Polycarbonate resin composition and molded article produced therefrom

Abstract

To provide a polycarbonate resin composition and a molded article produced from the composition, which exhibit superior flowability, rigidity, resistance to moisture and heat, and thermal stability, and in which resin degradation is suppressed even during high-temperature molding.SOLUTION: A polycarbonate resin composition contains, based on 100 pts.wt. of a resin component composed of (A) 50 to 95 pts.wt. of polycarbonate resin (component A) and (B) 5 to 50 pts.wt. of polyester resin (component B), (C) 5 to 80 pts.wt. of an inorganic filler (component C), (D) 0.005 to 3.0 pts.wt. of a trivalent phosphorus compound (component D), and (E) 0.035 to 3.0 pts.wt. of a phosphate metal salt (component E).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition which is excellent in flowability, rigidity, moist heat resistance and thermal stability and which is less susceptible to resin deterioration even when molded at high temperatures, and to a molded article made thereof. [Background technology]

[0002] Polycarbonate resins have excellent mechanical and thermal properties and are therefore used in a variety of applications, primarily in the automotive, office automation, and electronic / electrical equipment fields. Furthermore, resins obtained by alloying polycarbonate resins with polyester resins have been widely used in the automotive field due to their excellent mechanical and chemical resistance properties. Against this background, resin compositions consisting of polycarbonate resins and polyester resins reinforced with inorganic fillers to further improve mechanical properties have been disclosed, but they suffer from the problem of impaired thermal stability. Therefore, efforts to improve thermal stability have been undertaken. Patent Document 1 discloses a method of blending phosphate into a resin obtained by alloying polycarbonate resins with polyester resins. However, while this method improves thermal stability, it also deteriorates moist heat resistance. Patent Document 2 discloses a method of blending a phosphate metal salt into a resin obtained by alloying polycarbonate resins with alicyclic polyester resins. However, while this method improves thermal stability, the improvement in thermal stability is insufficient for high-temperature molding intended for thin-walled products, and further improvement is needed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5640734 [Patent Document 2] Patent No. 5040224 Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above, an object of the present invention is to provide a polycarbonate resin composition which is excellent in flowability, rigidity, moist heat resistance and thermal stability and which is less susceptible to resin deterioration even when molded at high temperatures, and a molded article made thereof. [Means for solving the problem]

[0005] According to the present invention, the above problems are solved by the following configuration. 1. A polycarbonate resin composition containing 100 parts by weight of resin components consisting of 50 to 95 parts by weight of (A) polycarbonate resin (component A) and 5 to 50 parts by weight of (B) polyester resin (component B), 5 to 80 parts by weight of (C) inorganic filler (component C), 0.005 to 3.0 parts by weight of (D) trivalent phosphorus compound (component D), and 0.035 to 3.0 parts by weight of (E) phosphate metal salt (component E). 2. The resin composition according to item 1 above, wherein component B is at least one polyester resin selected from the group consisting of polyethylene terephthalate resins and polybutylene terephthalate resins. 3. The resin composition according to the above item 1 or 2, wherein component C is glass fiber. 4. The resin composition according to any one of items 1 to 3 above, wherein component E is stearyl acid phosphate zinc salt. 5. A molded article made from the resin composition according to any one of items 1 to 4 above. [Effects of the Invention]

[0006] The polycarbonate resin composition of the present invention has excellent fluidity, rigidity, moist heat resistance, and thermal stability, and is less susceptible to resin degradation even when molded at high temperatures, and is therefore useful in a wide range of applications, including electrical and electronic applications, mechanical applications, office automation applications, automotive interior and exterior parts, medical applications, and various other applications. In particular, the present invention provides molded articles that are extremely useful as automotive interior and exterior parts, and the industrial effects of the present invention are extremely significant. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present invention will be further described in detail below.

[0008] (Component A: Polycarbonate resin) The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

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

[0010] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, special polycarbonate resins produced using other dihydric phenols can be used as component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as part or all of the dihydric phenol component are suitable for applications where dimensional change due to water absorption and shape stability are particularly strict requirements. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more, of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better moist heat resistance are required, it is particularly suitable that component A constituting the resin composition is a copolymer polycarbonate resin of the following (1) to (3). (1) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and BCF accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol components constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, and even more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, and even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and Bis-TMC accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%).

[0011] These special polycarbonate resins may be used alone or in a suitable mixture of two or more. They may also be used in a mixture with a commonly used bisphenol A polycarbonate resin. The production methods and properties of these special polycarbonate resins are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580.

[0012] Among the various polycarbonate resins mentioned above, those in which the copolymer composition and the like are adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges have good moist heat resistance of the polymer itself and are also remarkably excellent in terms of low warpage after molding, and are therefore particularly suitable in fields where dimensional stability is required. (I) a polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C; or (II) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0013] Here, the water absorption rate of polycarbonate resin is a value measured by using a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm and immersing it in water at 23°C for 24 hours in accordance with ISO 62-1980, and then measuring the moisture content. Also, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0014] Carbonate precursors that can be used include carbonyl halides, carbonic acid diesters, and haloformates, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

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

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

[0017] The structural units derived from polyfunctional aromatic compounds in the branched polycarbonate resin are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols and the structural units derived from such polyfunctional aromatic compounds. In particular, in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols. The proportion of such branched structures is 1 It can be calculated by H-NMR measurement.

[0018] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The bifunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0019] The reaction modes of the methods for producing the polycarbonate resin of the present invention, such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of a cyclic carbonate compound, are well known in various literatures and patent publications.

[0020] In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.5×10 4 ~4.0×10 4 and more preferably 1.7 × 10 4 ~3.5×10 4 , and more preferably 1.9 × 10 4 ~3.0×10 4 The viscosity average molecular weight is 1.5 × 10 4 Polycarbonate resins with a viscosity average molecular weight of less than 4.0 × 10 may not provide good mechanical properties. 4 Resin compositions obtained from polycarbonate resins exceeding this range are inferior in terms of fluidity during injection molding and therefore are inferior in versatility.

