Thermoplastic resin composition and molded article

Abstract

To provide a thermoplastic resin composition that employs an organic acid metal salt compound containing no fluorine, and that exhibits enhanced flame retardancy as well as superior heat resistance and impact resistance.SOLUTION: A thermoplastic resin composition comprises a polycarbonate resin (P) that includes a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a specific repeating unit (B), and a flame retardant (C) which is an organic acid metal salt compound containing no fluorine. (In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, wherein the alkyl groups of R1 and R2 may form a ring; and R3 and R4 each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition, more particularly to a thermoplastic resin composition having extremely high flame retardancy and excellent heat resistance and impact resistance, and to injection-molded and extrusion-molded articles of the thermoplastic resin composition. [Background technology]

[0002] Thermoplastic resins, such as polycarbonate resins, are resins with excellent mechanical strength, heat resistance, transparency, etc., and are widely used in various parts of electrical, electronic, and office equipment, automobile parts, building materials, medical applications, miscellaneous goods, and other fields.

[0003] Conventionally, polycarbonate resin compositions having high flame retardancy have been used not only with polycarbonates composed of bisphenol A, but also with polycarbonates having bisphenol C in the skeleton, which has even better flame retardancy. Furthermore, fluorine-containing organic sulfonic acid metal salt compounds are frequently used as flame retardants to impart flame retardancy to polycarbonate resin compositions.

[0004] Patent Document 1 shows that adding potassium perfluorobutanesulfonate as a flame retardant to a composition of polycarbonate resin made from bisphenol A and polycarbonate resin made from bisphenol C results in flame retardancy of V-0 as evaluated in a UL94 standard vertical flame test using a 0.8 mm test piece.

[0005] Patent Document 2 discloses that a molded sample of a flame-retardant composition consisting of a polycarbonate resin and a fluorine-free metal salt of aromatic sulfonic acid can achieve a UL94 V0 rating with a thickness of 3.0 mm.

[0006] Patent Document 3 shows that polycarbonate resin, a copolymer of tetramethylbisphenol F and bisphenol C, achieves flame retardancy of V-0 when evaluated in the UL94 standard vertical flame test using a 0.8 mm test piece using only the resin. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 6606083 [Patent Document 2] Special Publication No. 4009-526899 [Patent Document 3] International Publication No. 2021 / 039970 Summary of the Invention [Problem to be solved by the invention]

[0008] In recent years, molded articles have become thinner, smaller, and lighter in weight, and there is a demand for molded articles with even higher flame retardancy. There is also a demand for compositions that exhibit flame retardancy superior to that of the conventional polycarbonate resin compositions proposed in Patent Documents 1 to 3.

[0009] Furthermore, the fluorine-containing organic sulfonic acid metal salt used as a flame retardant in Patent Document 1 is a type of fluorine-containing organic compound (PFAS), which has been subject to stricter regulations in recent years due to concerns about its impact on the environment and human body. Therefore, it is expected that the development of polycarbonate resin compositions that have high flame retardancy without using fluorine-containing metal salts will become increasingly important in the future, and there is a demand for polycarbonate resin compositions that use fluorine-free organic acid metal salt compounds as flame retardants and have flame retardancy equal to or higher than that of compositions that use fluorine-containing organic acid metal salt compounds.

[0010] Under these circumstances, an object of the present invention is to provide a thermoplastic resin composition which uses a metal salt flame retardant and has higher flame retardancy, as well as excellent heat resistance and impact resistance. A further object of the present invention is to provide a thermoplastic resin composition which uses a fluorine-free organic acid metal salt compound and which has higher flame retardancy, as well as excellent heat resistance and impact resistance. [Means for solving the problem]

[0011] As a result of extensive research aimed at solving the above problems, the present inventors have found that a thermoplastic resin composition containing a polycarbonate resin having a specific structure and a specific flame retardant satisfies the above object, and have arrived at the present invention.

[0012] That is, the gist of the present invention is as follows.

[0013] [1] A thermoplastic resin composition comprising a polycarbonate resin (P) containing a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2), and a flame retardant (C), wherein the flame retardant (C) is a fluorine-free organic acid metal salt compound:

[0014] [ka]

[0015] (In general formula (1), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0016] [ka]

[0017] (In general formula (2), R 5 ~R 8 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0018] [2] The thermoplastic resin composition according to [1], wherein the content ratio of the repeating unit (A) to the repeating unit (B) in the polycarbonate resin (P) is, in molar ratio, repeating unit (A): repeating unit (B) = 30:70 to 10:90.

[0019] [3] The thermoplastic resin composition according to [1] or [2], wherein the polycarbonate resin (P1) contains a polycarbonate copolymer (P1A) in which the content ratio of the repeating unit (A) to the repeating unit (B) is, in molar ratio, repeating unit (A): repeating unit (B) = 50:50 to 10:90.

[0020] [4] The thermoplastic resin composition according to [3], wherein the polycarbonate resin (P1) contains 20 to 100 mass % of the polycarbonate copolymer (PA1).

[0021] [5] The thermoplastic resin composition according to any one of [1] to [4], comprising 5 parts by mass or more of a polycarbonate resin (P2) containing 95% by mass or more of a repeating unit (E) represented by the following general formula (3) relative to 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition:

[0022] [ka]

[0023] (In general formula (3), R 10 and R 11 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 10 and R 11 The alkyl groups in R may be bonded to each other to form a ring. 12 and R13 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0024] [6] The thermoplastic resin composition according to [5], comprising 70 parts by mass or less of the polycarbonate resin (P2) per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

[0025] [7] R in the general formula (1) 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0026] [8] The thermoplastic resin composition according to any one of [1] to [7], wherein the flame retardant (C) contains a benzene ring.

[0027] [9] The thermoplastic resin composition according to [8], wherein the flame retardant (C) is an aromatic sulfonic acid metal salt compound.

[0028]

[10] The thermoplastic resin composition according to [9], wherein the flame retardant (C) is potassium 3-(phenylsulfonyl)benzenesulfonate or sodium paratoluenesulfonate.

[0029]

[11] The thermoplastic resin composition according to any one of [1] to

[10] , wherein the content of the flame retardant (C) is 0.005 parts by mass or more per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

[0030]

[12] The thermoplastic resin composition according to any one of [1] to

[11] , wherein the content of the flame retardant (C) is 0.5 parts by mass or less per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

[0031]

[13] The thermoplastic resin composition according to any one of [1] to

[12] , wherein the thermoplastic resin composition contains at least one additive (D) other than the flame retardant (C).

[0032]

[14] In the general formula (1), R 1 and R 2 is a methyl group, or R 1 and R 2 The thermoplastic resin composition according to any one of [1] to

[13] , wherein the alkyl groups are bonded to each other to form a ring represented by the following formula (1a) or (1b):

[0033] [ka]

[0034]

[15] In the general formula (1), R 3 and R 4 The thermoplastic resin composition according to any one of [1] to

[14] , wherein is a methyl group.

[0035]

[16] The thermoplastic resin composition according to any one of [1] to

[15] , wherein the repeating unit (B) is a repeating unit represented by the following general formula (2A):

[0036] [ka]

[0037] (In general formula (2A), R 5 ~R 8 has the same meaning as in the general formula (2).

[0038]

[17] In the general formula (2), R 5 ~R 8 The thermoplastic resin composition according to any one of [1] to

[16] , wherein is a methyl group.

[0039]

[18] In the general formula (3), R 10 and R 11is a methyl group, and R 12 and R 13 The thermoplastic resin composition according to any one of [5] to

[17] , wherein is a hydrogen atom.

[0040]

[19] The thermoplastic resin composition according to any one of [1] to

[18] , wherein the viscosity average molecular weight (Mv) of the polycarbonate resin (P1) is in the range of 14,500 to 30,000.

[0041]

[20] The thermoplastic resin composition according to any one of [1] to

[19] , wherein the polycarbonate resin (P1) has a glass transition temperature of 125°C or higher.

[0042]

[21] The thermoplastic resin composition according to any one of [1] to

[20] , wherein a test piece having a thickness of 1.0 mm made from the thermoplastic resin composition is evaluated as V-0 or V-1 in a UL94 vertical flame test.

[0043]

[22] The thermoplastic resin composition according to

[21] , which is rated V-0 or V-1 in a UL94 vertical flame test using a 0.6 mm thick test piece made from the thermoplastic resin composition.

[0044]

[23] A thermoplastic resin composition comprising a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2), and a metal salt flame retardant (C1), wherein a test piece having a thickness of 1.0 mm, prepared using the thermoplastic resin composition, is evaluated as V-0 or V-1 in a UL94 vertical flame test.

[0045] [ka]

[0046] (In general formula (1), R 1 and R 2R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0047] [ka]

[0048] (In general formula (2), R 5 ~R 8 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0049]

[24] R in the general formula (1) 3 and R 4 and each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0050]

[25] The thermoplastic resin composition according to

[23] or

[24] , wherein a 0.6 mm thick test piece made from the thermoplastic resin composition is evaluated as V-0 or V-1 in a UL94 vertical flame test.

[0051]

[26] An injection-molded article obtained by injection molding the thermoplastic resin composition according to any one of [1] to

[25] .

[0052]

[27] An extrusion molded product obtained by extrusion molding the thermoplastic resin composition according to any one of [1] to

[25] .

[0053]

[28] The extrusion molded product according to

[27] , wherein the extrusion molded product is a sheet or a film. [Effects of the Invention]

[0054] According to the present invention, a metal salt flame retardant, preferably a fluorine-free organic acid metal salt compound, is used as a flame retardant, to provide a thermoplastic resin composition having excellent flame retardancy, heat resistance, and impact resistance. Because the thermoplastic resin composition of the present invention has such excellent properties, it can be widely used as a material for manufacturing parts in the fields of automobiles, electrical and electronic materials, and other industries. DETAILED DESCRIPTION OF THE INVENTION

[0055] The present invention will be described in detail below with reference to embodiments and examples, but the present invention should not be construed as being limited to the embodiments and examples shown below.

