0133] <Color difference(ΔL * )> Color difference (ΔL * ) was calculated as follows based on the above test results. The color value L obtained at light receiving angles of -15° and +15° using a spectrophotometer (Konica Minolta CM-M6) * The value before the abrasion resistance test was calculated as the color value L0. * (-15°), L0 * (+15°), color value after abrasion resistance test is L * (-15°), L * (+15°), and calculate ΔL using the formula below. * asked for. ΔL * (-15°)=L * (-15°)-L0 * (-15°) ΔL * (+15°)=L * (+15°)-L0 * (+15°) ΔL * =(ΔL * (-15°)+ΔL * (+15°)) / 2

[0134] (4) Charpy notched impact test The polycarbonate resin composition pellets were dried at 90°C for 6 hours or more using a hot air dryer. Next, the pellets were fed into an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.) to mold dumbbell-shaped test pieces for mechanical properties (i.e., ISO test pieces for mechanical properties). The molding temperature was 240°C, and the mold temperature was 60°C. A notched Charpy impact test of the ISO test pieces for mechanical properties was carried out in accordance with ISO179-1 (2010). The notch tip radius R was 0.25 mm. The higher the notched Charpy impact strength, the better the impact resistance. In this example, the notched Charpy impact strength was 40 kJ / m 2 The above cases were judged to be excellent in mechanical strength.

[0135] [Raw materials used] The compounds used in the following production examples, their abbreviations and manufacturers are as follows: Polycarbonate resin (A): A-1, A-2, A-3 <Dihydroxy compounds> ISB: Isosorbide [Rocket Fleuret] CHDM: 1,4-cyclohexanedimethanol [SK Chemical] <Carbonate diester> DPC: Diphenyl carbonate [Mitsubishi Chemical Corporation] <Catalyst deactivator> Phosphorous acid [Taihei Chemical Industry Co., Ltd.] (molecular weight 82.0) <Heat stabilizer (antioxidant)> Irganox 1010: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][BASF] AS2112: Tris(2,4-di-tert-butylphenyl) phosphite [ADEKA] (molecular weight 646.9) <Release agent> E-275: Ethylene glycol distearate [NOF Corporation]

[0136] [Production Example 1 Polycarbonate Resin (A-1)] Polycarbonate resin polymerization was carried out using a continuous polymerization system consisting of three vertical stirred reactors, one horizontal stirred reactor, and a twin-screw extruder. Specifically, ISB, CHDM, and DPC were melted in tanks and continuously fed into the first vertical stirred reactor at flow rates of 35.2 kg / hr for ISB, 14.9 kg / hr for CHDM, and 74.5 kg / hr for DPC (molar ratio ISB / CHDM / DPC = 0.700 / 0.300 / 1.010). An aqueous solution of calcium acetate monohydrate was also fed into the first vertical stirred reactor at a catalyst concentration of 1.5 μmol per mol of total dihydroxy compounds. The first vertical stirred reactor had a reaction temperature of 190°C, an internal pressure of 25 kPa, and a residence time of 90 minutes, the second vertical stirred reactor had a reaction temperature of 195°C, an internal pressure of 10 kPa, and a residence time of 45 minutes, the third vertical stirred reactor had a reaction temperature of 210°C, an internal pressure of 3 kPa, and a residence time of 45 minutes, and the fourth horizontal stirred reactor had a reaction temperature of 225°C, an internal pressure of 0.5 kPa, and a residence time of 90 minutes. The fourth horizontal stirred reactor was operated while finely adjusting the internal pressure so that the reduced viscosity of the resulting polycarbonate resin would be 0.42 dL / g or more and less than 0.50 dL / g.

