Thermoplastic resin composition and molded article

Abstract

To provide a thermoplastic resin composition that uses a phosphorus-based flame retardant, has high flame retardancy, and is excellent in heat resistance and flowability. [Solution] A thermoplastic resin composition comprising a polycarbonate resin (P) including a polycarbonate resin (P1) having a repeating unit (A) represented by the following general formula (1) and a specific repeating unit (B), and a phosphorus-based flame retardant (C). TIFF2026166220000031.tif49140 (R 1 to R 2 are each a hydrogen atom, a substituted / unsubstituted alkyl group having 1 to 20 carbon atoms, or an aryl group. The alkyl groups of R 1 and R 2 may be bonded to each other to form a ring. R 3 and R 4 are each a hydrogen atom, or a substituted / unsubstituted alkyl group having 1 to 20 carbon atoms, or an aryl group.)

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition having high flame retardancy and excellent fluidity. The present invention also relates to injection molded articles and extruded articles of this thermoplastic resin composition. [Background technology]

[0002] Thermoplastic resins, such as polycarbonate resin, are widely used in various fields including electrical, electronic, and office automation equipment components, automotive parts, building materials, medical applications, and general merchandise due to their excellent mechanical strength, heat resistance, and transparency.

[0003] Conventionally, thermoplastic resin compositions with high flame retardancy have included not only polycarbonates composed of bisphenol A, but also polycarbonates with a bisphenol C backbone, which have even better flame retardancy.

[0004] Patent Document 1 shows that by adding potassium perfluorobutanesulfonate as a flame retardant to a composition of polycarbonate resin composed of bisphenol A and polycarbonate resin composed of bisphenol C, the composition exhibits a V-0 flame retardancy rating in the UL94 standard vertical combustion test using a 0.8 mm test piece.

[0005] Patent Document 2 shows that by adding a phosphorus-based flame retardant to a polycarbonate resin composed of bisphenol A, excellent flame retardancy is achieved in tests compliant with UL94.

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

[0007] [Patent Document 1] Patent No. 6606083 [Patent Document 2] Japanese Patent Application Publication No. 59-45351 [Patent Document 3] International Publication No. 2021 / 039970 [Overview of the project] [Problems that the invention aims to solve]

[0008] In recent years, there has been a growing demand for molded products that are thinner, smaller, and lighter, and that possess even higher flame retardancy. Therefore, there is a need for compositions that exhibit even better flame retardancy than the conventional thermoplastic 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 organofluorine compound (PFAS) that has been subject to stricter regulations in recent years due to concerns about its impact on the environment and human health. Therefore, the development of thermoplastic resin compositions with high flame retardancy without using fluorine-containing metal salts is expected to become increasingly important in the future, and there is a need to obtain thermoplastic resin compositions that have flame retardancy equivalent to or better than that obtained when using fluorine-containing organic acid metal salt compounds, using fluorine-free organic acid metal salt compounds as flame retardants.

[0010] Under these circumstances, the object of the present invention is to provide a thermoplastic resin composition that has higher flame retardancy and excellent heat resistance and fluidity, using a phosphorus-based flame retardant. [Means for solving the problem]

[0011] As a result of diligent research to solve the above problems, the inventors of the present invention discovered that a thermoplastic resin composition containing a polycarbonate resin having a specific structure and a specific flame retardant is suitable for the above purpose, and thus arrived at the present invention.

[0012] In other words, the gist of this invention is as follows:

[0013] [1] A thermoplastic resin composition comprising a polycarbonate resin (P) 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 phosphorus-based flame retardant (C).

[0014] [ka]

[0015] (In general formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups may be bonded to each other to form a ring. 3 and R 4 Each of these 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 of these 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 repeating units (A) to repeating units (B) in the polycarbonate resin (P) is in a molar ratio of repeating units (A):repeating units (B) = 60:400 to 10:90.

[0019] [3] The thermoplastic resin composition according to [1] or [2], 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.

[0020] [4] The thermoplastic resin composition according to [3], wherein the polycarbonate resin (P1) contains 50 to 100 mass% of the polycarbonate copolymer (PA1).

[0021] [5] The thermoplastic resin composition according to any one of [1] to [4], wherein the phosphorus-based flame retardant (C) is a condensed phosphate ester and / or a phosphazene compound.

[0022] [6] The thermoplastic resin composition according to any one of [1] to [5], wherein the thermoplastic resin composition comprises at least one additive (D) other than the phosphorus-based flame retardant (C).

[0023] [7] The thermoplastic resin composition according to any one of [1] to [6], wherein the thermoplastic resin composition further comprises an elastomer (E).

[0024] [8] In the general formula (1), R 1 and R 2 are methyl groups, or the alkyl groups of R 1 and R 2 are bonded to each other to form a ring represented by the following formula (1a) or (1b), the thermoplastic resin composition according to any one of [1] to [7].

[0025]

Chemical Formula

[0026] [9] The thermoplastic resin composition according to any one of [1] to [8], wherein in the general formula (1), R 3 and R 4 are methyl groups.

[0027]

[10] The thermoplastic resin composition according to any one of [1] to [9], wherein the repeating unit (B) is a repeating unit represented by the following general formula (2A).

[0028] [ka]

[0029] (In general formula (2A), R 5 ~R 8 This is equivalent to the expression in general formula (2) above.

[0030]

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

[10] , wherein is a methyl group.

[0031]

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

[11] , comprising 5 parts by mass or more of polycarbonate resin (P2) containing 95 mol% or more of repeating units (C) represented by the following general formula (3) per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition.

[0032] [ka]

[0033] (In general formula (3), R 10 and R 11 Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. 10 and R 11 The alkyl groups may be bonded to each other to form a ring. 12 and R 13 Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0034]

[13] The thermoplastic resin composition according to

[12] , comprising 40 parts by mass or less of the polycarbonate resin (P2) per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition.

[0035]

[14] In the above general formula (3), R 10 and R 11 is a methyl group, R 12 and R 13 A thermoplastic resin composition according to

[12] or

[13] , wherein is a hydrogen atom.

[0036]

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

[14] , wherein the evaluation in the UL94 standard vertical combustion test using a 0.75 mm thick test piece prepared using the thermoplastic resin composition is V-0 or V-1.

[0037]

[16] In accordance with ISO 1133, the melting viscosity (melt volume rate (MVR)) measured under conditions of a measurement temperature of 300°C and a load of 11.8 N was 7 cm³. 3 A thermoplastic resin composition according to any one of [1] to

[15] , wherein the duration is 10 min or longer.

[0038]

[17] A thermoplastic resin composition according to any one of [1] to

[16] , wherein the DTUL (temperature of deflection under load) measured on an ISO multipurpose test specimen (4 mm thick) under the condition of a load of 1.80 MPa (Method A) in accordance with ISO 75-1 & 2 is 105°C or higher.

[0039]

[18] Notched Charpy impact strength of 6.0 kJ / m² was measured using a 3 mm thick impact resistance specimen according to ISO 179-1, 2, at a temperature of 23°C. 2 The thermoplastic resin composition described in any of [1] to

[17] above.

[0040]

[19] An injection-molded article obtained by injection molding any of the thermoplastic resin compositions described in [1] to

[18] .

[0041]

[20] An extruded article obtained by extruding any of the thermoplastic resin compositions described in [1] to

[18] .