[0056] In this specification, unless otherwise specified, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0057] [Thermoplastic resin composition] A thermoplastic resin composition according to one embodiment of the present invention (hereinafter, sometimes referred to as "thermoplastic resin composition I of the present invention") is a thermoplastic resin composition comprising: a polycarbonate resin (P) containing a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2); and a flame retardant (C), wherein the flame retardant (C) is a fluorine-free organic acid metal salt compound. A thermoplastic resin composition according to another embodiment of the present invention (hereinafter, sometimes referred to as "thermoplastic resin composition II of the present invention") is a thermoplastic resin composition comprising a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2), and a metal salt flame retardant (C1), and the thermoplastic resin composition is rated V-0 or V-1 in a UL94 standard vertical flame test using a 1.0 mm thick test piece prepared using the thermoplastic resin composition.

[0058] [ka]

[0059] (In general formula (1), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0060] [ka]

[0061] (In general formula (2), R 5 ~R 8 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0062] Hereinafter, the thermoplastic resin composition I of the present invention and the thermoplastic resin composition II of the present invention will be collectively referred to as the "thermoplastic resin composition of the present invention."

[0063] [Molar ratio of repeating unit (A) to repeating unit (B) in polycarbonate resin (P)] In the thermoplastic resin composition of the present invention, the content ratio of repeating units (A) to repeating units (B) in the polycarbonate resin (P) is not particularly limited, but the repeating unit (A): repeating unit (B) (molar ratio) is preferably 30:70 to 10:90, particularly 25:75 to 12:88, and especially 20:80 to 15:85. If it is within this range, the flame retardancy of the thermoplastic resin composition of the present invention is high, and therefore it is preferred.

[0064] [Polycarbonate resin (P1)] The polycarbonate resin (P1) contained in the thermoplastic resin composition of the present invention has a repeating unit (A) represented by the general formula (1) above and a repeating unit (B) represented by the general formula (2) above.

[0065] In addition, R in the general formula (1) representing the repeating unit (A) shown below 1 and R 2 a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, R 1 and R 2 The ring formed by bonding the alkyl groups of R 3 and R 4 a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, R in general formula (2) representing the repeating unit (B), 5 ~R 8 Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and the substituted or unsubstituted aryl group include those exemplified as the substituents in the general formula (3) representing the polycarbonate resin (P2) described below, but are preferably as follows:

[0066] <Repeating unit (A)> The repeating unit (A) is represented by the following general formula (1).

[0067] [ka]

[0068] (In general formula (1), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0069] In general formula (1), R 1 and R 2 From the viewpoint of improving heat resistance, R is a methyl group or 1 and R 2 It is preferable that the alkyl groups R are bonded to each other to form a ring represented by the following formula (1a) or (1b). 1 and R 2 is particularly preferably a methyl group.

[0070] [ka]

[0071] In general formula (1), R 3 and R 4 From the viewpoint of improving flame retardancy, is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0072] That is, the repeating unit (A) is preferably a repeating structural unit derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A) (hereinafter sometimes abbreviated as "BPA") and / or 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes abbreviated as "BPC"), and is particularly preferably a repeating unit derived from BPC represented by the following formula (4).

[0073] [ka]

[0074] The polycarbonate resin (P1) may contain only one type of repeating unit (A), or may contain two or more types.

[0075] <Repeating unit (B)> The repeating unit (B) is represented by the following general formula (2).

[0076] [ka]

[0077] (In general formula (2), R 5 ~R 8 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0078] In the general formula (2), R 5 ~R 8 There are no restrictions on the substitution position, but from the viewpoint of improving impact resistance, the substitution position of the following general formula (2A) is particularly preferred.

[0079] [ka]

[0080] (In general formula (2A), R 5 ~R 8 has the same meaning as in the general formula (2).

[0081] The repeating unit (B) is particularly preferably a repeating unit derived from 4,4-methylenebis(2,6-dimethylphenol) (hereinafter sometimes abbreviated as "TmBPF") and represented by the following general formula (5):

[0082] [ka]

[0083] The polycarbonate resin (P1) may contain only one type of repeating unit (B), or may contain two or more types.

[0084] <Other repeating units> The polycarbonate resin (P1) may contain one or more repeating units other than the repeating units (A) and (B) within the scope of the present invention. Examples of the other repeating units include repeating units derived from aromatic dihydroxy compounds such as 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane.

[0085] In order to reliably obtain the effects of the present invention due to the inclusion of the repeating unit (A) and the repeating unit (B), the sum of the repeating units (A) and (B) is preferably 50 mol % or more, more preferably 60 mol % or more, and even more preferably 70 mol % or more, of all carbonate structural units in the polycarbonate resin (P1) being 100 mol %, and this proportion may be 100 mol %.

[0086] <Preferred embodiment of polycarbonate resin (P1)> The polycarbonate resin (P1) is preferably a polycarbonate copolymer (P1A) in which the content ratio of the repeating unit (A) to the repeating unit (B) is, in molar ratio, repeating unit (A): repeating unit (B) = 50:50 to 10:90, and the polycarbonate resin (P1) preferably contains 20 to 100 mass % of this polycarbonate copolymer (P1A).

[0087] <Molecular weight of polycarbonate resin (P1)> Although there are no particular restrictions on the molecular weight of the polycarbonate resin (P1), it is preferable that the viscosity average molecular weight (Mv) calculated from the solution viscosity is 14,500 or more. A viscosity average molecular weight equal to or greater than the above lower limit is preferable because the heat resistance and flame retardancy of the thermoplastic resin composition and molded article of the present invention are improved. From this viewpoint, the viscosity average molecular weight of the polycarbonate resin (P1) is more preferably 16,000 or more, even more preferably 17,000 or more, particularly preferably 18,000 or more, and most preferably 18,500 or more.

[0088] On the other hand, the viscosity average molecular weight (Mv) of the polycarbonate resin (P1) is preferably 30,000 or less. When the viscosity average molecular weight is equal to or less than the above upper limit, the thermoplastic resin composition of the present invention containing the polycarbonate resin (P1) tends to have good fluidity, which is preferable. From this viewpoint, the viscosity average molecular weight of the polycarbonate resin (P1) is more preferably 29,000 or less, even more preferably 28,000 or less, particularly preferably 27,000 or less, and most preferably 26,500 or less.

[0089] The viscosity average molecular weight (Mv) of the polycarbonate resin (P1) was determined by using methylene chloride as a solvent and an Ubbelohde viscometer to determine the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at a temperature of 20°C, and then using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 This means the value calculated from The intrinsic viscosity (limiting viscosity) [η] is a value calculated by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dL) and using the following formula:

[0090]

number

[0091] The same applies to the viscosity average molecular weight (Mv) of the polycarbonate resin (P2) and the thermoplastic resin composition of the present invention, which will be described later.

[0092] <Glass transition temperature (Tg) of polycarbonate resin (P1)> The glass transition temperature (Tg) of the polycarbonate resin (P1) is not limited, but is preferably 125 to 200°C. If the Tg is 125°C or higher, the heat resistance of the thermoplastic resin composition of the present invention and the molded article is improved. On the other hand, if the Tg of the polycarbonate resin (P1) is 200°C or lower, the thermoplastic resin composition of the present invention containing the polycarbonate resin (P1) has good fluidity and can achieve high moldability. For this reason, the glass transition temperature (Tg) of the polycarbonate resin (P1) is preferably 125 to 200°C.

[0093] The Tg of the polycarbonate resin (P1), the polycarbonate resin (P2) described below, and the thermoplastic resin composition of the present invention is measured by the method described in the Examples section below.

[0094] <Production method of polycarbonate resin (P1)> The polycarbonate resin (P1) can be produced by a conventionally known polymerization method, and the polymerization method is not particularly limited. Examples of the polymerization method include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, and solid-phase transesterification of a prepolymer. Particularly preferred methods among these methods will be specifically described below.

[0095] (interfacial polymerization method) In the interfacial polymerization method, a dihydroxy compound as a raw material and a carbonate-forming compound are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher, and then interfacial polymerization is carried out in the presence of a polymerization catalyst to obtain a polycarbonate resin. If necessary, a molecular weight modifier (end terminator) may be present in the reaction system, and an antioxidant may also be present to prevent oxidation of the dihydroxy compound as a raw material.

[0096] The organic solvent inert to the reaction is not particularly limited, but examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; and the like. The organic solvent may be used alone or in any combination of two or more kinds in any ratio.

[0097] The alkaline compound contained in the alkaline aqueous solution is not particularly limited, but examples thereof include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate. Of these, sodium hydroxide and potassium hydroxide are preferred. The alkaline compounds may be used alone or in any combination of two or more in any ratio.

[0098] Although there are no limitations on the concentration of the alkali compound in the alkaline aqueous solution, the alkali compound concentration is usually 5 to 10 mass % to control the pH of the alkaline aqueous solution to 10 to 12. Furthermore, when blowing in phosgene, for example, in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11, it is preferable that the molar ratio of the starting dihydroxy compound to the alkali compound is usually 1:1.9 or more, preferably 1:2.0 or more, and usually 1:3.2 or less, preferably 1:2.5 or less.

[0099] As the starting dihydroxy compound, at least a dihydroxy compound capable of producing the repeating unit (A) and the repeating unit (B) upon reaction with a carbonate-forming compound is used.

[0100] As the carbonate-forming compound, a carbonyl halide is preferably used. Among them, phosgene is preferably used. The method using phosgene is particularly called the phosgene method.

[0101] The polymerization catalyst is not particularly limited, but examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; guanine; and salts of guanidine. The polymerization catalyst may be used alone or in any combination of two or more in any ratio.

[0102] The molecular weight modifier is not particularly limited, but examples thereof include aromatic phenols having a monovalent phenolic hydroxyl group, aliphatic alcohols such as methanol and butanol, mercaptans, phthalimide, etc. Among these, aromatic phenols are preferred.

[0103] Specific examples of such aromatic phenols include phenol, on-butylphenol, m-n-butylphenol, p-n-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, mn-nonylphenol, and pn-nonylphenol. phenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, monoalkylphenols having a linear or branched alkyl group having an average of 12 to 35 carbon atoms at the ortho, meta, or para position, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, 4-(1-adamantyl)phenol, and the like. Of these, pt-butylphenol, p-phenylphenol and p-cumylphenol are preferably used. The molecular weight modifier may be used alone or in any combination of two or more kinds in any ratio.

[0104] The amount of molecular weight modifier used is not particularly limited, but is, for example, usually 0.5 moles or more, preferably 1 mole or more, and usually 50 moles or less, preferably 30 moles or less, per 100 moles of the raw material dihydroxy compound.