[0021] The polycarbonate resin may be obtained by mixing resins having a viscosity average molecular weight outside the above range. 4), the entropy elasticity of the resin is improved. As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in molding processability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, component A has a viscosity average molecular weight of 7×10 4 ~3×10 5 Polycarbonate resin (A-1-1 component) and viscosity average molecular weight 1 × 10 4 ~3×10 4 The aromatic polycarbonate resin (component A-1-2) has a viscosity average molecular weight of 1.6 × 10 4 ~3.5×10 4 A polycarbonate resin (component A-1) (hereinafter, sometimes referred to as a "polycarbonate resin containing a high molecular weight component") having the formula:

[0022] In such a polycarbonate resin containing a high molecular weight component (component A-1), the molecular weight of component A-1-1 is 7 × 10 4 ~2×10 5 is preferable, and more preferably 8×10 4 ~2×10 5 , and more preferably 1 × 10 5 ~2×10 5 , particularly preferably 1 × 10 5 ~1.6×10 5 The molecular weight of component A-1-2 is 1 × 10 4 ~2.5×10 4 is preferable, and more preferably 1.1 × 10 4 ~2.4×10 4 , and more preferably 1.2 × 10 4 ~2.4×10 4 , particularly preferably 1.2 × 10 4 ~2.3×10 4 is.

[0023] The high-molecular-weight component-containing polycarbonate resin (component A-1) can be obtained by mixing the components A-1-1 and A-1-2 in various ratios and adjusting the ratio to satisfy a predetermined molecular weight range. Preferably, the component A-1-1 accounts for 2 to 40% by weight, more preferably 3 to 30% by weight, even more preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight, of 100% by weight of component A-1.

[0024] Methods for preparing component A-1 include: (1) a method in which component A-1-1 and component A-1-2 are polymerized independently and then mixed; (2) a method in which an aromatic polycarbonate resin that shows multiple polymer peaks in a molecular weight distribution chart obtained by GPC, as typified by the method disclosed in Japanese Patent Laid-Open No. 5-306336, is produced in the same system, and the aromatic polycarbonate resin is produced so as to satisfy the conditions for component A-1 of the present invention; and (3) a method in which an aromatic polycarbonate resin obtained by such a production method (production method (2)) is mixed with component A-1-1 and / or component A-1-2 that have been produced separately.

[0025] The viscosity average molecular weight in the present invention is determined by first calculating the specific viscosity (H SP ) was measured using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (Η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (H SP ) and calculate the viscosity average molecular weight M using the following formula: H SP / c=[H]+0.45×[H] 2 c (where [H] is the intrinsic viscosity) [H]=1.23×10 -4 M 0.83 c=0.7

[0026] The viscosity average molecular weight of the polycarbonate resin in the resin composition of the present invention is calculated as follows: The composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve the soluble components in the composition. The soluble components are collected by filtration through Celite. The solvent in the resulting solution is then removed. The solid obtained after solvent removal is thoroughly dried to obtain a solid of components soluble in methylene chloride. 0.7 g of this solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined in the same manner as above. The viscosity average molecular weight M is then calculated from the specific viscosity in the same manner as above.

[0027] The polycarbonate resin of the present invention may be a polycarbonate-polydiorganosiloxane copolymer resin, preferably prepared by copolymerizing a dihydric phenol represented by the following general formula (1) with a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3):

[0028] [ka]

[0029] [In the above general formula (1), R 1 and R 2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2):

[0030] [ka]

[0031] [In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple groups, they may be the same or different; g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0032] [ka]

[0033] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0034] Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane 4,4'-dihydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0035] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0036] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

[0037] [ka]

[0038] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, at the end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, with (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes being particularly preferred. The molecular weight distribution (Mw / Mn) of the hydroxyaryl-terminated polydiorganosiloxanes (II) is preferably 3 or less. To achieve even better low outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

[0039] Furthermore, in order to achieve high impact resistance, the diorganosiloxane degree of polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane degree of polymerization (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, while above the upper limit of this preferred range, poor appearance appears.

[0040] The polydiorganosiloxane content of the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are achieved, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is easily achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are 1 It can be calculated by H-NMR measurement.

[0041] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0042] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the present invention.

[0043] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution.

[0044] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary. The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0045] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0046] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Similarly, the proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0047] The solvent may be any of various inert solvents used in the production of known polycarbonates, either singly or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0048] The reaction pressure for oligomer formation is not particularly limited and may be atmospheric, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is similar to that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0049] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred while adding a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0050] [ka]

[0051] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0052] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0053] The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0054] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0055] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0056] The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0057] A branching agent can be used in combination with the above-mentioned dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1 ,1-bis(4-hydroxyphenyl)ethyl]benzene}-A,A-dimethylbenzylphenol, trisphenols such as tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, even more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by H-NMR measurement.

[0058] The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually, it can be preferably carried out at normal pressure or at about the autogenous pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 °C. Since heat is generated in many cases during polymerization, it is desirable to carry out water cooling or ice cooling. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally specified, but usually, it is carried out for 0.5 to 10 hours.

[0059] In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (such as mixing, fractionation, etc.) and / or chemical treatment (such as polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate-polydiorganosiloxane copolymer resin with a desired reduced viscosity [Η SP / c].

[0060] The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods and recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (degree of purification).

[0061] The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 60 nm. Such an average size is more preferably 3 to 55 nm, and still more preferably 5 to 50 nm. If it is less than the lower limit of such a preferred range, the impact resistance and flame retardancy are not sufficiently exhibited, and if it exceeds the upper limit of such a preferred range, the impact resistance may not be stably exhibited in some cases.

[0062] <Component B: Polyester resin> The polyester resin used as component B in the present invention is preferably a polymer or copolymer obtained by a condensation reaction of aromatic dicarboxylic acid or its reactive derivative and diol or its ester derivative as the main components. The aromatic dicarboxylic acid referred to here is preferably selected from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 4,4'-biphenylmethanedicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenylisopropylidenedicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, and 2,5-pyridinedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenyletherdicarboxylic acid, and β-hydroxyethoxybenzoic acid, with terephthalic acid and 2,6-naphthalenedicarboxylic acid being particularly preferred. Two or more aromatic dicarboxylic acids may be used in combination. In addition, it is possible to use a small amount of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid in combination with the dicarboxylic acid. Examples of diols that are components of the polyester resin of the present invention include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; diols containing aromatic rings such as 2,2-bis(β-hydroxyethoxyphenyl)propane; and mixtures thereof. Furthermore, in small amounts, one or more long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol, may be copolymerized.The polyester resin of the present invention can be branched by incorporating a small amount of a branching agent. While there is no particular limitation on the type of branching agent, examples include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol. Specific examples of the polyester resin include polyethylene terephthalate resin (PET), polypropylene terephthalate resin, polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene naphthalate resin (PEN), polybutylene naphthalate resin (PBN), and polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate resin, as well as copolymer polyester resins such as polyethylene isophthalate / terephthalate and polybutylene terephthalate / isophthalate. Among these, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and mixtures thereof are preferred, as they have a good balance of mechanical properties, etc., and at least one polyester resin selected from the group consisting of polyethylene terephthalate resin and polybutylene terephthalate resin is more preferred.