[0042]

[21] The extruded product according to

[20] , wherein the extruded product is a sheet or a film. [Effects of the Invention]

[0043] According to the present invention, a thermoplastic resin composition can be provided that has higher flame retardancy and excellent heat resistance and fluidity by using a non-fluorine-based phosphorus-based flame retardant as the flame retardant. Because the thermoplastic resin composition of the present invention possesses such excellent properties, it can be widely used as a material for manufacturing parts in the automotive, electrical and electronic materials, and other industrial fields. [Modes for carrying out the invention]

[0044] The present invention will be described in detail below with reference to embodiments and examples. The present invention is not limited to the embodiments and examples shown below.

[0045] In this specification, unless otherwise specified, "~" means that the numbers before and after it are included as the lower and upper limits.

[0046] [Thermoplastic resin composition] The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising a polycarbonate resin (P) 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 phosphorus-based flame retardant (C).

[0047] [ka]

[0048] (In general formula (1), R 1 and R 2Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups may be bonded to each other to form a ring. 3 and R 4 Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0049] [ka]

[0050] (In general formula (2), R 5 ~R 8 Each of these independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0051] [Molar ratio of repeating units (A) and repeating units (B) in polycarbonate resin (P)] In the thermoplastic resin composition of the present invention, the content ratio of repeating units (A) and repeating units (B) in the polycarbonate resin (P) is not particularly limited, but the repeating unit (A):repeating unit (B) (molar ratio) is preferably 60:40 to 10:90, particularly 50:50 to 12:88, and especially 40:60 to 15:85. Within this range, the thermoplastic resin composition of the present invention exhibits high flame retardancy, which is preferable.

[0052] [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) and a repeating unit (B) represented by the general formula (2).

[0053] Note that in the general formula (1) representing the repeating unit (A) shown below, R 1 and R 2A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, R 1 and R 2 A ring formed by the bonding of alkyl groups, R 3 and R 4 A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group, and R in general formula (2) representing the repeating unit (B). 5 ~R 8 Examples of substituted or unsubstituted C1 to C20 alkyl groups and substituted or unsubstituted aryl groups include those exemplified as substituents in the general formula (3) representing the polycarbonate resin (P2) described later, but are preferably as follows.

[0054] <Repeating Unit (A)> The repeating unit (A) is represented by the following general formula (1).

[0055] [ka]

[0056] (In general formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups may be bonded to each other to form a ring. 3 and R 4 Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0057] In general formula (1), R 1 and R 2 From the viewpoint of improving heat resistance, a methyl group or R 1 and R 2 It is preferable that the alkyl groups bond to each other to form a ring represented by the following formula (1a) or (1b). From the viewpoint of balancing heat resistance and fluidity, R1 and R 2 It is particularly preferable that the group is a methyl group.

[0058] [ka]

[0059] In general formula (1), R 3 and R 4 From the viewpoint of improving flame retardancy and dielectric properties, it is preferable that the group be a methyl group.

[0060] In other words, it is particularly preferable that the repeating unit (A) is a repeating structural unit derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes abbreviated as "BPC"), and is represented by the following formula (4).

[0061] [ka]

[0062] The polycarbonate resin (P1) may contain only one type of repeating unit (A), or it may contain two or more types.

[0063] <Repeating Unit (B)> The repeating unit (B) is represented by the following general formula (2).

[0064] [ka]

[0065] (In general formula (2), R 5 ~R 8 Each of these independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0066] In the above general formula (2), R 5 ~R 8There are no restrictions on the replacement position, but from the viewpoint of improving impact resistance, the replacement position is particularly preferable to be that of the general formula (2A) below.

[0067] [ka]

[0068] (In general formula (2A), R 5 ~R 8 This is equivalent to the expression in general formula (2) above.

[0069] The repeating unit (B) is, in particular, preferably a repeating unit represented by the following general formula (5), which is derived from 4,4-methylenebis(2,6-dimethylphenol) (hereinafter sometimes abbreviated as "TmBPF").

[0070] [ka]

[0071] The polycarbonate resin (P1) may contain only one type of repeating unit (B), or it may contain two or more types.

[0072] <Other repeating units> The polycarbonate resin (P1) may contain one or more types of repeating units other than repeating unit (A) and repeating unit (B), to the extent that it does not impair the purpose of the present invention. Examples of other repeating units include repeating units derived from aromatic dihydroxy compounds such as 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobindan.

[0073] In order to reliably obtain the effects of the present invention by including repeating unit (A) and repeating unit (B), with the total carbonate structural units in the polycarbonate resin (P1) being 100 mol%, the sum of repeating unit (A) and repeating unit (B) is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more, and this ratio may be 100 mol%.

[0074] <Preferred embodiment of polycarbonate resin (P1)> The polycarbonate resin (P1) is preferably a polycarbonate copolymer (P1A) in which the content ratio of repeating units (A) to repeating units (B) is in a molar ratio of repeating units (A):repeating units (B) = 50:50 to 10:90, and it is preferable that the polycarbonate resin (P1) contains 50 to 100% by mass of this polycarbonate copolymer (P1A).

[0075] <Molecular weight of polycarbonate resin (P1)> There are no particular restrictions on the molecular weight of the polycarbonate resin (P1), but it is preferable that the viscosity-average molecular weight (Mv) calculated from the solution viscosity is 14,500 or more. When the viscosity-average molecular weight is above the lower limit of the above value, it is preferable because the heat resistance and flame retardancy of the thermoplastic resin composition and molded articles 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.

[0076] 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 below 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.

[0077] The viscosity-average molecular weight (Mv) of polycarbonate resin (P1) is determined by using methylene chloride as the solvent, calculating the intrinsic viscosity (intrinsic viscosity) [η] (unit: dL / g) at 20°C using an Ubbelohde viscometer, and then using Schnell's viscosity formula, i.e., η = 1.23 × 10⁻¹⁰ -4 Mv 0.83 It refers to the value calculated from. Intrinsic viscosity (intrinsic viscosity) [η] is a value calculated by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dL) and using the following formula.

[0078]

number

[0079] The same applies to the viscosity-average molecular weight (Mv) of the polycarbonate resin (P2) and the thermoplastic resin composition of the present invention, as described later.

[0080] <Glass transition temperature (Tg) of polycarbonate resin (P1)> There are no restrictions on the glass transition temperature (Tg) of the polycarbonate resin (P1), but it is preferably between 125 and 200°C. If the Tg is 125°C or higher, the heat resistance of the thermoplastic resin composition and molded articles of the present invention is improved. On the other hand, if the Tg of the polycarbonate resin (P1) is 200°C or lower, the fluidity of the thermoplastic resin composition of the present invention containing the polycarbonate resin (P1) is good, and high moldability can be obtained. For this reason, the glass transition temperature (Tg) of the polycarbonate resin (P1) is preferably between 125 and 200°C.

[0081] The Tg of the polycarbonate resin (P1), the polycarbonate resin (P2) described later, and the thermoplastic resin composition of the present invention is measured by the method described in the Examples section below.

[0082] <Method for producing polycarbonate resin (P1)> Polycarbonate resin (P1) can be manufactured by conventional polymerization methods, and these polymerization methods are not particularly limited. Examples of polymerization methods include interfacial polymerization, molten transesterification, pyridine polymerization, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Particularly preferred methods among these will be described in detail below.

[0083] (interfacial polymerization method) In the interfacial polymerization method, polycarbonate resin is obtained by reacting a dihydroxy compound and a carbonate-forming compound in the presence of an organic solvent and an alkaline aqueous solution that are inert to the reaction, usually maintaining the pH at 9 or higher, and then carrying out interfacial polymerization in the presence of a polymerization catalyst. Molecular weight modifiers (end-terminating agents) may be present in the reaction system as needed, and antioxidants may be present to prevent oxidation of the dihydroxy compound.