[0105] The antioxidant is not particularly limited, but examples thereof include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6- triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0106] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Commercially available phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by BASF, and "Adekastab AO-50" and "Adekastab AO-60" manufactured by ADEKA.

[0107] The antioxidants may be used alone or in any combination of two or more in any ratio.

[0108] The amount of antioxidant used is not particularly limited, but is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the starting dihydroxy compound. By using an amount of antioxidant that is equal to or greater than the above-mentioned lower limit, the antioxidant's effect is sufficient. The amount of antioxidant used is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the starting dihydroxy compound. By using an amount of antioxidant that is equal to or less than the above-mentioned upper limit, gas generation during injection molding can be suppressed.

[0109] During the reaction, the order in which the reaction substrates (reaction raw materials), reaction solvent (organic solvent), catalyst, additives, etc. are mixed is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate-forming compound, the molecular weight modifier can be mixed at any time between the reaction of the raw material dihydroxy compound with phosgene (phosgenation) and the start of the polymerization reaction.

[0110] The reaction temperature is not particularly limited, but is preferably 0 to 40° C. The reaction time is not particularly limited, but is preferably several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

[0111] (melt transesterification method) In the melt transesterification method, for example, a transesterification reaction is carried out between a carbonate ester and a raw material dihydroxy compound. The starting dihydroxy compound is the same as that used in the interfacial polymerization method.

[0112] The carbonate ester may be, for example, a compound represented by the following general formula (I), and examples thereof include aryl carbonates, dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0113] [ka]

[0114] In the above general formula (I), R 101 and R 102 Each of R independently represents an alkyl group, an aryl group, or an arylalkyl group having 1 to 30 carbon atoms. 101 and R 102 When the alkyl group is an alkyl or arylalkyl group, it is called a dialkyl carbonate, and when the aryl group is an aryl carbonate, it is called a diaryl carbonate. 101 and R 102 and are preferably both aryl groups, and are more preferably diaryl carbonates represented by the following general formula (II).

[0115] [ka]

[0116] In the above general formula (II), R 103 and R 104 are each independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. p and q are each independently an integer of 0 to 5.

[0117] Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), bis(4-methylphenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-fluorophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(2,4-difluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, bis(2-nitrophenyl)carbonate, bis(methylsalicylphenyl)carbonate, and diaryl carbonates (which may have a substituent) such as ditolyl carbonate. Among these, diphenyl carbonate is preferred. These carbonate esters can be used alone or in combination of two or more.

[0118] The carbonate ester may be substituted with a dicarboxylic acid or a dicarboxylic acid ester, preferably in an amount of 50 mol % or less, more preferably 30 mol % or less. Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

[0119] The ratio of the starting dihydroxy compound to the carbonate ester may be any ratio as long as the desired polycarbonate resin is obtained, but it is preferred that the carbonate ester be used in excess of the starting dihydroxy compound when polymerizing with the dihydroxy compound. The amount of carbonate ester relative to the amount of dihydroxy compound is preferably 1.01 times (molar ratio) or more, more preferably 1.02 times or more. By setting the molar ratio to be equal to or more than the above lower limit, the thermal stability of the obtained polycarbonate resin is improved. The amount of carbonate ester relative to the amount of dihydroxy compound is preferably 1.30 times (molar ratio) or less, more preferably 1.20 times or less. By setting the molar ratio to the above upper limit or less, the reactivity is improved, the productivity of polycarbonate resin having a desired molecular weight is improved, and the amount of carbonate ester remaining in the resin is reduced, which is advantageous in that odor generation can be suppressed during molding processing or when a molded product is formed.

[0120] When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may also be used in combination as an auxiliary. The transesterification catalyst may be used alone or in any combination of two or more in any ratio.

[0121] In the melt transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 320°C. The pressure during the reaction is not particularly limited, but is usually reduced to 2 mmHg or less. Specifically, the melt polycondensation reaction may be carried out under the above conditions while removing by-products.

[0122] In the presence of an alkaline catalyst, polycarbonate resin (P1) and polycarbonate resin (P2) described below are significantly affected by thermal history and oxidation, leading to deterioration of color. Therefore, it is preferable to set the reaction temperature at 320°C or lower and to select reduced pressure conditions with a lower limit of about 0.05 mmHg to prevent oxygen leakage from the equipment due to excessive reduced pressure.

[0123] The reaction can be carried out in either a batch or continuous manner. In the batchwise manner, the order of mixing the reaction substrates, reaction solvent, catalyst, additives, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set.

[0124] In the melt transesterification method, a catalyst deactivator may be used as needed. As the catalyst deactivator, any compound that neutralizes the transesterification catalyst can be used. Examples of such a catalyst deactivator include sulfur-containing acidic compounds and their derivatives, and phosphorus-containing acidic compounds and their derivatives. The catalyst deactivator may be used alone or in any combination of two or more in any ratio.

[0125] The amount of the catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, relative to the transesterification catalyst, and usually 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less. The amount of the catalyst deactivator used is usually 1 ppm or more and 100 ppm or less, preferably 50 ppm or less, relative to the polycarbonate resin.

[0126] <Polycarbonate resin (P1) content> The content of the polycarbonate resin (P1) in the thermoplastic resin composition of the present invention is preferably 60 parts by mass or more per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition of the present invention in order to reliably obtain the effects of improving flame retardancy, heat resistance, and impact resistance due to the inclusion of the polycarbonate resin (P1). From this perspective, the content of the polycarbonate resin (P1) is more preferably 60 parts by mass or more, and the thermoplastic resin composition of the present invention may be one containing only the polycarbonate resin (P1) as the thermoplastic resin (content of polycarbonate resin (P1) 100 parts by mass). The thermoplastic resin composition of the present invention may contain only one type of polycarbonate resin (P1), or may contain two or more types of repeating units (A) and (B) that differ in type or composition.

[0127] In the present invention, the thermoplastic resin in the thermoplastic resin composition of the present invention is the total of the polycarbonate resin (P1), the polycarbonate resin (P2) described below that is contained as needed, and other thermoplastic resins.

[0128] [Flame retardant (C)] The thermoplastic resin composition II of the present invention contains a metal salt flame retardant (C1) as the flame retardant (C). The metal salt flame retardant (C1) contained in the thermoplastic resin composition II of the present invention is not particularly limited, but for the reasons mentioned above, a fluorine-free metal salt flame retardant is preferred. Examples of the fluorine-free metal salt flame retardant include the following, which are exemplified as the fluorine-free organic acid metal salt compounds contained as the flame retardant (C) in the thermoplastic resin composition I of the present invention.

[0129] The fluorine-free organic acid metal salt compound contained as the flame retardant (C) in the thermoplastic resin composition I of the present invention is preferably an organic sulfonic acid metal salt flame retardant, and among these, a flame retardant containing a benzene ring, particularly an aromatic sulfonic acid metal salt compound, is preferred.

[0130] The metal of the metal salt of the aromatic sulfonic acid metal salt compound is preferably an alkali metal such as sodium, lithium, potassium, rubidium, or cesium, or an alkaline earth metal such as beryllium, magnesium, calcium, strontium, or barium, etc. Among these, potassium is preferred from the viewpoints of flame retardancy and hydrolysis resistance.

[0131] Specific examples of the aromatic sulfonate metal salt compound include sodium 3-(phenylsulfonyl)benzenesulfonate, potassium 3-(phenylsulfonyl)benzenesulfonate, disodium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, sodium paratoluenesulfonate, potassium paratoluenesulfonate, sodium benzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, sodium (poly)styrenesulfonate, potassium (poly)styrenesulfonate, sodium (branched)dodecylbenzenesulfonate, and potassium (branched)dodecylbenzenesulfonate.

[0132] Among these, potassium 3-(phenylsulfonyl)benzenesulfonate and sodium paratoluenesulfonate are preferred, particularly from the viewpoint of flame retardancy. The flame retardants (C) such as organic sulfonic acid metal salt flame retardants may be used alone or in combination of two or more.

[0133] In the thermoplastic resin composition of the present invention, the content of the flame retardant (C) is preferably 0.005 parts by mass or more relative to 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition of the present invention. When the content of the flame retardant (C) is equal to or greater than the above-mentioned lower limit, high flame retardancy can be obtained by containing the flame retardant (C). On the other hand, the content of the flame retardant (C) is preferably equal to or less than 0.5 parts by mass relative to 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition of the present invention. When the content of the flame retardant (C) is equal to or less than the above-mentioned upper limit, other physical properties such as heat resistance and impact resistance are not impaired by excessive incorporation of the flame retardant (C). From this viewpoint, the content of the flame retardant (C) in the thermoplastic resin composition of the present invention is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.02 parts by mass or more, and most preferably 0.03 parts by mass or more, per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition. Also, the content of the flame retardant (C) in the thermoplastic resin composition of the present invention is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, even more preferably 0.2 parts by mass or less, particularly preferably 0.1 parts by mass or less, and most preferably 0.06 parts by mass or less, per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

[0134] [Polycarbonate resin (P2)] The thermoplastic resin composition of the present invention may contain, in addition to the polycarbonate resin (P1), a polycarbonate resin (P2) containing a repeating unit (E) represented by the following general formula (3). By containing the polycarbonate resin (P2), the effects of improving impact resistance and fluidity can be obtained.

[0135] [ka]

[0136] (In general formula (3), R 10 and R 11 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 10 and R 11 The alkyl groups in R may be bonded to each other to form a ring. 12 and R 13 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0137] R in general formula (3) 10 and R 11 , and R12 and R 13 Specific examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include the following. Methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl; Methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group, methylnonadecyl group; Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group, dimethyloctadecyl group; Trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; Ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group; Butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group, etc.

[0138] R is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in the general formula (3). 10 and R 11 may be bonded to each other to form a ring, and specific examples of the ring formed include a cyclohexane ring and a cyclododecane ring.

[0139] R 10 and R 11 , and R 12 and R 13 Specific examples of the substituted or unsubstituted aryl group include a phenyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.

[0140] R 10 and R 11 Among these, a hydrogen atom, a methyl group, or an ethyl group is preferable, a hydrogen atom or a methyl group is more preferable, and R 10 and R 11 Preferably, both of these are methyl groups.

[0141] R 12 and R 13Preferred examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, a phenyl group, and a tolyl group. Among these, a hydrogen atom and a methyl group are preferred, and it is most preferred that both groups be hydrogen atoms.