[0137] Polycarbonate resin was extracted from the fourth horizontal stirred reactor at a rate of 60 kg / hr. The resin was then fed in its molten state into a vented twin-screw extruder (TEX30α, manufactured by The Japan Steel Works, Ltd., L / D: 42.0, L (mm): screw length, D (mm): screw diameter). The polycarbonate resin passing through the extruder was then passed through a 10 μm SUS316 candle filter while still in its molten state to filter out impurities. The polycarbonate resin was then discharged in the form of strands from the die, water-cooled, solidified, and pelletized using a rotary cutter to obtain a polycarbonate resin with an ISB / CHDM molar ratio of 70 / 30 mol%. This polycarbonate resin is designated "A-1" as appropriate.

[0138] The extruder had three vacuum vents, through which residual low-molecular-weight components in the resin were removed by volatilization. Just before the second vent, 2000 ppm by weight of water was added to the resin, and water was poured in to remove the volatilization. Just before the third vent, 0.1 parts by weight of Irganox 1010, 0.05 parts by weight of AS2112, and 0.3 parts by weight of E-275 were added, respectively, per 100 parts by weight of polycarbonate resin. This yielded ISB / CHDM copolymer polycarbonate resin pellets. 0.65 ppm by weight of phosphorous acid (0.24 ppm by weight in terms of phosphorus atoms) was added to the polycarbonate resin as a catalyst deactivator. The phosphorous acid was added as follows: A masterbatch was prepared by mixing the polycarbonate resin pellets obtained in Production Example 1 with an ethanol solution of phosphorous acid, and the masterbatch was fed into the extruder just before the first vent port (on the resin feed port side of the extruder) so that the masterbatch was 1 part by weight per 100 parts by weight of the polycarbonate resin in the extruder.

[0139] [Production Example 2: Polycarbonate Resin (A-2)] A polycarbonate resin was produced in the same manner as in Production Example 1, except that the molar ratio of ISB to CHDM was ISB / CHDM = 0.500 / 0.500 and the reduced viscosity was adjusted to 0.50 dL / g or more and 0.63 dL / g or less. This polycarbonate resin is appropriately referred to as "A-2".

[0140] [Materials used in Examples and Comparative Examples] The abbreviations for the compounds used in the following Examples and Comparative Examples are as follows: [Polycarbonate resin (A)] Polycarbonate resins containing structural units derived from isosorbide include A-1 and A-2 below. A-1: Polycarbonate resin of Production Example 1. Glass transition temperature: 122°C. Reduced viscosity: 0.44 dL / g. A-2: Polycarbonate resin of Production Example 2. Glass transition temperature: 100°C. Reduced viscosity: 0.61 dL / g. A-3: S-3000R (Mitsubishi Engineering Plastics Corporation, commercially available product)

[0141] [Fatty acid amide (B)] B-1: BNT-22H (manufactured by Nippon Fine Chemical Co., Ltd., behenic acid amide, melting point: 110°C, number of carbon atoms in terminal alkyl group: 22). B-2: Slippers B (manufactured by Mitsubishi Chemical Corporation, ethylene bisbehenic acid amide, melting point: 142°C), number of carbon atoms in terminal alkyl group: 22). B-3: Slipax E (manufactured by Mitsubishi Chemical Corporation, ethylene bisstearic acid amide, melting point: 145°C, number of carbon atoms in terminal alkyl group: 18). B-4: Neutron 2 (manufactured by Nippon Fine Chemical Co., Ltd., stearic acid amide, melting point: 100°C, number of carbon atoms in terminal alkyl group: 18). B-5: Amizol CME (manufactured by Kawaken Fine Chemicals Co., Ltd., coconut oil fatty acid monoethanolamide, melting point: 71°C, number of carbon atoms in the terminal alkyl group of the main component: 12)

[0142] [Elastomer with core-shell structure (C)] Acrylic-styrene rubber, manufactured by Kaneka Corporation.