[0084] Organic solvents that are inert to the reaction are not particularly limited, but examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; and so on. One type of organic solvent may be used, or two or more types may be used in any combination and ratio.

[0085] The alkaline compounds contained in the alkaline aqueous solution are not particularly limited, but examples include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate, as well as alkaline earth metal compounds. Among these, sodium hydroxide and potassium hydroxide are preferred. Alkaline compounds may be used individually, or two or more may be used in any combination and ratio.

[0086] There are no restrictions on the concentration of the alkali compound in the alkaline aqueous solution, but typically, to control the pH of the alkaline aqueous solution to 10-12, the alkali compound concentration is used at 5-10% by mass. Furthermore, for example, when bubbling in phosgene, in order to control the pH of the aqueous phase to 10-12, preferably 10-11, it is preferable to set the molar ratio of the raw material dihydroxy compound to the alkali compound to 1:1.9 or higher, more preferably 1:2.0 or higher, and more preferably 1:3.2 or lower, more preferably 1:2.5 or lower.

[0087] As the starting material dihydroxy compound, at least one dihydroxy compound is used that can produce repeating units (A) and (B) in reaction with a carbonate-forming compound.

[0088] Carbonyl halides are preferably used as carbonate-forming compounds. Among these, phosgene is preferred. The method using phosgene is specifically called the phosgene method.

[0089] Polymerization catalysts are not particularly limited, but examples 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; salts of guanidine; and the like. The polymerization catalyst may be used alone, or two or more may be used in any combination and ratio.

[0090] Molecular weight modifiers are not particularly limited, but examples include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; and phthalimides. Aromatic phenols are preferred among these.

[0091] Examples of such aromatic phenols include phenol, on-butylphenol, mn-butylphenol, pn-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, pn-nonylphenol Examples include phenols, 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 with an average of 12 to 35 carbon atoms in 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, etc. Among these, pt-butylphenol, p-phenylphenol, and p-cumylphenol are preferably used. The molecular weight adjusting agent may be used alone, or two or more may be used in any combination and ratio.

[0092] The amount of molecular weight adjusting agent used is not particularly limited, but for example, it is 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 dihydroxy compound raw material.

[0093] While not particularly limited, examples of antioxidants include hindered phenol-based antioxidants. Specific examples 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]phosphoate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6- Examples include triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[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-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[0094] 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. Examples of commercially available phenolic antioxidants include BASF's "Irganox 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60."

[0095] The antioxidant may be used alone, or two or more may be used in any combination and ratio.

[0096] 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, per 100 parts by mass of the raw material dihydroxy compound. By using an amount of antioxidant above the lower limit, the antioxidant effect will be sufficient. The amount of antioxidant used is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the raw material dihydroxy compound. By using an amount of antioxidant below the upper limit, gas generation during injection molding can be suppressed.

[0097] The order in which the reaction substrate (reaction raw material), reaction solvent (organic solvent), catalyst, additives, etc. are mixed during the reaction is arbitrary as long as the desired polycarbonate resin is obtained, and any appropriate order can be 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 between the starting material dihydroxy compound and phosgene (phosgenation) and the start of the polymerization reaction.

[0098] 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 (e.g., 10 minutes) to several hours (e.g., 6 hours).

[0099] (Fresh transesterification method) In the molten transesterification method, for example, a transesterification reaction is carried out between a carbonate ester and a starting dihydroxy compound. The raw material dihydroxy compound is the same as that used in the interfacial polymerization method.

[0100] Examples of carbonate esters include compounds represented by the following general formula (I), such as aryl carbonates, dialkyl carbonates, biscarbonate forms of dihydroxy compounds, monocarbonate forms of dihydroxy compounds, and carbonate forms of dihydroxy compounds such as cyclic carbonates.

[0101] [ka]

[0102] In the above general formula (I), R 101 and R 102 Each of these independently represents an alkyl group, an aryl group, or an arylalkyl group having 1 to 30 carbon atoms. Hereinafter, R 101 and R 102 However, when it is an alkyl group or arylalkyl group, it is sometimes called a dialkyl carbonate, and when it is an aryl group, it is sometimes called a diaryl carbonate. In particular, from the viewpoint of reactivity with dihydroxy compounds, R 101 and R 102 Both are preferably aryl groups, and more preferably diaryl carbonates represented by the following general formula (II).

[0103] [ka]

[0104] In the above general formula (II), R 103 and R 104 Each of these is independently a halogen atom, a nitro group, a cyano group, a C1-C20 alkyl group, a C1-C20 alkoxycarbonyl group, a C4-C20 cycloalkyl group, or a C6-C20 aryl group. x and y each independently represent an integer from 0 to 5.

[0105] 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"), diaryl carbonates (which may have substituents) such as 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 ditril carbonate. Among these, diphenyl carbonate is preferred. These carbonate esters can be used individually or in combination of two or more.

[0106] The carbonate ester may be substituted with a dicarboxylic acid or dicarboxylic acid ester in an amount of preferably 50 mol% or less, and 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.

[0107] The ratio of the raw material dihydroxy compound to the carbonate ester is arbitrary as long as the desired polycarbonate resin can be obtained, however, it is preferable to use these carbonate esters in excess of the raw material dihydroxy compound when polymerizing them with the dihydroxy compound. The amount of the carbonate ester is preferably 1.01 times (molar ratio) or more, and more preferably 1.02 times (molar ratio) or more, relative to the dihydroxy compound. By setting the molar ratio to above the lower limit mentioned above, the resulting polycarbonate resin will have good thermal stability. The amount of the carbonate ester is preferably 1.30 times (molar ratio) or less relative to the dihydroxy compound, and more preferably 1.20 times (molar ratio) or less. By keeping the molar ratio below the above upper limit, reactivity is improved, resulting in good productivity of polycarbonate resin having the desired molecular weight. Furthermore, the amount of residual carbonate ester in the resin is reduced, which suppresses odor generation during molding and in the molded product, making it preferable.

[0108] When producing polycarbonate resin by the molten transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, alkali metal compounds and / or alkaline earth metal compounds are preferred. As an auxiliary, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. A single transesterification catalyst may be used, or two or more may be used in any combination and ratio.

[0109] In the molten transesterification process, the reaction temperature is not particularly limited, but is usually between 100 and 320°C. The pressure during the reaction is not particularly limited, but is usually under reduced pressure conditions of 2 mmHg or less. In terms of the specific procedure, the melt polycondensation reaction can be carried out under the aforementioned conditions while removing by-products.

[0110] Polycarbonate resin (P1) and the polycarbonate resin (P2) described later are significantly affected by thermal history and oxidation in the presence of an alkaline catalyst, leading to deterioration of color. Therefore, it is preferable to keep the reaction temperature below 320°C and to select reduced pressure conditions with a lower limit of approximately 0.05 mmHg to prevent oxygen leakage from the equipment due to excessive reduced pressure.

[0111] The reaction can be carried out using either a batch or continuous method. In the batch method, the order in which the reaction substrate, reaction solvent, catalyst, additives, etc. are mixed is arbitrary as long as the desired polycarbonate resin is obtained, and any appropriate order can be set.

[0112] In the molten transesterification process, a catalyst deactivator may be used as needed. Any compound that neutralizes the transesterification catalyst can be used as the catalyst deactivator. Examples include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc. The catalyst deactivator may be a single type, or two or more types may be used in any combination and ratio.

[0113] The amount of 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, and usually 50 equivalents or less, preferably 10 equivalents or less, and more preferably 8 equivalents or less, relative to the transesterification catalyst. The amount of catalyst deactivator used is usually 1 ppm or more and 100 ppm or less, and preferably 50 ppm or less, relative to the polycarbonate resin.