[0142] The polycarbonate resin (P2) may contain a repeating unit other than the repeating unit (E) represented by the general formula (3). However, in order to obtain the effects of containing the repeating unit (E), such as improved impact resistance and improved fluidity, the polycarbonate resin (P2) preferably contains 50 mol % or more of the repeating unit (E) of all carbonate structural units contained in the polycarbonate resin (P2), more preferably 60 mol % or more, and even more preferably 70 to 100 mol %.

[0143] Examples of repeating units contained in the polycarbonate resin (P2) other than the repeating unit (E) include those exemplified as other repeating units that may be contained in the polycarbonate resin (P1) described above that are not included in the repeating unit (E), or either the repeating unit (A) or the repeating unit (B). The polycarbonate resin (P2) may be a bisphenol A polycarbonate resin (A-PC) (in the general formula (3), R 10 and R 11 is a methyl group, and R 12 and R 13 is a hydrogen atom) is preferred from the viewpoint of the impact resistance and flame retardancy of the thermoplastic resin composition.

[0144] <Molecular weight of polycarbonate resin (P2)> For the same reasons as in the polycarbonate resin (P1), the molecular weight of the polycarbonate resin (P2) is preferably 14,500 to 30,000, more preferably 16,000 to 29,000, even more preferably 17,000 to 28,000, particularly preferably 18,000 to 27,000, and most preferably 18,500 to 26,500, in terms of viscosity average molecular weight (Mv) calculated from the solution viscosity.

[0145] <Glass transition temperature of polycarbonate resin (P2)> The glass transition temperature Tg of the polycarbonate resin (P2) is preferably 110 to 200°C for the same reasons as in the polycarbonate resin (P1).

[0146] <Manufacturing method of polycarbonate resin (P2)> The polycarbonate resin (P2) can be produced in the same manner as in the polycarbonate resin (P1) using a dihydroxy compound capable of producing the repeating unit (E).

[0147] <Polycarbonate resin (P2) content> When the thermoplastic resin composition of the present invention contains a polycarbonate resin (P2), from the viewpoint of effectively obtaining the above-mentioned effects of containing the polycarbonate resin (P2), the content of the polycarbonate resin (P2) is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition of the present invention. On the other hand, from the viewpoint of ensuring the content of the polycarbonate resin (P1) and reliably obtaining the effects of the flame retardancy, heat resistance, and impact resistance of the polycarbonate resin (P1), the content of the polycarbonate resin (P2) is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition of the present invention.

[0148] When the thermoplastic resin composition of the present invention contains a polycarbonate resin (P2), it may contain only one type of polycarbonate resin (P2), or it may contain two or more types of polycarbonate resins (P2) that differ in the type of repeating unit (E), the content thereof, physical properties, etc.

[0149] [Other ingredients] The thermoplastic resin composition of the present invention may contain other components in addition to the polycarbonate resin (P1), the polycarbonate resin (P2), and the flame retardant (C), as necessary, as long as the desired physical properties are not significantly impaired. Examples of the other components include resins other than the polycarbonate resin (P1) and the polycarbonate resin (P2), and various additives (D) other than the flame retardant (C). The other components may be contained alone or in any combination and ratio of two or more.

[0150] Examples of resins other than the polycarbonate resin (P1) and the polycarbonate resin (P2) include the following resins. Polycarbonate resins other than polycarbonate resin (P1) and polycarbonate resin (P2); Thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); Styrenic resins such as polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), and cyclic cycloolefin resin (COP resin); Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU resin); Polymethacrylate resin (PMMA resin); Liquid crystal polymer (LCP), etc.

[0151] The thermoplastic resin composition of the present invention may contain one type of resin other than the above-mentioned polycarbonate resin (P1) and polycarbonate resin (P2), or may contain two or more types in any combination and ratio.

[0152] When the thermoplastic resin composition of the present invention contains a resin other than the polycarbonate resin (P1) and the polycarbonate resin (P2), in order to more effectively obtain the effects of the present invention obtained by including the polycarbonate resin (P1) of the present invention, it is preferable that the content of the polycarbonate resin (P1) per 100 parts by mass of the thermoplastic resin contained in the thermoplastic resin composition of the present invention is equal to or greater than the above-mentioned lower limit.

[0153] Examples of the additive (D) other than the flame retardant (C) include a heat stabilizer, an antioxidant, a release agent, an ultraviolet absorber, a dye or pigment, an anti-dripping agent, an antistatic agent, an anti-fogging agent, a lubricant, an anti-blocking agent, a flow improver, a plasticizer, a dispersant, an antibacterial agent, glass fiber, carbon fiber, an inorganic filler, and an organic fiber. The thermoplastic resin composition of the present invention may contain one kind of these additives (D), or may contain two or more kinds in any combination and in any ratio.

[0154] When the thermoplastic resin composition of the present invention contains these additives (D), from the viewpoint of obtaining the effects of each additive (D) without impairing the inherent properties of the polycarbonate resin (P1), the content of each additive (D) is preferably 0.01 to 1.0 part by mass per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition of the present invention, and is preferably 2.0 parts by mass or less in total.

[0155] [Physical properties of thermoplastic resin composition] <Flame retardancy> The evaluation in the UL94 vertical flame test using a 1.0 mm thick test piece prepared using the thermoplastic resin composition I of the present invention is preferably V-0 or V-1, and more preferably V-0. Furthermore, it is more preferable that the evaluation in the UL94 standard vertical flame test using a 0.8 mm thick test piece prepared using the thermoplastic resin composition I of the present invention is V-0 or V-1, and it is even more preferable that the evaluation is V-0. In particular, it is preferable that the evaluation in the UL94 standard vertical flame test using a 0.6 m thick test piece made using the thermoplastic resin composition I of the present invention is V-0 or V-1, and this evaluation is most preferably V-0.

[0156] The thermoplastic resin composition II of the present invention was used to prepare a 1.0 mm thick test piece, and the result of the UL94 vertical flame test was V-0 or V-1, with V-0 being preferred. Furthermore, the evaluation in the UL94 vertical flame test using a 0.8 mm thick test piece prepared using the thermoplastic resin composition II of the present invention is preferably V-0 or V-1, and more preferably V-0. In particular, it is preferable that the evaluation in the UL94 vertical flame test using a 0.6 mm thick test piece prepared using the thermoplastic resin composition II of the present invention is V-0 or V-1, and most preferably this evaluation is V-0. That is, the thermoplastic resin composition of the present invention has a great feature in that it uses a metal salt flame retardant (C1), preferably a fluorine-free organic acid metal salt compound, and exhibits the above-mentioned high flame retardancy in an extremely thin test piece having a thickness of 1.0 mm, particularly 0.8 mm, and especially 0.6 mm. The specific measurement method for the UL94 standard vertical flame test is as described in the Examples section below.

[0157] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of the thermoplastic resin composition of the present invention is not limited, but is preferably 125 to 200°C. If the Tg is 125°C or higher, the heat resistance of the thermoplastic resin composition of the present invention and the molded article is improved. On the other hand, if the Tg is 200°C or lower, the flowability of the thermoplastic resin composition of the present invention is good, and high moldability can be obtained. For this reason, the glass transition temperature (Tg) of the thermoplastic resin composition of the present invention is preferably 125 to 200°C.

[0158] <Molecular weight of thermoplastic resin composition> Although there are no particular restrictions on the molecular weight of the thermoplastic resin composition of the present invention, it is preferable that the viscosity average molecular weight (Mv) calculated from the solution viscosity is 14,500 or more. A viscosity average molecular weight equal to or greater than the above lower limit is preferable because the heat resistance and flame retardancy of the thermoplastic resin composition of the present invention and molded articles are improved. From this perspective, the viscosity average molecular weight of the thermoplastic resin composition of the present invention is more preferably 16,000 or more, even more preferably 17,000 or more, particularly preferably 18,500 or more, and most preferably 20,000 or more.

[0159] On the other hand, the viscosity average molecular weight (Mv) of the thermoplastic resin composition of the present invention is preferably 30,000 or less. When the viscosity average molecular weight is equal to or less than the above upper limit, the flowability of the thermoplastic resin composition of the present invention tends to be good, which is preferable. From this viewpoint, the viscosity average molecular weight of the thermoplastic resin composition of the present invention is more preferably 28,000 or less, even more preferably 27,000 or less, particularly preferably 26,000 or less, and most preferably 24,000 or less.

[0160] <Melt viscosity (MVR) of thermoplastic resin composition> The melt viscosity (MVR) of the thermoplastic resin composition of the present invention is not particularly limited, but it is preferable that the melt viscosity (MVR) of the thermoplastic resin composition of the present invention is 15 cm as measured by the method described in the Examples section below. 3It is preferable that the melt viscosity is not more than the above upper limit, since the heat resistance and flame retardancy of the thermoplastic resin composition of the present invention and the molded article are improved. From this viewpoint, the melt viscosity of the thermoplastic resin composition of the present invention is more preferably 13 cm / min or less. 3 / 10 min or less, and more preferably 10 cm 3 / 10 min or less, and particularly preferably 8 cm 3 / 10 min or less, and most preferably 7 cm 3 / 10min or less.

[0161] On the other hand, the melt viscosity (MVR) of the thermoplastic resin composition of the present invention is 2.0 cm 3 It is preferable that the melt viscosity is 2.5 cm / 10 min or more. When the melt viscosity is equal to or more than the above lower limit, the flowability of the thermoplastic resin composition of the present invention tends to be good, which is preferable. From this viewpoint, the melt viscosity of the thermoplastic resin composition of the present invention is more preferably 2.5 cm / 10 min or more. 3 / 10 min or more, and more preferably 2.8 cm 3 / 10 min or more, and particularly preferably 3.0 cm 3 / 10 min or more, and most preferably 3.5 cm 3 / 10min or more.

[0162] [Method of producing thermoplastic resin composition] The method for producing the thermoplastic resin composition of the present invention is not limited, and a wide variety of known methods for producing thermoplastic resin compositions can be employed. Specifically, there is a method in which the polycarbonate resin (P1), the flame retardant (C), and the polycarbonate resin (P2), other resins, and additives (D) used as needed are melt-kneaded in a mixer such as a Banbury mixer, a roll, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader.