[0063] The melt volume rate (MVR) of the polyethylene terephthalate resin and polybutylene terephthalate resin of the present invention is not particularly limited, but when measured using a semi-automatic melt indexer [Semi-automatic melt indexer 2A manufactured by Toyo Seiki Seisakusho Co., Ltd.] under conditions of a temperature of 280°C and a load of 2.16 kg, the MVR should be 5 to 220 cm 3 / 10 min, and more preferably 7 to 120 cm 3 Before measuring the MVR, the polyethylene terephthalate resin is dried in a hot air circulating dryer at 150°C for 6 hours, and the polybutylene terephthalate resin is dried at 120°C for 6 hours.

[0064] The end group structure of the resulting polyester resin is not particularly limited, and the proportion of hydroxyl groups and carboxyl groups in the end groups may be approximately equal, or one of them may be greater than the other.Furthermore, the end groups may be blocked by reacting with a compound reactive with the end groups.

[0065] The polyester resin is produced by a conventional method in which a dicarboxylic acid component and the diol component are polymerized under heating in the presence of a polymerization catalyst containing titanium, germanium, antimony, etc., and the by-product water or lower alcohol is discharged from the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, etc. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. can be exemplified.

[0066] Preferred specific examples of the organotitanium compound polymerization catalyst include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, a reaction product of tetrabutyl titanate and trimellitic anhydride, etc. Furthermore, when a polyester resin is produced using a specific titanium-based catalyst other than those mentioned above, a polyester resin having superior thermal stability can be obtained, and therefore, it is more preferably used.

[0067] The specific titanium-based catalyst described above comprises a reaction product of the following titanium compound component (A) and phosphorus compound component (B).

[0068] The titanium compound component (A) is preferably at least one titanium compound component selected from the group consisting of titanium compound (1) represented by the following general formula (I) and titanium compound (2) obtained by reacting titanium compound (1) with an aromatic polycarboxylic acid or its anhydride represented by the following general formula (II):

[0069] [ka] [However, in formula (I), R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, and when k is 2 or 3, two or three R 2 and R 3 may be the same as or different from each other.

[0070] [ka] (In formula (II), m represents an integer of 2 to 4.)

[0071] The phosphorus compound component (B) is a phosphorus compound component comprising at least one phosphorus compound (3) represented by the following general formula (III). [ka] [wherein, in formula (III), R 5 represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms.

[0072] The polyester resin produced by using the specific titanium catalyst may have better thermal stability and moist heat resistance than those produced by using germanium, antimony, or other titanium catalysts. When the specific titanium catalyst is used, the quality is stable even when less additives such as color stabilizers and heat stabilizers are added during production than when other catalysts are used, and therefore, decomposition of the additives in a hot environment or a moist heat environment is reduced, which is presumably why the polyester resin has better thermal stability and moist heat resistance.

[0073] In the reaction product of the titanium compound component (A) and the phosphorus compound component (B), the reaction molar ratio (mTi / mP) of the molar amount of the titanium compound component (A) converted into titanium atoms (mTi) to the molar amount of the phosphorus compound component (B) converted into phosphorus atoms (mP) is preferably within the range of 1 / 3 to 1 / 1, and more preferably within the range of 1 / 2 to 1 / 1.

[0074] The molar amount of titanium compound component (A) in terms of titanium atoms is the sum of the products of the molar amounts of each titanium compound contained in titanium compound component (A) and the number of titanium atoms contained in one molecule of the titanium compound, and the molar amount of phosphorus compound component (B) in terms of phosphorus atoms is the sum of the products of the molar amounts of each phosphorus compound contained in phosphorus compound component (B) and the number of phosphorus atoms contained in one molecule of the phosphorus compound. However, since the phosphorus compound represented by formula (III) contains one phosphorus atom per molecule, the molar amount of the phosphorus compound in terms of phosphorus atoms is equal to the molar amount of the phosphorus compound.

[0075] If the reaction molar ratio (mTi / mP) is greater than 1 / 1, i.e., if the amount of titanium compound component (A) is too large, the polyester resin obtained using the catalyst may have poor color tone (too high b value) and reduced heat resistance. If the reaction molar ratio (mTi / mP) is less than 1 / 3, i.e., if the amount of titanium compound component (A) is too small, the catalytic activity of the resulting catalyst for the polyester synthesis reaction may be insufficient.

[0076] Examples of the titanium compound (1) represented by the general formula (I) used in the titanium compound component (A) include titanium tetraalkoxides such as titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxide, as well as alkyl titanates such as octaalkyltrititanates and hexaalkylditanates. Among these, it is preferable to use titanium tetraalkoxides that have good reactivity with the phosphorus compound component used in the present invention, and it is particularly preferable to use titanium tetrabutoxide.

[0077] The titanium compound (2) used in the titanium compound component (A) is obtained by reacting the titanium compound (1) with an aromatic polycarboxylic acid represented by the general formula (II) or its anhydride. The aromatic polycarboxylic acid and its anhydride represented by the general formula (II) are preferably selected from the group consisting of phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid, and their anhydrides. It is particularly preferable to use trimellitic anhydride, which has good reactivity with the titanium compound (1) and has a high affinity for polyesters with the resulting polycondensation catalyst.

[0078] The reaction of titanium compound (1) with the aromatic polycarboxylic acid or its anhydride of general formula (II) is carried out by mixing the aromatic polycarboxylic acid or its anhydride with a solvent, dissolving the mixture in part or in whole, adding titanium compound (1) dropwise to the mixture, and heating the mixture at a temperature of 0 to 200°C for at least 30 minutes, more preferably at a temperature of 30 to 150°C for 40 to 90 minutes. The reaction pressure is not particularly limited, and normal pressure is sufficient. The catalyst can be appropriately selected from those capable of dissolving the required amount of the compound of formula (II) or its anhydride in part or in whole, but is preferably selected from ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene, etc.

[0079] There is no limitation on the molar ratio of the titanium compound (1) to the compound represented by formula (II) or its anhydride in the reaction. However, if the proportion of titanium compound (1) is too high, the color tone of the resulting polyester resin may deteriorate or the softening point may decrease. Conversely, if the proportion of titanium compound (1) is too low, the polycondensation reaction may not proceed smoothly. For this reason, it is preferable to control the molar ratio of the titanium compound (1) to the compound represented by formula (II) or its anhydride in the reaction within the range of 2 / 1 to 2 / 5. The reaction product obtained by this reaction may be directly subjected to the reaction with the aforementioned phosphorus compound (3), or it may be purified by recrystallization using a solvent such as acetone, methyl alcohol, and / or ethyl acetate, and then reacted with the phosphorus compound (3).