[0114] <Polycarbonate resin (P1) content> In the thermoplastic resin composition of the present invention, the content of polycarbonate resin (P1) is preferably 25 parts by mass or more per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition of the present invention, in order to reliably obtain the effects of improved flame retardancy, heat resistance, and impact resistance due to the inclusion of polycarbonate resin (P1). From this viewpoint, the content of polycarbonate resin (P1) is more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. The thermoplastic resin composition of the present invention may contain only polycarbonate resin (P1) as the thermoplastic resin (polycarbonate resin (P1) content of 100 parts by mass). The thermoplastic resin composition of the present invention may contain only one type of polycarbonate resin (P1), or it may contain two or more types of repeating units (A) and (B) with different types and compositions.

[0115] In this invention, the thermoplastic resin in the thermoplastic resin composition of the present invention is the sum of the polycarbonate resin (P1), the polycarbonate resin (P2) described later which may be included as needed, and other thermoplastic resins.

[0116] [Phosphorus-based flame retardant (C)] The thermoplastic resin composition of the present invention contains a phosphorus-based flame retardant (C). The thermoplastic resin composition of the present invention contains a polycarbonate resin (P1) having a repeating unit (A) represented by the general formula (1) and a repeating unit (B) represented by the general formula (2), and a phosphorus-based flame retardant (C), thereby improving flame retardancy, heat resistance, and fluidity in a well-balanced manner.

[0117] As the phosphorus-based flame retardant (C), any compound containing phosphorus in its molecule may be a low-molecular-weight compound, an oligomer, or a polymer. However, from the viewpoint of thermal stability, phosphate ester compounds represented by the following general formula (6) or phosphazene compounds represented by the following general formula (7) or (8) are preferred. When using phosphate ester compounds, it is more preferable to use condensed phosphate ester compounds from the viewpoint of improving flame retardancy. These phosphorus-based flame retardants (C) may be used individually or in combination of two or more types.

[0118] [ka]

[0119] <Phosphate ester compounds> The phosphate ester compound represented by the above general formula (6) may be a mixture of compounds having different k values. In the case of a mixture of condensed phosphate esters with different k values, k is the average value of the mixture. k is usually an integer between 0 and 5. In the case of a mixture of compounds with different k values, the average k value is preferably in the range of 0.5 to 2, more preferably 0.6 to 1.5, even more preferably 0.8 to 1.2, and particularly preferably 0.95 to 1.15.

[0120] Also, X 1 This group exhibits a divalent arylene group and is a divalent group derived from dihydroxy compounds such as resorcinol, hydroquinone, bisphenol A, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. Of these, divalent groups derived from resorcinol, hydroquinone, bisphenol A, and 3,3'-dihydroxybiphenyl are particularly preferred, and divalent groups derived from resorcinol and hydroquinone are more preferred.

[0121] Furthermore, in general formula (6), p, q, r, and s each represent 0 or 1, with 1 being preferred.

[0122] Also, R 21 , R 22 , R 23 and R 24 Each of these represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms that may be substituted with an alkyl group. Examples of such aryl groups include phenyl, cresyl, xylyl, isopropylphenyl, butylphenyl, tert-butylphenyl, di-tert-butylphenyl, and p-cumylphenyl groups, but phenyl, cresyl, and xylyl groups are more preferred, and phenyl is particularly preferred.

[0123] Specific examples of phosphate ester compounds represented by general formula (6) include: Aromatic phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis-(tert-butylphenyl)phenyl phosphate, tris-(tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl) phosphate; Condensed phosphate esters such as hydroquinone bis-diphenyl phosphate, resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), and biphenyl bis-diphenyl phosphate; These are some examples. Among these, hydroquinone bis-diphenyl phosphate and resorcinol bis-diphenyl phosphate (RDP) are particularly preferred.

[0124] The acid value of the phosphate ester compound represented by general formula (6) is preferably 0.2 mg KOH / g or less, more preferably 0.15 mg KOH / g or less, even more preferably 0.1 mg KOH or less, and particularly preferably 0.05 mg KOH / g or less. The lower limit of this acid value can be substantially set to 0. On the other hand, the half-ester content is more preferably 1.1% by mass or less, and even more preferably 0.9% by mass or less. If the acid value exceeds 0.2 mg KOH / g or the half-ester content exceeds 1.1% by mass, it leads to a decrease in the thermal stability and hydrolysis resistance of the thermoplastic resin composition of the present invention.

[0125] In addition to those mentioned above, phosphate ester compounds also naturally include 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,3-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,4-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, polyester resins, polycarbonate resins, or epoxy resins containing phosphate ester moieties.

[0126] <Phosphazene compounds> Examples of phosphazene compounds represented by the above general formulas (7) and (8) include phenoxyphosphazene, (poly)tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o,m-tolyloxyphosphazene, o,p-tolyloxyphosphazene, m,p-tolyloxyphosphazene, o,m,p-tolyloxyphosphazene, etc.), and cyclic and / or linear C(C) such as (poly)xylyloxyphosphazene. 1-6 Alkyl C 6-20 aryloxyphosphazenes, (poly)phenoxytriloxyphosphazenes (e.g., phenoxy-o-tolyloxyphosphazene, phenoxy-m-tolyloxyphosphazene, phenoxy-p-tolyloxyphosphazene, phenoxy-o,m-tolyloxyphosphazene, phenoxy-o,p-tolyloxyphosphazene, phenoxy-m,p-tolyloxyphosphazene, phenoxy-o,m,p-tolyloxyphosphazene, etc.), (poly)phenoxyxylyloxyphosphazene, (poly)phenoxytriloxyxylyloxyphosphazene, and other cyclic and / or linear C12C 6-20 Aryl C 1-10 Alkyl C 6-20 Examples include aryloxyphosphazenes. Of these, preferably, cyclic and / or linear phenoxyphosphazene, cyclic and / or linear C 1-3 Alkyl C 6-20 Aryloxyphosphazene, C 6-20 Aryloxy C1-3 Alkyl C 6-20 It is an aryloxyphosphazene (for example, cyclic and / or linear tolyloxyphosphazene, cyclic and / or linear phenoxytolylphenoxyphosphazene, etc.).

[0127] R in the cyclic phosphazene compound represented by general formula (7) 25 and R 26 may be the same or different, and each represents an aryl group or an alkylaryl group. Examples of such aryl groups or alkylaryl groups include phenyl groups, naphthyl groups, methylphenyl groups, benzyl groups and the like. Among them, R 25 and R 26 A cyclic phenoxyphosphazene in which is a phenyl group is particularly preferred. Examples of such cyclic phenoxyphosphazene compounds include, from a mixture of cyclic and linear chlorophosphazenes obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130°C, after taking out cyclic chlorophosphazenes such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, and decachlorocyclopentaphosphazene, and then substituting with phenoxy groups, compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaphenoxycyclopentaphosphazene can be mentioned.

[0128] Further, in general formula (7), t represents an integer of 3 to 25, among which compounds where t is an integer of 3 to 8 are preferred, and a mixture of compounds with different t values may also be used. Among them, a mixture of compounds in which the content of t=3 is 50% by mass or more, the content of t=4 is 10 to 40% by mass, and the total content of t=5 or more is 30% by mass or less is preferred.