[0163] [Molded products] To produce a molded article using the thermoplastic resin composition of the present invention, the thermoplastic resin composition produced as described above may be pelletized and the pellets may be molded by various molding methods to produce a molded article, or the thermoplastic resin composition of the present invention may be melt-kneaded in an extruder and directly molded into a molded article, without going through the pelletizing step.

[0164] The shape of the molded article of the present invention is not particularly limited and can be appropriately selected depending on the use and purpose of the molded article, and examples thereof include plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-like, box-like, and panel-like shapes. Furthermore, the molded article may have, for example, an uneven surface or a three-dimensional shape having a three-dimensional curved surface. Furthermore, when used as a sheet, film, plate-like, or the like, it may be laminated with another resin sheet to form a multilayer structure.

[0165] The method for forming the molded article is not particularly limited, and any conventionally known molding method can be used. Examples include injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, sheet molding, thermoforming, laminate molding, and press molding. Of these, injection molding and extrusion molding are particularly preferred.

[0166] The molding temperature when molding the thermoplastic resin composition of the present invention is preferably 200°C or higher, more preferably 250°C or higher, and most preferably 280°C or higher. By setting the molding temperature to the above lower limit or higher, fluidity and moldability are improved. The molding temperature when molding the thermoplastic resin composition of the present invention is preferably 350°C or lower, particularly preferably 320°C or lower. By setting the molding temperature to the above upper limit or lower, the color tone of the thermoplastic resin composition can be made good.

[0167] When injection molding or extrusion molding is carried out, pigments, dyes, mold release agents, heat stabilizers, etc. may be added to the thermoplastic resin composition of the present invention as appropriate within the range that does not impair the object of the present invention.

[0168] <Injection molded products> The thermoplastic resin composition of the present invention can be suitably used as an injection-molded product by injection molding. The injection molding method is not particularly limited, and any molding method commonly used for thermoplastic resins can be used. Examples include ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted or other hollow molding methods, molding using an insulated mold, molding using a rapidly heated mold, foam molding (including supercritical fluids), insert molding, and IMC (in-mold coating) molding. Molding methods using a hot runner system can also be used.

[0169] When an injection molding machine or the like is used, the mold temperature is preferably 150°C or lower, more preferably 120°C or lower, and most preferably 100°C or lower. By setting the mold temperature at or below the upper limit, the cooling time during molding can be shortened, shortening the production cycle of molded products and improving productivity. When an injection molding machine or the like is used, the mold temperature is preferably 30°C or higher, and particularly preferably 50°C or higher. Setting the mold temperature at or above the lower limit is preferable because it allows for the production of uniform molded products.

[0170] <Extrusion molded products> The thermoplastic resin composition of the present invention can be suitably used as an extrusion-molded product by extrusion molding. There are no particular limitations on the method for producing an extrusion-molded product from the thermoplastic resin composition of the present invention, but an extrusion molding machine is usually used. The extrusion molding machine is generally equipped with a T-die, a round die, or the like, and extrusion-molded products of various shapes can be obtained. Examples of extrusion-molded products include sheets, films, plates, tubes, pipes, and the like. Among these, sheets or films are preferred.

[0171] The extrusion molded article of the thermoplastic resin composition of the present invention may be laminated on one or both sides of the extrusion molded article with a hard coat layer to improve adhesion, paintability, and printability, or may be heat-laminated on one or both sides of the extrusion molded article with a film for improving weather resistance and / or scratch resistance. Furthermore, the surface may be subjected to a graining process or a semi-transparent or opaque process.

[0172] <Application> Molded articles such as injection-molded articles and extrusion-molded articles made from the thermoplastic resin composition of the present invention have excellent flame retardancy, heat resistance, and impact resistance, and in particular, can achieve unprecedentedly high flame retardancy by using a fluorine-free organic acid metal salt compound, and can be used in a variety of applications requiring these properties, such as parts for various automobile components, electrical and electronic devices, information terminal devices, office automation equipment, machine parts, home appliances, vehicle parts, building components, various containers, leisure goods and miscellaneous goods, lighting equipment, etc. Among these, the molded articles of the present invention are particularly suitable for use in parts for electrical and electronic devices, information terminal devices, office automation equipment, home appliances, etc. due to their excellent flame retardancy, heat resistance, and impact resistance, and can be particularly suitable for use as molding materials for the housings of electrical and electronic devices, information terminal devices, office automation equipment, automotive interior parts, and home appliances. [Example]

[0173] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to the following examples.

[0174] [Evaluation method] The physical properties of the polycarbonate resins obtained in the following Examples and Comparative Examples were evaluated by the following methods.

[0175] (1) Viscosity: Viscosity average molecular weight (Mv) The polycarbonate resin or polycarbonate resin composition was dissolved in methylene chloride (concentration: 6.0 g / L), and the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at 20°C was determined using an Ubbelohde viscosity tube (manufactured by Moritomo Rika Kogyo Co., Ltd.), and the viscosity average molecular weight (Mv) was calculated using Schnell's viscosity formula (the following formula). η = 1.23 × 10-4 Mv 0.83

[0176] (2) Viscosity: Melt viscosity (Melt Volume Rate (MVR)) The polycarbonate resin composition was dried at 100°C for 5 hours, and then measured for MVR (unit: cm) using a melt indexer manufactured by Toyo Seiki Co., Ltd. in accordance with ISO1133 under the conditions of a measurement temperature of 300°C and a load of 11.8N. 3 / 10min) was measured.

[0177] (3) Heat resistance: Glass transition temperature (Tg) Using a differential scanning calorimeter (DSC6220 manufactured by SII), approximately 10 mg of a sample of polycarbonate resin or polycarbonate resin composition was heated at a heating rate of 20°C / min to measure the calorific value, and the extrapolated glass transition onset temperature was determined in accordance with JIS K7121. This extrapolated glass transition temperature was defined as the glass transition temperature (Tg).

[0178] (4) Heat resistance: Deflection temperature under load (DTUL) Using an injection molding machine (NEX80-V9EG manufactured by Nissei Plastic Industrial Co., Ltd.), polycarbonate resin compositions were injection molded at a resin temperature of 300°C and a mold temperature of 80°C to prepare ISO multipurpose test specimens (4 mm thick). The DTUL (temperature deflection under load, unit: °C) of the obtained test specimens was measured at a load of 1.80 MPa (method A) in accordance with ISO 75-1&2 to evaluate heat resistance.

[0179] (5) Impact resistance: Charpy impact strength Using an injection molding machine (NEX80-V9EG manufactured by Nissei Plastic Industrial Co., Ltd.), polycarbonate resin compositions were injection molded under conditions of a resin temperature of 300°C and a mold temperature of 80°C to prepare ISO multipurpose test specimens (4 mm thick). The test specimens were cut into the shape of notched Charpy test specimens as specified in ISO 179. In accordance with ISO 179, the unnotched and notched Charpy impact strengths (unit: kJ / m) of the ISO multipurpose test specimens (4 mm thick) were measured at a temperature of 23°C. 2 ) was measured.

[0180] (6) Flame retardancy: 20mm vertical burning test (1.0mmt) Pellets of polycarbonate resin or polycarbonate resin composition were dried at 120°C for 4 hours, and then molded into combustion test specimens measuring 125 mm x 13 mm x 1.0 mm thick using an injection molding machine (SE100EV-A-SHR manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300°C and a mold temperature of 80°C. The obtained test specimens for the combustion test were subjected to a 20 mm vertical combustion test in accordance with UL94 (October 29, 1996, 5th edition). The results of the flammability test were classified into V-0, V-1, V-2, and non-conforming according to the material classification described in UL94. If the classification result was V-2, the maximum time required for the smoke or drips to ignite the cotton marker was recorded and compared.

[0181] (7) Flame retardancy: 20mm vertical burning test (0.8mmt) Pellets of polycarbonate resin or polycarbonate resin composition were dried at 120°C for 4 hours, and then molded into combustion test specimens measuring 125 mm x 13 mm x 0.8 mm thick using an injection molding machine (SE100EV-A-SHR manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300°C and a mold temperature of 80°C. The obtained test specimens for the combustion test were subjected to a 20 mm vertical combustion test in accordance with UL94 (October 29, 1996, 5th edition). The results of the flammability test were classified into V-0, V-1, V-2, and non-conforming according to the material classification described in UL94. If the classification result was V-2, the maximum time required for the smoke or drips to ignite the cotton marker was recorded and compared.

[0182] (8) Flame retardancy: 20mm vertical burning test (0.6mmt) Pellets of polycarbonate resin or polycarbonate resin composition were dried at 120°C for 4 hours, and then molded into combustion test specimens measuring 125 mm x 13 mm x 0.6 mm thick using an injection molding machine (SE100EV-A-SHR manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300°C and a mold temperature of 80°C. The obtained test specimens for the combustion test were subjected to a 20 mm vertical combustion test in accordance with UL94 (October 29, 1996, 5th edition). The results of the flammability test were classified into V-0, V-1, V-2, and non-conforming according to the material classification described in UL94. If the classification result was V-2, the maximum time required for the smoke or drips to ignite the cotton marker was recorded and compared.

[0183] [Compounds that serve as raw materials for repeating unit (B)] 4,4-methylenebis(2,6-dimethylphenol) (TmBPF) was used as the raw material compound for the repeating unit (B) that constitutes the polycarbonate resin (P1). The following four types of TmBPF with different Fe contents were prepared for use in the production of the polycarbonate resin (P1).

[0184] [Table 1]

[0185] The Fe content in TmBPF was determined by the following method. Approximately 0.2 g of the sample was weighed out and subjected to microwave pressure decomposition with nitric acid in a sealed container using an Anton Paar Multiwave 7000. The decomposed product was collected, the volume was measured, and quantitative ICP-MS analysis was performed using an Agilent Technologies ICP-MS 8900 to determine the Fe content in TmBPF.

[0186] [Polycarbonate resin (P1)] As the polycarbonate resin (P1), the following TmBPF / BPC=8 / 2 copolymers-1 to 8, TmBPF / BPC=4 / 6 copolymer-9, and TmBPF / BPA=8 / 2 copolymer-10 were produced according to the following Production Examples.