[0080] In the phosphorus compound (3) of the general formula (III) used in the phosphorus compound component (B), R 5 The aryl group having 6 to 20 carbon atoms or the alkyl group having 1 to 20 carbon atoms represented by the formula (I) may be unsubstituted or substituted with one or more substituents, such as a carboxy group, an alkyl group, a hydroxyl group, and an amino group.

[0081] Examples of the phosphorus compound (3) of the general formula (III) include monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono(4-dodecyl)phenyl phosphate, mono(4-methyl The phosphorus compounds include monoalkyl phosphates and monoaryl phosphates such as mono(4-phenyl)phosphate, mono(4-ethylphenyl)phosphate, mono(4-propylphenyl)phosphate, mono(4-dodecylphenyl)phosphate, monotolyl phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, and monoanthryl phosphate, and these may be used alone or as a mixture of two or more, for example, a mixture of a monoalkyl phosphate and a monoaryl phosphate. However, when the phosphorus compounds are used as a mixture of two or more, the ratio of the monoalkyl phosphate preferably accounts for 50% or more, more preferably 90% or more, and even more preferably 100%.

[0082] To prepare a catalyst from titanium compound component (A) and phosphorus compound component (B), for example, phosphorus compound component (B) consisting of at least one phosphorus compound (3) of formula (III) is mixed with a solvent to dissolve part or all of phosphorus compound component (B) in the solvent, titanium compound component (A) is added dropwise to this mixture, and the reaction system is usually heated at a temperature of preferably 50°C to 200°C, more preferably 70°C to 150°C, for preferably 1 minute to 4 hours, more preferably 30 minutes to 2 hours. There are no particular restrictions on the reaction pressure in this reaction, and the reaction may be carried out under elevated pressure (0.1 to 0.5 MPa), atmospheric pressure, or reduced pressure (0.001 to 0.1 MPa), but is usually carried out under atmospheric pressure.

[0083] The solvent for the phosphorus compound component (B) of formula (III) used in the catalyst preparation reaction is not particularly limited as long as it can dissolve at least a part of the phosphorus compound component (B), but for example, a solvent consisting of at least one selected from ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene, etc. is preferably used. In particular, it is preferable to use as the solvent the same compound as the glycol component constituting the polyester to be finally obtained.

[0084] The reaction product of the titanium compound component (A) and the phosphorus compound component (B) may be separated from the reaction system by means of centrifugal sedimentation, filtration, or the like, and then used as a catalyst for producing a polyester resin without purification, or the separated reaction product may be purified by recrystallization with a recrystallization agent such as acetone, methyl alcohol, and / or water, and the purified product thus obtained may be used as a catalyst. Alternatively, the reaction mixture containing the reaction product may be used as a catalyst-containing mixture without separating the reaction product from the reaction system.

[0085] As the titanium-based catalyst, it is preferable to use a reaction product of at least one titanium compound (1) of the formula (I) (where k represents 1), i.e., a titanium compound component (A) consisting of a titanium tetraalkoxide, and a phosphorus compound component (B) consisting of at least one phosphorus compound of the formula (III). Furthermore, as the titanium catalyst, a compound represented by the following general formula (IV) is preferably used.

[0086] [ka]

[0087] [In the above formula, R 6 and R 7 each independently represents an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0088] A catalyst containing a titanium / phosphorus compound represented by formula (IV) has high catalytic activity, and a polyester resin produced using the catalyst has good color tone (low b value), has practically sufficiently low contents of acetaldehyde, residual metals, and cyclic trimers of esters of aromatic dicarboxylic acids and alkylene glycols, and may have practically sufficient polymer performance.

[0089] In the titanium-based catalyst, the titanium / phosphorus compound of the general formula (IV) is preferably contained in an amount of 50% by weight or more, more preferably 70% by weight or more.

[0090] The amount of titanium catalyst used is preferably such that its millimolar titanium content is 2 to 40 millimoles, more preferably 5 to 35 millimoles, and even more preferably 10 to 30 millimoles, relative to the total millimolar amount of aromatic dicarboxylic acid components contained in the polymerization starting materials. If the amount is less than 2 millimoles, the catalyst's ability to promote the polycondensation reaction of the polymerization starting materials will be insufficient, resulting in insufficient polyester production efficiency and making it impossible to obtain a polyester resin with the desired degree of polymerization. If the amount exceeds 40 millimoles, the color tone (b value) of the resulting polyester resin will be insufficient and will become yellowish, reducing its practical utility.

[0091] There are no limitations on the method for producing alkylene glycol esters of aromatic dicarboxylic acids and / or oligomers thereof. They are typically produced by thermally reacting an aromatic dicarboxylic acid or its ester-forming derivative with an alkylene glycol or its ester-forming derivative. For example, ethylene glycol esters of terephthalic acid and / or oligomers thereof, which are used as raw materials for polyethylene terephthalate resin, are produced by directly esterifying terephthalic acid with ethylene glycol, transesterifying a lower alkyl ester of terephthalic acid with ethylene glycol, or adding ethylene oxide to terephthalic acid. The alkylene glycol esters of aromatic dicarboxylic acids and / or oligomers thereof may contain other dicarboxylic acid esters copolymerizable therewith as additional components, in an amount that does not substantially impair the effects of the method of the present invention, specifically, preferably 10 mol % or less, more preferably 5 mol % or less, based on the total molar amount of the acid components.

[0092] The copolymerizable additional component is preferably selected from esters or anhydrides of one or more of the following: an acid component, such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, aliphatic and alicyclic dicarboxylic acids, and hydroxycarboxylic acids, such as β-hydroxyethoxybenzoic acid and p-oxybenzoic acid; and a glycol component, such as alkylene glycols having two or more carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A, bisphenol S, and aliphatic, alicyclic, and aromatic diol compounds and polyoxyalkylene glycols. The additional component esters may be used alone or in combination of two or more. However, the copolymerization amount is preferably within the above range.