[0129] In general formula (8), R 27 and R 28 may be the same or different, and each represents an aryl group or an alkylaryl group. Examples of such aryl groups or alkylaryl groups include phenyl groups, naphthyl groups, methylphenyl groups, benzyl groups and the like, and R 27 and R28 A chain-like phenoxyphosphazene in which the group is a phenyl group is particularly preferred. Examples of such linear phenoxyphosphazene compounds include those obtained by oxidative polymerization of hexachlorocyclotriphosphazene obtained by the above method at a temperature of 220 to 250°C, and then substituting the resulting linear dichlorophosphazene with a degree of polymerization of 3 to 10,000 with a phenoxy group.

[0130] Also, R 29 -N=P(OR 27 )3 units, -N=P(OR 28 )3 units, -N=P(O)OR 27 Base, -N=P(O)OR 28 It shows at least one selected from the elements, R 30 -P(OR 27 ) 4 units, -P(OR 28 ) 4 units, -P(O)(OR 27 )2 units, -P(O)(OR 28 ) Indicates at least one type selected from the two units.

[0131] Furthermore, in general formula (8), u represents an integer between 3 and 10,000, preferably between 3 and 1,000, more preferably between 3 and 100, and even more preferably between 3 and 25.

[0132] Furthermore, the phosphazene compound may be a cross-linked phosphazene compound in which a portion of the compound is cross-linked. Having such a cross-linked structure tends to improve heat resistance. Examples of such crosslinked phosphazene compounds include compounds having a crosslinked structure of a 4,4'-diphenylene group, such as a crosslinked structure of a 4,4'-sulfonyldiphenylene (bisphenol S residue) represented by the following general formula (9), for example, compounds having a crosslinked structure of a 2,2-(4,4'-diphenylene)isopropylidene group, compounds having a crosslinked structure of a 4,4'-oxydiphenylene group, compounds having a crosslinked structure of a 4,4'-thiodiphenylene group, and other compounds having a crosslinked structure of a 4,4'-diphenylene group.

[0133] [ka] (In general formula (9), X 2 (where v is -C(CH3)2-, -SO2-, -S-, or -O-, and v is 0 or 1.)

[0134] Furthermore, as a crosslinked phosphazene compound, R in general formula (7) 25 and R 26 A cyclic phenoxyphosphazene compound in which is a phenyl group is crosslinked by a crosslinking group represented by the general formula (9), or a crosslinked phenoxyphosphazene compound in which R is represented by the general formula (8). 27 and R 28 A crosslinked phenoxyphosphazene compound, in which a chain-like phenoxyphosphazene compound having a phenyl group is crosslinked by a crosslinking group represented by the above general formula (9), is preferred from the viewpoint of flame retardancy, and a crosslinked phenoxyphosphazene compound, in which a cyclic phenoxyphosphazene compound is crosslinked by a crosslinking group represented by the above general formula (9), is more preferred.

[0135] Furthermore, the phenylene group content in the crosslinked phenoxyphosphazene compound is typically 50 to 99.9%, preferably 70 to 90%, based on the total number of phenyl and phenylene groups in the cyclic phosphazene compound represented by general formula (7) and / or the linear phenoxyphosphazene compound represented by general formula (8). It is also particularly preferable that the crosslinked phenoxyphosphazene compound does not have free hydroxyl groups within its molecule.

[0136] In the present invention, it is preferable from the viewpoint of flame retardancy and mechanical properties that the phosphazene compound is at least one selected from the group consisting of a cyclic phenoxyphosphazene compound represented by the general formula (7) and a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound represented by the general formula (8) with a crosslinking group.

[0137] In the thermoplastic resin composition of the present invention, the content of the phosphorus-based flame retardant (C) is preferably 1 part by mass or more per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition of the present invention. If the content of the phosphorus-based flame retardant (C) is above the above lower limit, high flame retardancy and fluidity can be obtained by including the phosphorus-based flame retardant (C). On the other hand, the content of the phosphorus-based flame retardant (C) is preferably 20 parts by mass or less per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition of the present invention. If the content of the phosphorus-based flame retardant (C) is below the above upper limit, other physical properties such as heat resistance and impact resistance will not be impaired by excessive inclusion of the phosphorus-based flame retardant (C). From this viewpoint, the content of the phosphorus-based flame retardant (C) in the thermoplastic resin composition of the present invention is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and most preferably 7 parts by mass or more, per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition. Furthermore, the content of the phosphorus-based flame retardant (C) in the thermoplastic resin composition of the present invention is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, and most preferably 9 parts by mass or less, per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition.

[0138] [Polycarbonate resin (P2)] The thermoplastic resin composition of the present invention may contain, together with the aforementioned polycarbonate resin (P1), a polycarbonate resin (P2) containing a repeating unit (C) represented by the following general formula (3). By including the polycarbonate resin (P2), effects such as improved impact resistance and fluidity can be obtained.

[0139] [ka]

[0140] (In general formula (3), R 10 and R 11Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. 10 and R 11 The alkyl groups may be bonded to each other to form a ring. 12 and R 13 Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0141] R in general formula (3) 10 and R 11 , and R 12 and R 13 Specific examples of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms include the following: Methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group; Methyl ethyl group, methyl propyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methyl heptyl group, methyl octyl group, methyl nonyl group, methyl decyl group, methyl undecyl group, methyl dodecyl group, methyl tridecyl group, methyl tetradecyl group, methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group, methyl nonadecyl 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.

[0142] R is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in the general formula (3) above. 10 and R 11 These elements may be bonded to each other to form a ring, and specific examples of the rings formed include cyclohexane rings and cyclododecane rings.

[0143] R 10 and R 11 , and R 12 and R 13 Specific examples of substituted or unsubstituted aryl groups include phenyl group, tolyl group, 4-methylphenyl group, naphthyl group, and the like.

[0144] R 10 and R 11Among these, hydrogen atoms, methyl groups, and ethyl groups are preferred, hydrogen atoms and methyl groups are more preferred, and especially R 10 and R 11 It is preferable that both are methyl groups.

[0145] R 12 and R 13 Preferably, the group can be 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, a tolyl group, and so on. Among these, hydrogen atoms and methyl groups are preferred, and it is most preferable that both be hydrogen atoms.

[0146] The polycarbonate resin (P2) may contain repeating units other than the repeating unit (C) represented by the general formula (3) above. However, in order to obtain effects such as improved impact resistance and improved fluidity due to the inclusion of the repeating unit (C), it is preferable that the polycarbonate resin (P2) contains 50 mol% or more of the repeating unit (C) in the total carbonate structural units contained in the polycarbonate resin (P2), more preferably 60 mol% or more, even more preferably 75 mol% or more, and most preferably 95 to 100 mol%.

[0147] Other repeating units that the polycarbonate resin (P2) may contain besides repeating unit (C) include those listed above as examples of other repeating units that the polycarbonate resin (P1) may contain but are not included in repeating unit (C), or either repeating unit (A) or repeating unit (B). As for the polycarbonate resin (P2), bisphenol A type polycarbonate resin (A-PC) (in the general formula (3) above, R 10 and R 11 is a methyl group, R 12 and R 13A polycarbonate resin having repeating units (C) in which hydrogen atoms are present is preferred from the viewpoint of impact resistance and flame retardancy of the thermoplastic resin composition.

[0148] <Molecular weight of polycarbonate resin (P2)> The molecular weight of 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, based on the viscosity-average molecular weight (Mv) calculated from the solution viscosity, for the same reasons as for polycarbonate resin (P1).

[0149] <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 case of the polycarbonate resin (P1).

[0150] <Method for producing polycarbonate resin (P2)> Polycarbonate resin (P2) can be manufactured in the same manner as polycarbonate resin (P1) using a dihydroxy compound capable of generating repeating units (C).