[0187] [Manufacturing Example 1] 2,2-bis(3-methyl-4-hydroxyphenyl)propane (BPC) (Honshu Chemical Co., Ltd.) 6.70 kg (26.14 mol), 4,4-methylenebis(2,6-dimethylphenol) (TmBPF-1) (Deepak) 26.80 kg (104.54 mol), and diphenyl carbonate (DPC) 29.53 kg (137.87 mol) were placed in a SUS reactor (internal volume 200 liters) equipped with a stirrer and a distillation condenser. The reactor was then purged with nitrogen gas and heated to 220 ° C. in a nitrogen gas atmosphere over 30 minutes. The reaction solution in the reactor was then stirred, and a 25% by mass aqueous solution of cesium carbonate was added to the molten reaction solution as a transesterification catalyst, with the cesium carbonate concentration being 16 μmol per 1 mol of total dihydroxy compounds. The reaction solution was stirred and fermented at 220 ° C. for 30 minutes under a nitrogen gas atmosphere. Next, the pressure inside the reactor was reduced to 100 Torr over 40 minutes at the same temperature, and the reaction was continued for a further 100 minutes to distill off phenol.

[0188] Next, the temperature inside the reactor was raised to 285°C over 60 minutes while the pressure was reduced to 3 Torr, and almost the entire theoretical amount of phenol was distilled out. The pressure inside the reactor was then maintained at less than 1 Torr at the same temperature, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. The agitator's rotation speed was 8 rpm, and the reaction liquid temperature just before the end of the reaction was 285°C, with a stirring power of 1.04 kW.

[0189] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter.

[0190] To the above pellets, 1.1 times the molar amount of cesium carbonate was added butyl p-toluenesulfonate, and the mixture was fed into a twin-screw extruder and kneaded. The reaction mixture was then extruded into strands through the die of the twin-screw extruder and cut with a cutter to obtain pellets of the carbonate resin (P1), a TmBPF / BPC copolymer. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-1 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-1") are shown in Table 2.

[0191] [Manufacturing Example 2] 1.34 kg (5.23 mol) of 2,2-bis(3-methyl-4-hydroxyphenyl)propane (BPC) (Honshu Chemical Co., Ltd.), 5.36 kg (20.91 mol) of 4,4-methylenebis(2,6-dimethylphenol) (TmBPF-1) (Deepak) and 5.77 kg (26.95 mol) of diphenyl carbonate (DPC) were placed in a SUS reactor (internal volume 40 liters) equipped with a stirrer and a distillation condenser. The reactor was then purged with nitrogen gas and heated to 220 ° C. under a nitrogen gas atmosphere for 30 minutes. The reaction solution in the reactor was then stirred, and a 5% by mass aqueous solution of cesium carbonate was added to the molten reaction solution as a transesterification catalyst, with the cesium carbonate content being 16 μmol per 1 mol of total dihydroxy compounds. The reaction solution was stirred and fermented at 220 ° C. for 30 minutes under a nitrogen gas atmosphere. Next, the pressure inside the reactor was reduced to 100 Torr over 40 minutes at the same temperature, and the reaction was continued for a further 100 minutes to distill off phenol.

[0192] Next, the temperature inside the reactor was raised to 285°C over 60 minutes while the pressure was reduced to 3 Torr, and phenol equivalent to almost the entire theoretical distillation amount was distilled out. The pressure inside the reactor was then maintained at less than 1 Torr at the same temperature, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. The stirring speed of the stirrer was 20 rpm, and the reaction liquid temperature just before the end of the reaction was 286°C, with a stirring power of 0.54 kW.

[0193] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter.

[0194] To the above pellets, 1.1 times the molar amount of cesium carbonate was added butyl p-toluenesulfonate, and the mixture was fed into a twin-screw extruder and kneaded. The reaction mixture was then extruded into strands through the die of the twin-screw extruder and cut with a cutter to obtain pellets of the carbonate resin (P1), a TmBPF / BPC copolymer. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-2 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-2") are shown in Table 2.

[0195] [Manufacturing Example 3] The procedure was carried out in the same manner as in Production Example 2, except that the amount of diphenyl carbonate (DPC) charged was 5.76 kg (26.87 mol), the reaction liquid temperature just before the end of the reaction was 284°C, and the stirring power was 0.49 kW, and evaluation was similarly performed. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-3 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-3") are shown in Table 2.

[0196] [Manufacturing Example 4] The procedure was carried out in the same manner as in Production Example 2, except that the amount of diphenyl carbonate (DPC) charged was 5.76 kg (26.87 mol), the reaction liquid temperature just before the end of the reaction was 285°C, and the stirring power was 0.53 kW, and evaluation was similarly carried out. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-4 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-4") are shown in Table 2.

[0197] [Manufacturing Example 5] Under a nitrogen gas atmosphere, a molten mixture prepared by mixing 4,4-methylenebis(2,6-dimethylphenol) (TmBPF-1) (Deepak Chemicals) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (BPC) (Honshu Chemical Co., Ltd.) with diphenyl carbonate (DPC) in a constant molar ratio (TmBPF-1 / BPC = 8 / 2, DPC / total dihydroxy compounds molar ratio = 1.016) at 150°C was continuously fed through a raw material inlet pipe into a first vertical reactor controlled at 13.3 × 103 Pa and 220°C. The liquid level was kept constant by controlling the valve opening of the polymer discharge line at the bottom of the reactor so that the average residence time was 75 minutes. Simultaneously with the start of the supply of the above raw materials, an aqueous cesium carbonate solution was continuously supplied as a catalyst at a flow rate such that the amount of cesium carbonate per mole of total dihydroxy compounds was 16.0 × 10 mol (16.0 μmol / 1 mole of total dihydroxy compounds). The distillate products produced, such as phenol, were continuously liquefied and recovered using a heat exchanger installed in the distillation line of the first vertical reactor. The reaction liquid discharged from the first vertical reactor was then continuously introduced into the second and third vertical reactors and the fourth horizontal reactor. The operating conditions of each reactor were as follows: temperature and vacuum increased as the reaction progressed. Second vertical reactor: 260°C, 5.50 x 103 Pa, 100 rpm Third vertical reactor: 280°C, 250 Pa, 65 rpm Fourth horizontal reactor: outlet resin temperature 290°C, 70 to 100 Pa, 4 to 10 rpm During the reaction, the liquid level was controlled so that the average residence time in the second and third vertical reactors was 80 minutes and the average residence time in the fourth horizontal reactor was 65 minutes, and at the same time, the by-product phenol was distilled off.

[0198] Next, the polymer melt discharged from the fourth horizontal reactor was introduced into a vented twin-screw extruder (screw diameter 30 mm, partially intermeshing screw type, co-rotating), and butyl p-toluenesulfonate was fed as a catalyst deactivator so as to be 28.5 mass ppm relative to the polycarbonate resin. After devolatilization at each vent port (vented twin-screw extruder outlet temperature: 300°C), the polymer melt was filtered through a leaf disc-type polymer filter, water-cooled, and pelletized. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-5 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-5") are shown in Table 2.

[0199] [Manufacturing Example 6] A raw material mixture was prepared by adding 93.37 g (approximately 0.364 mol) of TmBPF-2 (manufactured by Deepak Chemicals) and 23.34 g (approximately 0.091 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) (manufactured by Honshu Chemical Co., Ltd.) and 100.65 g (approximately 0.470 mol) of diphenyl carbonate (DPC), as well as a 4 mass% aqueous solution of cesium carbonate as a catalyst, so that the cesium carbonate concentration was 16 μmol per 1 mol of all dihydroxy compounds, to a 150 ml glass reactor equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device.

[0200] Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. The stirrer was then rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute over 40 minutes, while distilling off phenol, which was a by-product of the oligomerization reaction of the dihydroxy compound and DPC inside the reactor.

[0201] Next, the pressure inside the reactor was maintained at 13.3 kPa, and a transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute over 40 minutes, and the distilled phenol was removed from the system. The temperature outside the reactor was then raised to 285°C, and the absolute pressure inside the reactor was reduced to 30 Pa (approximately 0.2 Torr), and a polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power.

[0202] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-6 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-6") are shown in Table 2.

[0203] [Manufacturing Example 7] The procedure was carried out in the same manner as in Production Example 6, except that 93.37 g (approximately 0.364 mol) of TmBPF-3 (manufactured by Deepak) and 100.94 g (approximately 0.471 mol) of diphenyl carbonate (DPC) were used, and evaluation was carried out in the same manner. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-7 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-7") are shown in Table 2.

[0204] [Manufacturing Example 8] The procedure was carried out in the same manner as in Production Example 6, except that 93.37 g (approximately 0.364 mol) of TmBPF-4 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100.94 g (approximately 0.471 mol) of diphenyl carbonate (DPC) were used, and evaluation was carried out in the same manner. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=8 / 2 copolymer-8 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-8") are shown in Table 2.

[0205] [Manufacturing Example 9] A raw material mixture was prepared using 2.68 kg (10.45 mol) of TmBPF-1 (manufactured by Deepak), 4.02 kg (15.68 mol) of BPC, 5.71 kg (26.66 mol) of diphenyl carbonate (DPC), and a 4 mass% aqueous solution of cesium carbonate as a catalyst, with the addition of 10.0 μmol of cesium carbonate per 1 mol of all dihydroxy compounds. The reaction was carried out in the same manner as in Production Example 2, except that the reaction liquid temperature immediately before the end of the reaction was 285°C and the stirring power was 0.61 kW, and evaluation was carried out in the same manner. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPC=4 / 6 copolymer-9 (hereinafter sometimes referred to as "TmBPF / BPC copolymer-9") are shown in Table 2.

[0206] [Manufacturing Example 10] A raw material mixture was prepared using 5.48 kg (21.38 mol) of TmBPF-1 (Deepak Chemicals), 1.22 kg (5.34 mol) of BPA (Mitsubishi Chemical Corporation) instead of BPC (Honshu Chemical Co., Ltd.), 5.95 kg (26.87 mol) of diphenyl carbonate (DPC), and a 4 mass% aqueous solution of cesium carbonate as a catalyst, added so that the cesium carbonate was 18.0 μmol per 1 mol of total dihydroxy compounds. The reaction was carried out in the same manner as in Production Example 2, except that the reaction liquid temperature immediately before the end of the reaction was 286°C and the stirring power was 0.58 kW, and evaluation was carried out in the same manner. The viscosity average molecular weight (Mv) and glass transition temperature (Tg) of this polycarbonate resin (P1) TmBPF / BPA=8 / 2 copolymer-10 (hereinafter sometimes referred to as "TmBPF / BPA copolymer-10") are shown in Table 2.