[0093] When terephthalic acid and / or dimethyl terephthalate are used as starting materials, recovered dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate resin or recovered terephthalic acid obtained by hydrolyzing the recovered dimethyl terephthalate can be used in an amount of 70% by weight or more, based on the weight of all acid components constituting the polyester resin. In this case, the polyalkylene terephthalate resin is preferably polyethylene terephthalate resin. In particular, from the viewpoint of efficient resource utilization, it is preferable to use recycled PET bottles, recycled textile products, recycled polyester film products, and even polymer waste generated in the manufacturing process of these products as raw materials for polyester resin production. Here, there are no particular limitations on the method for depolymerizing recycled polyalkylene terephthalate resin to obtain dimethyl terephthalate, and any conventionally known method can be used. For example, a recovered polyalkylene terephthalate resin can be depolymerized using ethylene glycol, followed by transesterification of the depolymerized product with a lower alcohol, such as methanol. The resulting reaction mixture can be purified to recover a lower alkyl ester of terephthalic acid. This lower alkyl ester can then be subjected to transesterification with an alkylene glycol, and the resulting phthalic acid / alkylene glycol ester can be polycondensed to obtain a polyester resin. The method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method can be used. For example, dimethyl terephthalate can be recovered from the reaction mixture obtained by the transesterification reaction by recrystallization and / or distillation, and then hydrolyzed by heating with water at high temperature and pressure to recover terephthalic acid. Among the impurities contained in the terephthalic acid obtained by this method, the total content of 4-carboxybenzaldehyde, paratoluic acid, benzoic acid, and dimethyl hydroxyterephthalate is preferably 1 ppm or less. The content of monomethyl terephthalate is preferably in the range of 1 to 5,000 ppm. The terephthalic acid recovered by the above-mentioned method can be directly esterified with an alkylene glycol, and the resulting ester can be polycondensed to produce a polyester resin.

[0094] In the polyester resin used in the present invention, the catalyst may be added to the polymerization starting materials at any stage before the start of the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its oligomer, and the method of addition is not limited. For example, the aromatic dicarboxylic acid alkylene glycol ester may be prepared, and a solution or slurry of the catalyst may be added to the reaction system to start the polycondensation reaction. Alternatively, the catalyst solution or slurry may be added to the reaction system together with the starting materials or after the starting materials are charged when the aromatic dicarboxylic acid alkylene glycol ester is prepared.

[0095] There are no particular limitations on the reaction conditions for producing the polyester resin used in the present invention. In general, the polycondensation reaction is preferably carried out at a temperature of 230 to 320°C under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa), or under a combination of these conditions, for 15 to 300 minutes.

[0096] In the polyester resin used in the present invention, a reaction stabilizer, such as trimethyl phosphate, may be added to the reaction system at any stage in the polyester production process, as needed. Furthermore, if necessary, one or more of the following additives may be blended into the reaction system: antioxidant, ultraviolet absorber, flame retardant, fluorescent brightener, matting agent, tinting agent, antifoaming agent, and other additives. It is particularly preferred that the polyester resin contains at least one antioxidant containing a hindered phenol compound, and the content of this antioxidant is preferably 1 wt% or less based on the weight of the polyester resin. If the content exceeds 1 wt%, thermal degradation of the antioxidant itself may occur, resulting in the disadvantage of deteriorating the quality of the resulting product.

[0097] The hindered phenolic antioxidant compounds used in the polyester resins of the present invention are selected from pentaerythritol tetradecyl [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, and are preferably used in combination with thioether secondary antioxidants. The method for adding the hindered phenolic antioxidant to the polyester resin is not particularly limited, but it is preferably added at any stage between the end of the transesterification or esterification reaction and the completion of the polymerization reaction.

[0098] Furthermore, to finely adjust the color tone of the resulting polyester resin, a tinting agent consisting of one or more organic blue pigments, such as azo-based, triphenylmethane-based, quinoline-based, anthraquinone-based, and phthalocyanine-based, and inorganic blue pigments, can be added to the reaction system during the polyester resin production process. Naturally, in the production method of the present invention, it is not necessary to use inorganic blue pigments containing cobalt or the like as tinting agents, as these pigments reduce the melt thermal stability of the polyester resin. Therefore, the polyester resin used in the present invention is substantially free of cobalt.

[0099] The content of cyclic trimers of esters of aromatic dicarboxylic acids and alkylene glycols is preferably 0.5 wt% or less and the content of acetaldehyde is preferably 5 ppm or less. The cyclic trimers include alkylene terephthalate resins such as ethylene terephthalate resins, trimethylene terephthalate resins, tetramethylene terephthalate resins, and hexamethylene terephthalate resins, and alkylene naphthalate resins such as ethylene naphthalate resins, trimethylene naphthalate resins, tetramethylene naphthalate resins, and hexamethylene naphthalate resins.

[0100] In the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in the transesterification reaction, which is the previous stage of the conventionally known polycondensation, can be used in combination, and after the transesterification reaction is completed, it is also possible to deactivate such a catalyst with a compound such as phosphoric acid or phosphorous acid compound and then perform polycondensation.

[0101] The method for producing the polyester resin can be either a batch method or a continuous polymerization method.

[0102] The content of component B is 5 to 50 parts by weight out of a total of 100 parts by weight of components A and B, preferably 6 to 48 parts by weight, and more preferably 8 to 45 parts by weight. When the content of component B is less than 5 parts by weight, the fluidity decreases. On the other hand, when it exceeds 50 parts by weight, the thermal stability and moisture and heat resistance deteriorate.

[0103] <Component C: Inorganic filler> Examples of the inorganic filler used in the present invention include mica, wollastonite, talc, and glass fiber. Among them, glass fiber is preferable. The glass fiber is not particularly limited to the glass composition such as A glass, C glass, E glass, etc., and may contain components such as TiO2, SO3, P2O5, etc. in some cases. However, E glass (alkali-free glass) is more preferable. The glass fiber is obtained by rapidly cooling molten glass while stretching it by various methods into a predetermined fibrous shape. The rapid cooling and stretching conditions in such cases are not particularly limited either. In addition to a circular cross-section, shapes other than circular such as elliptical, mayu-shaped, and three-lobed-shaped may also be used. Furthermore, a mixture of circular glass fiber and glass fiber with a shape other than circular may also be used.

[0104] The fiber diameter of the glass fiber is preferably 1 to 25 μm, more preferably 3 to 17 μm. When the fiber diameter is too thin, the fiber may be easily broken and the rigidity may decrease. Also, since the surface area increases, relatively more coating agents are required, which may have an adverse effect when flame retardancy is required. When the fiber diameter is too large, the appearance of the molded product may deteriorate.

[0105] The number-average fiber length of the glass fibers in pellets or molded articles made from the resin composition of the present invention is preferably 50 to 500 μm, more preferably 100 to 400 μm, and even more preferably 120 to 300 μm. The number-average fiber length is calculated by an image analyzer from observations using an optical microscope of the glass fiber residue collected after dissolving the molded article in a solvent or decomposing the resin with a basic compound. In calculating this value, fibers with a length of 10 μm or less are not counted.