[0151] <Polycarbonate resin (P2) content> When the thermoplastic resin composition of the present invention contains polycarbonate resin (P2), from the viewpoint of effectively obtaining the aforementioned effects due to the inclusion of polycarbonate resin (P2), the content of 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 thermoplastic resin in the thermoplastic resin composition of the present invention. On the other hand, from the viewpoint of ensuring the content of polycarbonate resin (P1) and reliably obtaining the flame retardancy, heat resistance, and impact resistance effects of polycarbonate resin (P1), the content of polycarbonate resin (P2) is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 25 parts by mass or less, per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition of the present invention.

[0152] When the thermoplastic resin composition of the present invention contains polycarbonate resin (P2), it may contain only one type of polycarbonate resin (P2), or it may contain two or more types of repeating units (C) that differ in type, content, physical properties, etc.

[0153] [Elastomer (E)] The thermoplastic resin composition of the present invention may also preferably contain elastomer (E). As the elastomer (E), a copolymer obtained by graft copolymerizing a rubber component with a monomer component that can copolymerize with it is preferred.

[0154] The method for producing such graft copolymers may be any of the following: bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and the copolymerization method may be single-stage grafting or multi-stage grafting.

[0155] The above rubber components typically have a glass transition temperature of 0°C or lower, preferably -20°C or lower, and more preferably -30°C or lower. Specific examples of rubber components include polybutadiene rubber, polyisoprene rubber, polyalkyl acrylate rubber such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymer, silicone rubber such as organopolysiloxane rubber, butadiene-acrylic composite rubber, composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α-olefin rubber such as ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber, ethylene-acrylic rubber, and fluororubber. These may be used individually or in combination of two or more. Among these, polybutadiene rubber, polyalkyl acrylate rubber, composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferred in terms of mechanical properties and surface appearance.

[0156] Specific examples of monomer components that can be graft copolymerized with rubber components include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; and α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (e.g., maleic anhydride). These monomer components may be used individually or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferred in terms of mechanical properties and surface appearance, and (meth)acrylic acid ester compounds are more preferred. Specific examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate.

[0157] The elastomer (E) used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. In particular, a core / shell type graft copolymer is preferred, which has a core layer consisting of at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, and composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, and a shell layer formed by copolymerizing (meth)acrylic acid ester around it, and a core / shell type elastomer having a core made of composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber is particularly preferred. In the above core / shell type graft copolymer, it is preferable that it contains 40% by mass or more of the rubber component, and more preferably 60% by mass or more. It is also preferable that it contains 10% by mass or more of the (meth)acrylic acid component.

[0158] Preferred specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic / butadiene rubber copolymer, methyl methacrylate-acrylic / butadiene rubber-styrene copolymer, and methyl methacrylate-(acrylic / silicone rubber) copolymer. Such rubbery polymers may be used individually or in combination of two or more.

[0159] When the thermoplastic resin composition of the present invention contains the above-mentioned elastomer (E), it is preferable that the elastomer (E) is contained in an amount of 0.5 to 40 parts by mass, particularly 1 to 30 parts by mass, and especially 2 to 20 parts by mass, per 100 parts by mass of the thermoplastic resin in the thermoplastic resin composition of the present invention.

[0160] [Other ingredients] The thermoplastic resin composition of the present invention may contain other components besides polycarbonate resin (P1), polycarbonate resin (P2), phosphorus-based flame retardant (C), and elastomer (E), as needed, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resin (P1) and polycarbonate resin (P2), and various additives (D) other than phosphorus-based flame retardant (C) and elastomer (E). Other ingredients may be present in any single form, or in any combination and ratio of two or more forms.

[0161] Examples of resins other than polycarbonate resin (P1) and 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 resin (PTT resin), and polybutylene terephthalate resin (PBT resin); Styrene-based 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.

[0162] The thermoplastic resin composition of the present invention may contain one of the resins other than the polycarbonate resin (P1) and polycarbonate resin (P2) described above, and may contain two or more resins in any combination and ratio.

[0163] When the thermoplastic resin composition of the present invention contains resins other than polycarbonate resin (P1) and polycarbonate resin (P2), it is preferable that the content of polycarbonate resin (P1) per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition of the present invention be equal to or greater than the aforementioned lower limit, in order to more effectively obtain the effects of the present invention due to the inclusion of polycarbonate resin (P1).

[0164] Examples of additives (D) other than phosphorus-based flame retardants (C) include other flame retardants (C), heat stabilizers, antioxidants, mold release agents, ultraviolet absorbers, impact resistance modifiers, dyes and pigments, anti-dripping agents, antistatic agents, anti-fogging agents, lubricants, anti-blocking agents, flow modifiers, plasticizers, dispersants, antibacterial agents, glass fibers, carbon fibers, inorganic fillers, and organic fibers. The thermoplastic resin composition of the present invention may contain one of these additives (D), or two or more may be contained in any combination and ratio.

[0165] 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), it is preferable that the content of each additive (D) be 0.01 to 1.0 part by mass per 100 parts by mass of thermoplastic resin in the thermoplastic resin composition of the present invention, and the total amount of each additive (D) be 2.0 parts by mass or less.

[0166] [Physical properties of thermoplastic resin compositions] <Flame-retardant> In the UL94 standard vertical combustion test using a 0.75 mm thick test specimen prepared using the thermoplastic resin composition of the present invention, the evaluation is preferably V-0 or V-1, and more preferably V-0. In other words, a major feature of the thermoplastic resin composition of the present invention is that it exhibits the above-mentioned high flame retardancy in an extremely thin test piece of 0.75 mm thickness using a phosphorus-based flame retardant (C). The specific measurement method for the UL94 standard vertical combustion test is as described in the Examples section below. In this UL94 standard vertical combustion test, the total burning time is preferably 50 seconds or less, the maximum burning time is preferably 30 seconds or less, particularly preferably 10 seconds or less, and the number of dripping rods is preferably 0.

[0167] <Liquidity> The thermoplastic resin composition of the present invention has a melt viscosity (melt volume rate (MVR)) of 7 cm² as measured by the method described in the Examples section below. 3 Preferably 10 min or longer, 9 cm 3 It is more preferable that the MVR is 10 min or more. If the MVR is above the lower limit, excellent fluidity and good moldability can be obtained. On the other hand, the MVR of the thermoplastic resin composition of the present invention is 25 cm from the viewpoint of flame retardancy stabilization. 3 Preferably 10 min or less, 20 cm 3 Less than 10 minutes is preferable.

[0168] <Heat resistance> From the viewpoint of heat resistance, the thermoplastic resin composition of the present invention preferably has a load deflection temperature (DTUL) of 105°C or higher, and more preferably 107°C or higher, as measured by the method described in the Examples section below. On the other hand, from the viewpoint of improving moldability, this load deflection temperature (DTUL) is preferably 130°C or lower, and more preferably 120°C or lower.

[0169] <Glass transition temperature (Tg)> While there are no restrictions on the glass transition temperature (Tg) of the thermoplastic resin composition of the present invention, it is preferably between 125 and 200°C. If the Tg is 125°C or higher, the heat resistance of the thermoplastic resin composition and molded articles of the present invention is improved. On the other hand, if the Tg is 200°C or lower, the fluidity 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 between 125 and 200°C.

[0170] <Molecular weight> There are no particular restrictions on the molecular weight of the thermoplastic resin composition of the present invention, but it is preferable that the viscosity-average molecular weight (Mv) calculated from the solution viscosity is 14,500 or more. When the viscosity-average molecular weight is above the lower limit of the above value, it is preferable because the heat resistance and flame retardancy of the thermoplastic resin composition and molded articles of the present invention are improved. From this viewpoint, 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.