[0207] [Table 2]

[0208] [Flame retardancy of polycarbonate resin (P1)] [Reference example 1] The TmBPF / BPC=8 / 2 copolymer-6 was subjected to a 20 mm vertical flame test (0.8 mmt), and the result was V-0.

[0209] [Reference example 2] The TmBPF / BPC=8 / 2 copolymer-7 was subjected to a 20 mm vertical flame test (0.8 mmt), and the result was V-0.

[0210] [Reference example 3] A 20 mm vertical flame test (0.8 mmt) was conducted on TmBPF / BPC=8 / 2 copolymer-8, and the result was V-0.

[0211] The results of the above Reference Examples 1 to 3 are summarized in Table 3.

[0212] [Table 3]

[0213] [Polycarbonate resin (P2)] As the polycarbonate resin (P2), the following polycarbonate resin was used.

[0214] (1) A-PC-1 Mitsubishi Chemical Corporation product name: XANTAR TM 7022J" Polycarbonate resin produced by the melt process using bisphenol-A as the starting material Viscosity average molecular weight (Mv): 20,850 Glass transition temperature (Tg): 145℃

[0215] (2) A-PC-2 Manufactured by Mitsubishi Chemical Corporation, product name "XANTAR TM M7028B" Polycarbonate resin produced by the melt process using bisphenol-A as the starting material Viscosity average molecular weight (Mv): 28,000 Glass transition temperature (Tg): 145℃

[0216] (3) A-PC-3 An aromatic polycarbonate resin obtained by interfacial polymerization using bisphenol-A as a starting material in accordance with Example 1 (PC-1) of WO 2011 / 132510. Viscosity average molecular weight (Mv): 78,000 Glass transition temperature (Tg): 149℃

[0217] (4) A-PC-4 Manufactured by Mitsubishi Chemical Corporation, product name "XANTAR TM 7022PJ" Polycarbonate resin produced by the interfacial method using bisphenol-A as a starting material Viscosity average molecular weight (Mv): 20,850 Glass transition temperature (Tg): 147℃

[0218] (5) A-PC-5 Manufactured by Mitsubishi Chemical Corporation, product name "XANTARTM 7022PJ 3LV" Polycarbonate resin produced by the interfacial method using bisphenol-A as a starting material Viscosity average molecular weight (Mv): 17,130 Glass transition temperature (Tg): 147℃

[0219] (6) A-PC-6 Manufactured by Mitsubishi Chemical Corporation, product name "XANTAR TM 7015PJ" Polycarbonate resin produced by the interfacial method using bisphenol-A as a starting material Viscosity average molecular weight (Mv): 15,000 Glass transition temperature (Tg): 145℃

[0220] (7) C-PC Polycarbonate resin made from bisphenol C as a starting material by melt polymerization according to the following method: 6.70 kg (26.14 mol) of 2,2-bis(3-methyl-4-hydroxyphenyl)propane (BPC) (manufactured by Honshu Chemical Co., Ltd.) and 5.85 kg (27.31 mol) of diphenyl carbonate (DPC) were placed in a 40-liter stainless steel reactor equipped with a stirrer and a distillation condenser. The reactor was then purged with nitrogen gas and heated to 220°C over 30 minutes under a nitrogen gas atmosphere. The reaction mixture in the reactor was then stirred, and a 0.81% by mass aqueous solution of cesium carbonate as a transesterification catalyst was added to the molten reaction mixture so that the cesium carbonate concentration was 1.5 μmol per mol of total dihydroxy compounds. The reaction mixture was stirred and fermented at 220°C for 30 minutes under a nitrogen gas atmosphere. The pressure in the reactor was then reduced to 100 Torr over 40 minutes at the same temperature, and the mixture was allowed to react for another 100 minutes, during which phenol was distilled off.

[0221] Next, the temperature inside the reactor was raised to 285°C over 60 minutes while the pressure was reduced to 3 Torr, and phenol equivalent to almost the entire theoretical distillation amount was distilled out. The pressure inside the reactor was then maintained at less than 1 Torr at the same temperature, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. The stirring speed of the stirrer was 20 rpm, and the reaction liquid temperature just before the end of the reaction was 285°C, with a stirring power of 0.44 kW.

[0222] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter.

[0223] To the above pellets, 4.0 times the molar amount of cesium carbonate was added butyl p-toluenesulfonate, and the mixture was fed into a twin-screw extruder and kneaded. The reaction liquid was then extruded into strands through the die of the twin-screw extruder and cut with a cutter to obtain pellets of polycarbonate resin C-PC. Viscosity average molecular weight (Mv): 19,000 Glass transition temperature (Tg): 145℃

[0224] [Examples 1 to 12 and Comparative Examples 1 and 2: Production and Evaluation of Thermoplastic Resin Compositions] [Example 1] 0.04 parts by mass of potassium 3-(phenylsulfonyl)benzenesulfonate (KSS-FR) (manufactured by Arichem) and an antioxidant (ADK STAB) were added to 100 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-1) obtained in Production Example 1. TM 2112 (ADEKA Corporation) 0.03 parts by mass, antioxidant: Adekastab TM AO-60 (ADEKA Corporation) 0.1 parts by weight, release agent: Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by weight, release agent: Unistar TM M9676 (NOF Corporation) 0.1 mass parts, UV absorber: ADK STAB TMThe mixture was blended with 0.3 parts by mass of LA-31 (ADEKA Corporation) and mixed in a tumbler for 20 minutes, then fed into a φ30 mm twin-screw extruder (TEX30α) equipped with one vent, manufactured by The Japan Steel Works, Ltd., and kneaded under conditions of a screw rotation speed of 160 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 310°C. The molten resin extruded in the form of strands was quenched in a water tank and pelletized using a pelletizer to obtain a thermoplastic resin composition (polycarbonate resin composition). The viscosity average molecular weight and melt viscosity (MVR) of the obtained thermoplastic resin composition were measured, and the flame retardancy and heat resistance were evaluated. The results are shown in Table 4. The thermoplastic resin composition was also evaluated for impact resistance. The notched Charpy impact value was 3 kJ / m 2 , unnotched Charpy impact value is 169kJ / m 2 It was.

[0225] [Example 2] The procedures described in Example 1 were repeated, except that the TmBPF / BPC copolymer-2 obtained in Production Example 2 was used as the polycarbonate resin (P1) instead of the TmBPF / BPC copolymer-1. The viscosity-average molecular weight and melt viscosity (MVR) were measured, and the flame retardancy and heat resistance were evaluated. The results are shown in Table 4.

[0226] [Example 3] 0.04 parts by mass of potassium 3-(phenylsulfonyl)benzenesulfonate (KSS-FR) (manufactured by Arichem) and an antioxidant (ADK STAB) were used relative to 100 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-2) obtained in Production Example 2. TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was used, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0227] [Example 4] 0.04 parts by mass of potassium 3-(phenylsulfonyl)benzenesulfonate (KSS-FR) (manufactured by Arichem) and Adekastab TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM M9676 (NOF Corporation) 0.1 parts by weight, UV absorber: Seesorb TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of 709 (manufactured by Shipro Kasei Co., Ltd.) was used, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0228] [Example 5] 0.08 parts by mass of potassium 3-(phenylsulfonyl)benzenesulfonate (KSS-FR) (manufactured by Arichem) and Adekastab TM 2112 (ADEKA Corporation) 0.03 mass parts, ADK STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was used, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0229] [Example 6] 0.08 parts by mass of potassium 3-(phenylsulfonyl)benzenesulfonate (KSS-FR) (manufactured by Arichem) and Adekastab TMAO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), Seesorb TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of 709 (manufactured by Shipro Kasei Co., Ltd.) was used, and evaluation was carried out in the same manner.

[0230] [Example 7] For 100 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-1) obtained in Production Example 1, 0.04 parts by mass of sodium paratoluenesulfonate (CG-NATS) (manufactured by Hengqiao Industrial Co., Ltd.), ADK STAB TM 2112 (ADEKA Corporation) 0.03 mass parts, ADK STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was used, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0231] [Example 8] 100 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-1) obtained in Production Example 1, 0.04 parts by mass of a sulfonate mixture (HES2-FR) (manufactured by Arichem), ADK STAB TM 2112 (ADEKA Corporation) 0.03 mass parts, ADK STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was used, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0232] [Example 9] To 90 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-3) obtained in Production Example 1, 10 parts by mass of A-PC-1 (7022J) (manufactured by Mitsubishi Chemical Corporation) as a bisphenol A type polycarbonate resin (P2), 0.08 parts by mass of potassium 3-(phenylsulfonyl)benzenesulfonate (KSS-FR) (manufactured by Arichem), and Adeka STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), Seesorb TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of 709 (manufactured by Shipro Kasei Co., Ltd.) was added, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0233] [Example 10] To 70 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-2) obtained in Production Example 2, 30 parts by mass of A-PC-2 (M7028B) (manufactured by Mitsubishi Chemical Corporation) as a bisphenol A type polycarbonate resin (P2), 0.04 parts by mass of potassium 3-(phenylsulfonyl)benzenesulfonate (KSS-FR) (manufactured by Arichem), and Adeka STAB TM 2112 (ADEKA Corporation) 0.03 mass parts, ADK STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was added, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0234] [Example 11] To 70 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-2) obtained in Production Example 2, 30 parts by mass of A-PC-2 (M7028B) (manufactured by Mitsubishi Chemical Corporation) as a bisphenol A type polycarbonate resin (P2), 0.04 parts by mass of sodium paratoluenesulfonate (CG-NATS) (manufactured by Hengqiao Industrial Co., Ltd.), and Adeka STAB TM 2112 (ADEKA Corporation) 0.03 mass parts, ADK STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was added, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0235] [Example 12] To 70 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-2) obtained in Production Example 1, 30 parts by mass of A-PC-2 (M7028B) (manufactured by Mitsubishi Chemical Corporation) as a bisphenol A type polycarbonate resin (P2), 0.08 parts by mass of sodium paratoluenesulfonate (CG-NATS) (manufactured by Hengqiao Industrial Co., Ltd.), and 0.08 parts by mass of sodium paratoluenesulfonate (CG-NATS) (manufactured by Adeka STAB TM 2112 (ADEKA Corporation) 0.03 mass parts, ADK STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 2, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was added, and evaluation was carried out in the same manner. The results are shown in Table 4.