[0106] Examples of the plate-shaped glass filler include glass flakes, including metal-coated glass flakes and metal oxide-coated glass flakes. The glass flakes that serve as the substrate for the plate-shaped glass filler are plate-shaped glass flakes produced by methods such as cylinder blowing and sol-gel processes. The size of the raw glass flakes can be selected from a variety of sizes depending on the degree of crushing and classification. The average particle size of the glass flakes used as the raw material is preferably 10 to 1,000 μm, more preferably 20 to 500 μm, and even more preferably 30 to 300 μm. This is because glass flakes within the above range are excellent in both handleability and moldability. Typically, plate-shaped glass fillers crack during melt-kneading with resin, reducing their average particle size. The number-average particle size of the plate-shaped glass filler in the resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and even more preferably 20 to 80 μm. The number-average particle size is a value calculated by an image analyzer from an optical microscope image of the plate glass filler residue collected after high-temperature incineration of a molded product, dissolution in a solvent, decomposition with chemicals, or other treatments. The value is calculated using the flake thickness as a guide and excluding flakes with lengths less than that. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1.5 to 6 μm. A plate glass filler having the above number-average particle size and thickness may achieve good mechanical strength, appearance, and moldability.

[0107] Glass fillers that have been surface-treated with well-known surface treatment agents such as silane coupling agents, titanate coupling agents, or aluminate coupling agents are preferred from the viewpoint of improving mechanical strength. Also, glass fibers and glass flakes that have been sized with olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins, urethane resins, etc. are preferably used. The amount of sizing agent adhered to the sized filler is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight, based on 100% by weight of the filler.

[0108] Furthermore, the fibrous glass fillers and plate-like glass fillers of the present invention include those having a surface coated with a different material. Suitable examples of such different materials include metals and metal oxides. Examples of the metal include silver, copper, nickel, and aluminum. Examples of the metal oxide include cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide. The method of surface coating such different materials is not particularly limited, and examples thereof include various known plating methods (e.g., electroplating, electroless plating, fusion plating, etc.), vacuum evaporation method, ion plating method, CVD method (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD method, and sputtering method.

[0109] The content of component C is 5 to 80 parts by weight, preferably 5 to 75 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the resin component composed of components A and B. If the content of component C is less than 5 parts by weight, the improvement in rigidity is insufficient. On the other hand, if it exceeds 80 parts by weight, the fluidity and thermal stability deteriorate.

[0110] <Component D: Trivalent phosphorus compound> Examples of the trivalent phosphorus compound used in the present invention include phosphite compounds, phosphonite compounds, and tertiary phosphines.

[0111] Examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, and distearyl pentaerythritol diphosphite. pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

[0112] Other phosphite compounds that can be used include those that react with dihydric phenols to form a cyclic structure, such as 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

[0113] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl ... Examples of suitable phosphonite compounds include (2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Among these, tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. Such phosphonite compounds can be used in combination with, and are preferred for, the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups.

[0114] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, diphenylbenzylphosphine, etc. A particularly preferred tertiary phosphine is triphenylphosphine.

[0115] The trivalent phosphorus compound is preferably a phosphite compound, and more preferably bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

[0116] The content of component D is 0.005 to 3.0 parts by weight, preferably 0.01 to 2.0 parts by weight, and more preferably 0.02 to 1.0 parts by weight, based on 100 parts by weight of the resin component composed of components A and B. When the content of component D is less than 0.005 parts by weight, the thermal stability deteriorates, and when it exceeds 3.0 parts by weight, the heat and humidity resistance deteriorates.

[0117] <Component E: Metal phosphate> The metal phosphate used in the present invention includes those produced by a dry method obtained by the direct reaction of a fatty acid with a metal oxide or a fatty acid with a metal hydroxide, and those produced by a wet method in which a sodium salt of a fatty acid and a metal salt are reacted in an aqueous solution. Various combinations of fatty acids with carbon numbers from 1 to 22 can be used, but those with 18 carbon atoms are more preferred. The metal phosphate is most preferably zinc stearyl acid phosphate. When component E is a phosphate compound other than the metal phosphate, the heat and humidity resistance deteriorates.

[0118] The content of component E is 0.035 to 3.0 parts by weight, preferably 0.04 to 2.0 parts by weight, and more preferably 0.05 to 1.0 parts by weight, based on 100 parts by weight of the resin component composed of components A and B. When the content of component E is less than 0.035 parts by weight, the thermal stability deteriorates, and when it exceeds 3.0 parts by weight, the heat and humidity resistance deteriorates.

[0119] <Other components> (I) Hindered phenol antioxidant The hindered phenol-based antioxidant used in the present invention is not particularly limited, and various compounds that are usually compounded in resins can be used. Examples of such hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxyphenyl Dibenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butyl 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate Phthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-Dithiobis(2,6-di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)iso Cyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate Pionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,Examples include 6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. Particularly preferred is 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0120] The above hindered phenol-based antioxidants can be used alone or in combination of two or more. The content of the hindered phenol-based antioxidant is preferably 0.05 to 1.0 part by weight, more preferably 0.07 to 0.8 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of the resin component. If the content is less than 0.05 part by weight, the effect of inhibiting thermal decomposition during processing will not be exerted, and mechanical properties may deteriorate. However, if the content exceeds 1.0 part by weight, mechanical properties may deteriorate.

[0121] (II) Heat stabilizers other than phosphorus-based and hindered phenol-based antioxidants The resin composition of the present invention can contain heat stabilizers other than the phosphorus-based and hindered phenol-based antioxidants. It is preferable to use such heat stabilizers in combination with these antioxidants, and it is particularly preferable to use both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). This compound is commercially available under the trade name Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers containing this compound mixed with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the same company is a suitable example. Such premixed stabilizers can also be used in the present invention. The amount of the lactone stabilizer to be added is preferably 0.0005 to 0.05 parts by weight, and more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of the resin component.

[0122] Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is used for rotational molding. The amount of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of the resin component.