[0171] 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 below the above upper limit, the thermoplastic resin composition of the present invention tends to have good fluidity, 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.

[0172] <Impact Resistance> There are no particular limitations on the impact resistance of the thermoplastic resin composition of the present invention, but the notched Charpy impact strength measured by the method described in the Examples section below should be 2 kJ / m 2 It is preferable that the above is true. From the viewpoint of increasing the toughness of the molded article, the notched Charpy impact strength is more preferably 2.52 kJ / m 2 The above is preferable, and more preferably 5.52 kJ / m 2The above is the most preferred, and is particularly preferably 6.0 kJ / m 2 The above is the most preferable, and in particular, 7.02 kJ / m 2 The above is the most preferred value, and most preferably 9.02 kJ / m³ 2 That's all.

[0173] [Method for producing thermoplastic resin compositions] There are no limitations on the method for producing the thermoplastic resin composition of the present invention, and a wide range of known methods for producing thermoplastic resin compositions can be employed. Specifically, one method involves melt-kneading a polycarbonate resin (P1), a phosphorus-based flame retardant (C), and, if necessary, a polycarbonate resin (P2) or other resins and additives (D) in a mixer such as a Banbury mixer, rolls, a single-screw extruder, a twin-screw extruder, or a kneader.

[0174] [Molded products] To produce a molded article using the thermoplastic resin composition of the present invention, the pellets obtained by pelletizing the thermoplastic resin composition produced as described above may be molded into a molded article using various molding methods, or the thermoplastic resin composition of the present invention, which has been melt-kneaded in an extruder, may be directly molded into a molded article without going through pellets.

[0175] There are no particular limitations on the shape of the molded article of the present invention, and it can be appropriately selected according to the application and purpose of the molded article. Examples include plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, and panel-shaped articles. Furthermore, for example, it may have an uneven surface or a three-dimensional shape with a curved surface. When used as a sheet, film, or plate, it may be a multilayer laminate formed by laminating it with other resin sheets.

[0176] The method for molding the molded product is not particularly limited, and conventionally known molding methods can be used. Examples include injection molding, injection compression molding, extrusion molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow 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, lamination molding, and press molding. Of these, injection molding or extrusion molding is particularly preferred.

[0177] 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. Setting the molding temperature above the lower limit improves fluidity and moldability. The molding temperature when molding the thermoplastic resin composition of the present invention is preferably 350°C or lower, and particularly preferably 320°C or lower. Setting the molding temperature below the upper limit improves the color tone of the thermoplastic resin composition.

[0178] When performing injection molding or extrusion molding, pigments, dyes, mold release agents, heat stabilizers, etc., can be appropriately added to the thermoplastic resin composition of the present invention, as long as they do not impair the objectives of the present invention.

[0179] <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 arbitrarily employed. Examples include ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding methods using insulated molds, molding methods using rapidly heated molds, foam molding (including supercritical fluids), insert molding, and IMC (in-mold coating) molding. Furthermore, a molding method using a hot runner system can also be used.

[0180] When using an injection molding machine, the mold temperature is preferably 150°C or lower, more preferably 120°C or lower, and most preferably 100°C or lower. By keeping the mold temperature below the above upper limit, the cooling time during molding can be shortened, shortening the manufacturing cycle of molded products and improving productivity. When using an injection molding machine, the mold temperature is preferably 30°C or higher, and particularly preferably 50°C or higher. Keeping the mold temperature above the above lower limit is preferable because it allows for the acquisition of uniform molded products.

[0181] <Extruded product> The thermoplastic resin composition of the present invention can be suitably used as an extruded product by extrusion molding. There are no particular limitations on how an extruded product can be manufactured from the thermoplastic resin composition of the present invention, but an extruder is usually used. The extruder is generally equipped with T-dies, round dies, etc., and can produce extruded products of various shapes. Examples of extruded products include sheets, films, plates, tubes, pipes, etc. Among these, sheets or films are preferred.

[0182] Extruded articles of the thermoplastic resin composition of the present invention may have a hard coat layer laminated on both or one side of the extruded article to improve adhesion, paintability, and printability, or a weather-resistant and / or scratch-resistant film heat-laminated on both or one side of the extruded article. Furthermore, the surface may be subjected to treatments such as textured finishes or semi-transparent and opaque finishes.

[0183] <Application> Molded articles such as injection-molded articles and extrusion-molded articles made of the thermoplastic resin composition of the present invention are excellent in flame retardancy, heat resistance and fluidity, and in particular, can achieve unprecedentedly high flame retardancy by using the fluorine-free phosphorus-based flame retardant (C). They can be used as parts for various applications requiring these properties, for example, various automobile members, electric and electronic devices, information terminal devices, OA equipment, machine parts, home electric appliances, vehicle parts, architectural members, 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 of electric and electronic devices, information terminal devices, OA equipment, home electric appliances and the like due to their excellent flame retardancy, heat resistance and impact resistance, and can be particularly suitably used as molding materials for housings of electric and electronic devices, information terminal devices, OA equipment, automobile interior parts, and home electric appliances.

Examples

[0184] Hereinafter, the present invention will be described in more detail based on Examples. The present invention is not limited to the following Examples.

[0185] 〔Evaluation Methods〕 The physical properties of the polycarbonate resins obtained in the following Examples and Comparative Examples were evaluated by the following methods.

[0186] (1) Viscosity: Viscosity average molecular weight (Mv) A polycarbonate resin 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 viscometer (manufactured by Moritomo Rika Kogyo Co., Ltd.), and the viscosity average molecular weight (Mv) was calculated from Schnell's viscosity equation (the following equation). η=1.23×10 -4 Mv 0.83

[0187] (2) Viscosity: Melt viscosity (Melt Volume Rate (MVR)) After the thermoplastic resin composition was dried at 100°C for 5 hours, the MVR (unit: cm 3 / 10min) was measured using a melt indexer manufactured by Toyo Seiki Co., Ltd. under the conditions of a measurement temperature of 300°C and a load of 11.8 N in accordance with ISO 1133.

[0188] (3) Heat resistance: Deflection temperature under load (DTUL) After pellets of the thermoplastic resin composition were dried at 100°C for 5 hours, injection molding of the thermoplastic resin composition was carried out using an injection molding machine ("NEX80-V9EG" manufactured by Nissei Plastic Industrial Co., Ltd.) under conditions of a resin temperature of 280°C and a mold temperature of 80°C, to produce an ISO multipurpose test specimen (4 mm thick). The obtained test specimen was measured for DTUL (deflection temperature under load, unit: °C) under the condition of a load of 1.80 MPa (Method A) in accordance with ISO 75-1&2, to evaluate heat resistance.

[0189] (4) Flame retardancy: 20 mm vertical combustion test (0.75 mmt) After pellets of the thermoplastic resin composition were dried at 100°C for 5 hours, a test specimen for combustion test of 125 mm × 13 mm × 0.75 mm thick was molded at a cylinder temperature of 300°C and a mold temperature of 80°C using an injection molding machine ("SE100EV-A-SHR" manufactured by Sumitomo Heavy Industries, Ltd.). The obtained test specimen for combustion test was subjected to a 20 mm vertical combustion test in accordance with UL94 (October 29, 1996, 5th Edition). The combustion test results were classified into V-0, V-1, V-2, and non-conforming according to the material classification described in UL94. When the classification result was V-2, the maximum time required for ignition of the marking cotton by fuming substances or dripping substances to occur was recorded and compared.