[0236] [Comparative Example 1] 100 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-4) obtained in Production Example 4 was mixed with 0.03 parts by mass of ADK STAB 2112 (manufactured by ADEKA CORPORATION), TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 1, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was added, and evaluation was carried out in the same manner. The results of viscosity average molecular weight, flame retardancy, and heat resistance are shown in Table 4. The thermoplastic resin composition was also evaluated for impact resistance. The notched Charpy impact value was 3 kJ / m 2 , unnotched Charpy impact value is 182kJ / m 2 It was.

[0237] Comparative Example 2 100 parts by mass of the polycarbonate resin (P1) (TmBPF / BPC copolymer-4) obtained in Production Example 4 was mixed with 0.04 parts by mass of potassium perfluorobutanesulfonate (IHT-FR21) (manufactured by INSIGHT HIGH TECHNOLOGY Co., LTD.), ADK STAB TM 2112 (ADEKA Corporation) 0.03 mass parts, ADK STAB TM AO-60 (ADEKA) 0.1 parts by mass, Roxiol TM VPG861 (Emery Oleochemicals Japan Co., Ltd.) 0.075 parts by mass, Unistar TM 0.1 parts by weight of M9676 (NOF Corporation), ADK STAB TM The procedure was carried out in the same manner as in Example 1, except that 0.3 parts by mass of LA-31 (manufactured by ADEKA Corporation) was added, and evaluation was carried out in the same manner. The results of viscosity average molecular weight, flame retardancy, and heat resistance are shown in Table 4. The thermoplastic resin composition was also evaluated for impact resistance. The notched Charpy impact value was 3 kJ / m 2 , unnotched Charpy impact value is 134kJ / m2 It was.

[0238] Table 4 shows the amounts of polycarbonate resin (P1), polycarbonate resin (P2), flame retardant, and additives other than flame retardant, the viscosity average molecular weight (Mv) and melt viscosity (MVR) of the thermoplastic resin composition obtained after compounding with flame retardants, etc. (Mv and MVR after compounding with flame retardants, etc.), and the evaluation results of flame retardancy and heat resistance.

[0239] [Table 4]

[0240] [Examples 13 to 34] The raw materials were prepared in the proportions shown in Tables 5 and 6, fed into a φ25 mm twin-screw extruder (TEM-26SX) manufactured by Shibaura Machine Co., Ltd., and kneaded under conditions of a screw rotation speed of 200 rpm, a discharge rate of 25 kg / hour, and a barrel temperature of 260°C. Except for this, the procedure was carried out in the same manner as in Example 1, and evaluations were carried out in the same manner. The results are shown in Tables 5 and 6. The details of the dyes and pigments listed in Tables 5 and 6 are as follows: MACROLEX Blue RR FG: Blue dye manufactured by LANXESS Plast Red 8370: Red dye manufactured by Arimoto Chemical Industry Co., Ltd. Kronos2233: White pigment manufactured by KRONOS PFC312: White pigment manufactured by Ishihara Sangyo Kaisha DCF-T-17007: White pigment manufactured by Resinocolor

[0241] [Table 5]

[0242] [Table 6]

[0243] [Examples 35 to 40, Comparative Examples 3 and 4] The raw materials were prepared in the proportions shown in Table 7, fed into a φ25 mm twin-screw extruder (TEM-26SX) manufactured by Shibaura Machine Co., Ltd., and kneaded under conditions of a screw rotation speed of 200 rpm, a discharge rate of 25 kg / hour, and a barrel temperature of 260°C. Except for this, the procedure was carried out in the same manner as in Example 1, and evaluations were carried out in the same manner. The results are shown in Table 7.

[0244] [Table 7]

[0245] [Consideration] From the above results, the following can be seen: Although Examples 1 to 34 differ in the type and amount of polycarbonate resin (P1) and polycarbonate resin (P2) and in the additive formulation, they are highly flame retardant, with a rating of V-0 or V-1 in the UL94 (0.6 mm) combustion test. On the other hand, in Comparative Example 1, which did not contain a flame retardant, and Comparative Example 2, in which a fluorine-containing metal salt flame retardant was added, the results of the combustion test were V-2, and the flame retardancy was inferior to Examples 1-34. Examples 1 and 8 have impact resistance comparable to that of Comparative Example 1, which does not contain a flame retardant. However, Comparative Example 2, which contains a fluorine-containing metal salt flame retardant, has inferior impact resistance (unnotched Charpy impact value) to that of Comparative Example 1. Examples 35 to 40 differ in the type and amount of polycarbonate resin (P1) and polycarbonate resin (P2) and in the additive formulation, but are highly flame retardant, achieving V-0 or V-1 in the UL94 (1.0 mm) combustion test. On the other hand, in Comparative Examples 3 and 4, which did not contain a flame retardant, the result of the combustion test was V-2, and the flame retardancy was inferior to that of Examples 35 to 40.

[0246] From the above, it can be seen that the thermoplastic resin compositions of Examples 1 to 40, which are polycarbonate resin compositions of the present invention, have superior flame retardancy, heat resistance, and impact resistance compared to the polycarbonate resins of Comparative Examples 1 to 4.

Claims

1. A thermoplastic resin composition comprising: a polycarbonate resin (P) containing a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2); and a flame retardant (C), wherein the flame retardant (C) is a fluorine-free organic acid metal salt compound: 【Chemical 1】 (In general formula (1), R １ and R ２ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. １ and R ２ The alkyl groups in R may be bonded to each other to form a ring. ３ and R ４ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 【Chemistry 2】 (In general formula (2), R ５ ~R ８ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

2. 2. The thermoplastic resin composition according to claim 1, wherein the content ratio of the repeating unit (A) to the repeating unit (B) in the polycarbonate resin (P) is, in molar ratio, repeating unit (A): repeating unit (B) = 30:70 to 10:

90.

3. 2. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin (P1) comprises a polycarbonate copolymer (P1A) in which the content ratio of the repeating unit (A) to the repeating unit (B) is, in molar ratio, repeating unit (A): repeating unit (B) = 50:50 to 10:

90.

4. The thermoplastic resin composition according to claim 3, wherein the polycarbonate resin (P1) contains 20 to 100% by mass of the polycarbonate copolymer (PA1).

5. 2. The thermoplastic resin composition according to claim 1, comprising 5 parts by mass or more of a polycarbonate resin (P2) containing 95% by mass or more of a repeating unit (E) represented by the following general formula (3) relative to 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition: 【Chemistry 3】 (In general formula (3), R １０ and R １１ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. １０ and R １１ The alkyl groups in R may be bonded to each other to form a ring. １２ and R １３ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

6. The thermoplastic resin composition according to claim 5, wherein the polycarbonate resin (P2) is contained in an amount of 70 parts by mass or less relative to 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

7. R in the general formula (1) ３ and R ４ each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

8. The thermoplastic resin composition according to claim 1 , wherein the flame retardant (C) contains a benzene ring.

9. The thermoplastic resin composition according to claim 8, wherein the flame retardant (C) is an aromatic sulfonic acid metal salt compound.

10. The thermoplastic resin composition according to claim 9, wherein the flame retardant (C) is potassium 3-(phenylsulfonyl)benzenesulfonate or sodium paratoluenesulfonate.

11. The thermoplastic resin composition according to claim 1, wherein the content of the flame retardant (C) is 0.005 parts by mass or more relative to 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

12. The thermoplastic resin composition according to claim 1, wherein the content of the flame retardant (C) is 0.5 parts by mass or less per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

13. The thermoplastic resin composition according to claim 1, further comprising at least one additive (D) other than the flame retardant (C).

14. In the general formula (1), R １ and R ２ is a methyl group, or R １ and R ２ The thermoplastic resin composition according to claim 1, wherein the alkyl groups of the formula (1a) or (1b) are bonded to each other to form a ring represented by the following formula (1a) or (1b): 【Chemistry 4】

15. In the general formula (1), R ３ and R ４ The thermoplastic resin composition according to claim 1 , wherein is a methyl group.

16. The thermoplastic resin composition according to claim 1, wherein the repeating unit (B) is a repeating unit represented by the following general formula (2A): 【Chemistry 5】 (In general formula (2A), R ５ ~R ８ has the same meaning as in the general formula (2).

17. In the general formula (2), R ５ ~R ８ The thermoplastic resin composition according to claim 1 , wherein is a methyl group.

18. In the general formula (3), R １０ and R １１ is a methyl group, and R １２ and R １３ The thermoplastic resin composition according to claim 5, wherein is a hydrogen atom.

19. 2. The thermoplastic resin composition according to claim 1, wherein the viscosity average molecular weight (Mv) of the polycarbonate resin (P1) is in the range of 14,500 to 30,000.

20. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin (P1) has a glass transition temperature of 125°C or higher.

21. The thermoplastic resin composition according to claim 1, wherein the evaluation in a UL94 standard vertical flame test using a 1.0 mm thick test piece prepared using the thermoplastic resin composition is V-0 or V-1.

22. The thermoplastic resin composition according to claim 21, wherein the evaluation in a UL94 standard vertical flame test using a 0.6 mm thick test piece prepared using the thermoplastic resin composition is V-0 or V-1.

23. A thermoplastic resin composition comprising a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2), and a metal salt flame retardant (C1), wherein a test piece having a thickness of 1.0 mm, prepared using the thermoplastic resin composition, is evaluated as V-0 or V-1 in a UL94 vertical flame test. 【Chemistry 6】 (In general formula (1), R １ and R ２ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. １ and R ２ The alkyl groups in R may be bonded to each other to form a ring. ３ and R ４ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 【Chemistry 7】 (In general formula (2), R ５ ~R ８ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

24. R in the general formula (1) ３ and R ４ each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. The thermoplastic resin composition according to claim 23.

25. The thermoplastic resin composition according to claim 23, wherein the evaluation in a UL94 standard vertical flame test using a 0.6 mm thick test piece prepared using the thermoplastic resin composition is V-0 or V-1.

26. An injection-molded article obtained by injection molding the thermoplastic resin composition according to claim 1 or 23.

27. An extrusion molded article obtained by extrusion molding the thermoplastic resin composition according to claim 1 or 23.

28. 28. The extruded article of claim 27, wherein the extruded article is a sheet or film.

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