[0123] (III) Mold release agent The resin composition of the present invention may contain a release agent to improve productivity during molding and reduce distortion of molded products, provided that the effects of the present invention are not impaired. Known release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, silicone compounds, fluorine compounds (such as fluorinated oils typified by polyfluoroalkyl ethers), paraffin wax, and beeswax. Fatty acid esters are preferred release agents. Fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol (dihydric or higher). The carbon number of the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred for the fatty acid ester of the present invention. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of such aliphatic carboxylic acids include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, icosanoic acid, and docosanoic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, the aliphatic carboxylic acids are preferably those having 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are more preferred. Stearic acid and palmitic acid are particularly preferred.The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are typically produced from natural oils and fats, such as animal oils and fats (e.g., beef tallow and lard) and vegetable oils and fats (e.g., palm oil and sunflower oil). Therefore, these aliphatic carboxylic acids are typically mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid esters of the present invention, aliphatic carboxylic acids produced from such natural oils and fats and in the form of mixtures containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used. The fatty acid esters may be either partial esters or full esters (full esters). However, partial esters typically have a high hydroxyl value, which can easily induce resin decomposition at high temperatures. Therefore, full esters are more preferred. From the viewpoint of thermal stability, the acid value of the fatty acid esters of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12. The acid value can be substantially zero. The hydroxyl value of the fatty acid esters is more preferably in the range of 0.1 to 30. The iodine value is preferably 10 or less. The iodine value can be substantially zero. These properties can be determined by the method specified in JIS K 0070.

[0124] The content of the release agent is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the resin component.

[0125] (IV) Other resins The resin composition of the present invention may contain other resins in small proportions as long as the effects of the present invention are achieved. Examples of such other resins include polypropylene resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenolic resin, and fluororesin.

[0126] (V) Dyes and pigments The resin composition of the present invention can further contain various dyes and pigments to provide molded articles with a variety of designs. By blending fluorescent brighteners or other fluorescent dyes that emit light, it is possible to impart even better design effects by taking advantage of the emitted color. It is also possible to provide resin compositions that are colored with extremely small amounts of dyes and pigments and have vivid color development.

[0127] Examples of fluorescent dyes (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and are less susceptible to deterioration during molding and processing of polycarbonate resins.

[0128] Examples of dyes other than the bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Suitable metallic pigments include those having a metal coating or a metal oxide coating on various plate-like fillers.

[0129] The content of the dye or pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, relative to 100 parts by weight of the resin component.

[0130] (VI) Flame retardants The resin composition of the present invention can be applied to various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins. Among these, the following are more preferred: (I) halogen-based flame retardants (e.g., brominated polycarbonate compounds), (II) phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate trigomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (III) metal salt-based flame retardants (e.g., alkali (earth) metal organic sulfonates, borate-based flame retardants, and stannate-based flame retardants), and (IV) silicone-based flame retardants consisting of silicone compounds. The incorporation of the compounds used as flame retardants not only improves flame retardancy, but also, depending on the properties of each compound, improves antistatic properties, fluidity, rigidity, and thermal stability, among others.

[0131] The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and even more preferably 0.08 to 25 parts by weight, relative to 100 parts by weight of the resin component. If the content of the flame retardant is less than 0.01 part by weight, sufficient flame retardancy may not be obtained, whereas if it exceeds 30 parts by weight, mechanical properties may be significantly reduced.

[0132] (VII) Highly reflective white pigment The resin composition of the present invention can be blended with a highly light-reflective white pigment to impart a light-reflecting effect. Examples of such white pigments include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. The content of such highly light-reflective white pigment is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, per 100 parts by weight of the resin component. Two or more types of highly light-reflective white pigments can be used in combination.

[0133] (VIII) Carbon black The resin composition of the present invention can be colored by blending it with carbon black. The raw material type and production method of the carbon black are not limited, and any conventionally known carbon black can be used. For example, acetylene black, ketjen black, channel black, oil furnace black, etc. can be used. Furthermore, there are no limitations on the average particle size, structure, or surface properties, and commercially available carbon black can be appropriately selected and used.

[0134] (IX) Other additives In addition, the resin composition of the present invention can contain small amounts of known additives to impart various functions to molded articles or improve their properties. These additives can be added in conventional amounts as long as they do not impair the objectives of the present invention. Examples of such additives include sliding agents (e.g., PTFE particles), light diffusing agents (e.g., acrylic cross-linked particles, silicon cross-linked particles, ultrathin glass flakes, calcium carbonate particles), inorganic phosphors (e.g., phosphors with aluminate as the host crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., titanium dioxide microparticles, zinc oxide microparticles), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

[0135] (Method for preparing resin composition) The resin composition of the present invention is preferably prepared by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. Melt-kneading using a twin-screw extruder is preferred as the mixer, and if necessary, any component is preferably fed into the other melt-mixed components through a second feed port using a side feeder or the like. The extruded resin as described above is either directly cut into pellets or formed into strands, which are then cut into pellets using a pelletizer. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. The resulting pellets can have common shapes such as cylinders, prisms, and spheres, but cylinders are more preferred. The diameter of the cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. The length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0136] (Regarding molded articles made from the resin composition of the present invention) The resin composition of the present invention can be used to produce various products by injection molding the pellets obtained by the above-mentioned method. In such injection molding, molded products can be obtained using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Furthermore, molding can be performed using either a cold runner system or a hot runner system. [Example]

[0137] The present invention will be further explained below with reference to examples. In the examples, parts are by weight and % is by weight unless otherwise specified. Evaluations were carried out by the following methods.

[0138] (1) Raw materials used (Component A) A-1: Polycarbonate resin powder with a molecular weight of 22,400 obtained by the following method: A baffled reaction vessel was equipped with a three-stage, six-blade stirrer and a reflux condenser. 45.6 parts of bisphenol A, 2.78 mol % of p-tert-butylphenol relative to bisphenol A, 265 parts of dichloromethane, and 200 parts of water were placed in the reaction vessel, and a nitrogen purge was performed to remove oxygen from the reaction vessel. At this stage, the contents of the reaction vessel were slightly less than 80% of the vessel's capacity. Next, approximately 80 parts of an aqueous solution for supplying 0.09 parts of sodium hydrosulfite and 21.8 parts of sodium hydroxide were added to the suspension, and bisphenol A was dissolved at 15°C. While stirring, 23.35 parts of phosgene were added to the mixture over 30 minutes. Then, 0.016 parts of triethylamine (0.08 mol % relative to bisphenol A) was added and stirred for 60 minutes to terminate the reaction. The reaction mixture was then allowed to stand, and the organic phase was separated. Methylene chloride was added to the dichloromethane solution of the obtained polycarbonate resin to make a solution with a concentration of 14% by weight, and the solution was further treated using a centrifugal extractor with a perforated plate (KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.) by feeding a 0.5% aqueous sodium hydroxide solution at a flow rate of 1,000 ml / min and an organic phase at a flow rate of 1,000 ml / min at 3,500 rpm.The organic phase was then acidified with hydrochloric acid, and then repeatedly washed with water.When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated to obtain polycarbonate resin powder.