[0143] [Examples 1 to 4, Comparative Examples 1 to 6] Using a twin-screw extruder (TEX-33) manufactured by The Japan Steel Works, Ltd., equipped with one vent, polycarbonate resin and fatty acid amide were mixed to obtain the composition shown in Table 1, and the mixture was extruded into strands so that the resin temperature at the outlet reached 250°C. The extrudate was cooled and solidified with water, and then pelletized using a rotary cutter. The vent was connected to a vacuum pump, and the pressure at the vent was controlled to 500 Pa. A polycarbonate resin composition was thus produced. The evaluation results are shown in Table 1.

[0144] [Examples 5 to 6, Comparative Example 7] Using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd., equipped with one vent, polycarbonate resin, fatty acid amide, and a core-shell elastomer were mixed to the composition shown in Table 2, and extruded into strands so that the resin temperature at the outlet was 250°C. The extrudate was cooled and solidified with water and then pelletized using a rotary cutter. The vent was connected to a vacuum pump, and the pressure at the vent was controlled to 500 Pa. Polycarbonate resin compositions were produced in this manner. The evaluation results are shown in Table 2.

[0145] [Table 1]

[0146] [Table 2]

[0147] As can be seen from Table 1, Examples 1 to 4, which contain fatty acid amides (B-1) and (B-2) with alkyl terminals, have smaller color difference values ​​in the abrasion resistance test compared to Comparative Example 1, which does not contain fatty acid amide (B). This suggests that a crystalline film is formed by the fatty acid amides (B-1) and (B-2), improving abrasion resistance. Furthermore, as can be seen from a comparison between Examples 1 to 4 and Comparative Examples 2 and 3, it is believed that the fact that the fatty acid amides have alkyl terminals with 19 or more carbon atoms and one or more amide groups contributes to improved abrasion resistance. Furthermore, as can be seen from a comparison between Examples 1 to 4 and Comparative Examples 5 and 6, it is believed that the effect of fatty acid amides (specifically, fatty acid amides B-1 and B-2) in improving abrasion resistance is enhanced in polycarbonate resins having structural units derived from dihydroxy compounds.

[0148] Furthermore, as can be seen from Table 2, Examples 5 and 6 exhibit improved abrasion resistance without any deterioration in appearance or impact resistance. This is thought to be because Examples 5 and 6 contain an elastomer (C) having a core-shell structure, along with a fatty acid amide having an alkyl terminal with 19 or more carbon atoms and one or more amide groups.

[0149] As described above, the molded articles of Examples 1 to 6 had excellent appearance and good abrasion resistance. This is thought to be a unique effect of Examples 1 to 6 containing the specified polycarbonate resin (A) and the specified fatty acid amide (B).

Claims

1. a polycarbonate resin (A) having a content of structural units derived from a dihydroxy compound represented by the following formula (1) of 50 mol % or more and a content of structural units derived from a dihydroxy compound containing an aromatic group of less than 50 mol %; A polycarbonate resin composition containing a fatty acid amide (B) having an alkyl terminal with 19 or more carbon atoms and one or more amide groups. 【Chemistry 1】

2. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) has structural units derived from at least one dihydroxy compound selected from the group consisting of ether group-containing dihydroxy compounds other than the dihydroxy compound represented by formula (1), aliphatic dihydroxy compounds, and alicyclic dihydroxy compounds, and structural units derived from the dihydroxy compound represented by formula (1).

3. 3. The polycarbonate resin composition according to claim 1, wherein the fatty acid amide (B) has a melting point of 90°C or higher.

4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the content of the fatty acid amide (B) per 100 parts by mass of the polycarbonate resin (A) is 0.001 parts by mass or more and 5 parts by mass or less.

5. The polycarbonate resin composition according to any one of claims 1 to 4, further comprising an elastomer (C) having a core-shell structure.

6. 6. The polycarbonate resin composition according to claim 5, wherein the content of the elastomer (C) having a core-shell structure is 0.1 to 20 parts by weight per 100 parts by weight of the polycarbonate resin composition.

7. A molded article formed from the polycarbonate resin composition according to any one of claims 1 to 6.

8. The molded article according to claim 7, which is an automobile part.

Images