[0139] (B component) B-1: Polyethylene terephthalate resin (Teijin Ltd.: TRN-8550FF (trade name), MVR (280°C, 2.16 kg): 28 cm 3 / 10min) B-2: Polybutylene terephthalate resin (BASF: B4500 (trade name), MVR (280 °C, 2.16 kg): 50 cm 3 / 10min) B-3: Polybutylene terephthalate resin (manufactured by Polyplastics Co., Ltd.: 500FP EF201R (trade name), MVR (280 °C, 2.16 kg): 59 cm 3 / 10min) B-4: Polybutylene terephthalate resin (Polyplastics Co., Ltd.: 300FP EF201R (trade name), MVR (280 °C, 2.16 kg): 198 cm 3 / 10min) B-5: Polybutylene terephthalate resin (Polyplastics Co., Ltd.: 700FP EF201R (trade name), MVR (280°C, 2.16 kg): 22 cm 3 / 10min) B-6: Polybutylene terephthalate resin (manufactured by Changchun Plastics Co., Ltd.: 1100-211MD (trade name), MVR (280°C, 2.16 kg): 61 cm 3 / 10min)

[0140] (C component) C-1: Circular cross-section chopped glass fiber (Nitto Boseki Co., Ltd.: CSG 3PE-944) C-2: Circular cross-section chopped glass fiber (Nitto Boseki Co., Ltd.: CSG 3PE-455) C-3: Glass flakes (Nippon Sheet Glass Co., Ltd.: MEG160FY-M02)

[0141] (D component) D-1: Phosphite ester (bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite) (6260PW (trade name) manufactured by SONGWON) D-2: Phosphite ester (3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane) (PEP-36 (trade name) manufactured by ADEKA Corporation)

[0142] (E component) E-1: Stearyl acid phosphate zinc salt (JP-518Zn (trade name) manufactured by Johoku Chemical Industry Co., Ltd.) E-2 (Comparative Example): Approximately equimolar mixture of mono- and di-stearyl acid phosphate (AX-71 (trade name) manufactured by ADEKA Corporation) E-3 (Comparative Example): Triethyl phosphonoacetate (JC-224 (trade name) manufactured by Johoku Chemical Industry Co., Ltd.)

[0143] (Other ingredients) F-1: Release agent (fatty acid ester, NOF Corporation, Unistar H-476-S (product name)) G-1: Carbon black (ROYAL BLACK 90003S (product name) manufactured by Koshigaya Chemical Industry Co., Ltd.)

[0144] (2) Production of resin composition The components listed in Tables 1 and 2 were mixed in the proportions listed, and the mixture was fed into the first feed port of the extruder. This mixture was obtained by mixing in a V-blender. The extrusion was performed using a 30 mm diameter vented twin-screw extruder (TEX30A-38.5BW-3V, manufactured by The Japan Steel Works, Ltd.) at a screw rotation speed of 200 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa to obtain melt-kneaded pellets. The extrusion temperature from the first feed port to the die was 270°C.

[0145] (3) Method for preparing test specimens for evaluation The resulting pellets were dried in a hot air circulation dryer at 120°C for 6 hours, and then molded into ISO flexural test specimens using an injection molding machine (Toshiba Machine Co., Ltd., EC130XII-4Y) at a cylinder temperature of 320°C and a mold temperature of 70°C. The resin pellets were then molten and retained in the cylinder of the injection molding machine under the same conditions for 10 minutes, after which a 3mm-thick plate-shaped test specimen was molded. This was the retention molded product.

[0146] (4) Evaluation items The following items were evaluated, and the results are shown in Tables 1 and 2. (4-1) Liquidity The obtained pellets were dried in a hot air circulation dryer at 120°C for 6 hours, and then the melt volume rate (MVR) was measured using a semi-automatic melt indexer (Semi-automatic melt indexer 2A manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a temperature of 280°C and a load of 2160 g.

[0147] (4-2) Rigidity The flexural modulus (MPa) was measured using an ISO flexural test piece according to ISO 178.

[0148] (4-3) Moisture and heat resistance The resulting pellets were subjected to moist heat treatment for 48 hours at 110°C and 100% RH in a pressure cooker tester TPC-412 (manufactured by ESPEC Corporation). After the moist heat treatment, the pellets were dried in a hot air circulation dryer at 120°C for 6 hours, after which the MVR was measured in the same manner as in "(3-1) Fluidity" and the MVR increase rate was calculated using the following formula. A smaller MVR increase rate indicates better moist heat resistance. MVR increase rate (%) = [MVR of pellets after moist heat treatment / MVR of pellets before moist heat treatment] × 100

[0149] (4-4) Thermal stability The viscosity-average molecular weight of the polycarbonate resin in the pellets and the viscosity-average molecular weight of the polycarbonate resin in the retention molded product were measured according to the methods described in the specification. The polycarbonate resin in the pellets and retention molded product was extracted using the following method. First, the pellets and retention molded product were mixed with 20 to 30 times their weight of methylene chloride to dissolve the soluble components in the pellets and retention molded product. The soluble components were collected by filtration through Celite. The solvent in the resulting solution was then removed. Finally, the solid after solvent removal was thoroughly dried to obtain a solid containing components soluble in methylene chloride. The molecular weight retention was calculated from these viscosity-average molecular weights using the following formula. A higher molecular weight retention indicates better thermal stability. Molecular weight retention rate (%) = [viscosity average molecular weight of polycarbonate resin in retention molded product / viscosity average molecular weight of polycarbonate resin in pellets] x 100

[0150]

Table 1

[0151]

Table 2

Claims

1. A polycarbonate resin composition comprising 100 parts by weight of a resin component consisting of 50 to 95 parts by weight of (A) a polycarbonate resin (component A) and 5 to 50 parts by weight of (B) a polyester resin (component B), and containing 5 to 80 parts by weight of (C) an inorganic filler (component C), 0.005 to 3.0 parts by weight of (D) a trivalent phosphorus compound (component D), and 0.035 to 3.0 parts by weight of (E) a phosphate metal salt (component E).

2. 2. The resin composition according to claim 1, wherein component B is at least one polyester resin selected from the group consisting of polyethylene terephthalate resins and polybutylene terephthalate resins.

3. 3. The resin composition according to claim 1, wherein component C is glass fiber.

4. 3. The resin composition according to claim 1, wherein component E is a zinc salt of stearyl acid phosphate.

5. A molded article made from the resin composition according to claim 1 or 2.

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