[0190] (5) Impact resistance: Notched Charpy impact strength After pellets of the thermoplastic resin composition were dried at 100°C for 5 hours, injection molding of the thermoplastic resin composition was carried out using an injection molding machine ("NEX80-V9EG" manufactured by Nissei Plastic Industrial Co., Ltd.) under conditions of a resin temperature of 280°C and a mold temperature of 80°C, to produce a 3 mm thick impact resistance test specimen based on ISO 179-1 and 2. Using the obtained test specimen, under a temperature environment of 23°C, the notched Charpy impact strength (unit: kJ / m 2 ) was measured.

[0191] [Polycarbonate Resin (P1)] As polycarbonate resin (P1), the following TmBPF / BPC copolymers-1 and 2 were produced according to the following production examples 1 and 2, respectively.

[0192] [Manufacturing Example 1] 6.70 kg (26.14 mol) of 2,2-bis(3-methyl-4-hydroxyphenyl)propane (BPC) (manufactured by Honshu Chemical Co., Ltd.), 26.80 kg (104.54 mol) of 4,4-methylenebis(2,6-dimethylphenol) (TmBPF) (manufactured by Deepak), and 29.53 kg (137.87 mol) of diphenyl carbonate (DPC) 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 the temperature was raised to 220°C over 30 minutes under a nitrogen gas atmosphere. Next, the reaction mixture in the reactor was stirred, and a 25% by mass aqueous solution of cesium carbonate was added to the molten reaction mixture as a transesterification catalyst, so that the amount of cesium carbonate was 16 μmol per mol of total dihydroxy compounds. The reaction mixture was then stirred and matured 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 another 100 minutes to distill the phenol.

[0193] Next, the temperature inside the reactor was raised to 285°C over 60 minutes, and the pressure was reduced to 3 Torr, allowing almost the entire theoretical amount of phenol to be distilled off. Then, the pressure inside the reactor was maintained at less than 1 Torr at the same temperature, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. At this time, the stirring speed of the stirrer was 8 revolutions / minute, the reaction solution temperature just before the end of the reaction was 285°C, and the stirring power was 1.04 kW.

[0194] Next, the reactor was repressurized to an absolute pressure of 101.3 kPa using nitrogen, and then increased to a gauge pressure of 0.2 MPa. The polycarbonate resin was then extracted in strand form from the bottom of the reactor tank, and after obtaining the strand-shaped polycarbonate resin, it was pelletized using a rotary cutter.

[0195] To the above pellets, butyl p-toluenesulfonate was added in an amount 1.1 times the molar amount relative to cesium carbonate, fed into a twin-screw extruder and kneaded. The reaction mixture was then extruded in strand form through the die of the twin-screw extruder and cut with a cutter to obtain pellets of polycarbonate resin (P1), which is TmBPF / BPC copolymer-1. Table 1 shows the viscosity-average molecular weight (Mv) of this polycarbonate resin (P1)TmBPF / BPC copolymer-1.

[0196] [Manufacturing Example 2] Under a nitrogen gas atmosphere, a molten mixture at 150°C was prepared by mixing TmBPF, BPC, and DPC in a constant molar ratio (TmBPF / BPC = 8 / 2, DPC / total dihydroxy compound molar ratio = 1.016), and then introduced through a raw material introduction tube at a rate of 13.3 × 10⁻⁶ 3 The material was continuously supplied into the first vertical reactor, controlled to Pa and 220°C, and the liquid level was kept constant while controlling the valve opening at the polymer discharge line at the bottom of the reactor so that the average residence time was 75 minutes. Simultaneously with the commencement of the supply of the above raw materials, an aqueous solution of cesium carbonate was added as a catalyst, with a cesium carbonate content of 16.0 × 10¹⁶ per mole of total dihydroxy compound. -6 The mixture was continuously supplied at a flow rate of 16.0 μmol / 1 mole of total dihydroxy compound. The distillates, such as phenol, were continuously liquefied and recovered in a heat exchanger installed in the distillation line of the first vertical reactor. The reaction liquid discharged from the first vertical reactor was subsequently introduced sequentially into the second and third vertical reactors and the fourth horizontal reactor. The operating conditions for each reactor were set as follows, with increasing temperature and vacuum as the reaction progressed. Second vertical reactor: 260℃, 5.50 × 10 3 Pa, 100 rpm Third vertical reactor: 280°C, 250 Pa, 65 rpm Fourth horizontal reactor: Outlet resin temperature 290°C, 70-100 Pa, 4-10 rpm Furthermore, 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, while simultaneously removing the by-product phenol by distillation. Next, the polymer melt withdrawn 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 as a catalyst deactivator was supplied in an amount of 28.5 mass ppm relative to the polycarbonate resin. After devolatilization at each vent port (vented twin-screw extruder outlet temperature: 300°C), the mixture was filtered through a leaf disk type polymer filter, then water-cooled and pelletized to obtain pellets of TmBPF / BPC copolymer-2 which is the polycarbonate resin (P1). The viscosity-average molecular weight (Mv) of this polycarbonate resin (P1) TmBPF / BPC copolymer-2 is shown in Table 1.

[0197]

Table 1

[0198] 〔Polycarbonate Resin (P2)〕 As the polycarbonate resin (P2), the bisphenol A polycarbonate resin shown in Table 2 below was used.

[0199]

Table 2

[0200] 〔Phosphorus-based Flame Retardant (C)〕 As the phosphorus-based flame retardant (C), the phosphorus-based flame retardant shown in Table 3 below was used.

[0201]

Table 3

[0202] 〔Elastomer (E) · Additive (D)〕 As the elastomer (E) and the additive (D), those shown in Table 4 below were used.

[0203]

Table 4

[0204] [Examples 1-20, Comparative Examples 1-2: Production and Evaluation of Thermoplastic Resin Compositions] The thermoplastic resin compositions shown in Tables 5 and 6 were prepared by mixing each raw material in a tumbler for 20 minutes. The mixture was then supplied to a φ30 mm twin-screw extruder (TEX30α) manufactured by Japan Steel Works, Ltd., equipped with one vent. The mixture was kneaded under the 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 into strands was rapidly cooled in a water bath and pelletized using a pelletizer to obtain thermoplastic resin compositions. The obtained thermoplastic resin compositions were evaluated for their fluidity, heat resistance, and flame retardancy. The results are shown in Tables 5 and 6.

[0205] [Table 5]

[0206] [Table 6]

[0207] From the above results, the following can be concluded. Examples 1 to 20 differ in the type and amount of polycarbonate resin (P1) and polycarbonate resin (P2), as well as the additive formulation. However, they all exhibit excellent heat resistance and fluidity, and have high flame retardancy, achieving V-0 or V-1 in the UL94 (0.75mmt) combustion test. On the other hand, Comparative Example 1, which does not contain polycarbonate resin (P1), even though it contains a phosphorus-based flame retardant (C), showed a combustion test result of V-2, which is inferior to Examples 1-20 in terms of flame retardancy. Comparative Example 2, which consists only of polycarbonate resin (P1) and does not contain a phosphorus-based flame retardant (C), exhibits excellent flame retardancy, but suffers from poor fluidity and poor moldability.

[0208] From the above, it can be seen that the thermoplastic resin compositions of Examples 1 to 20, which are the thermoplastic resin compositions of the present invention, have superior flame retardancy, as well as superior heat resistance and fluidity (moldability) compared to the thermoplastic resin compositions of Comparative Examples 1 and 2.

Claims

1. A thermoplastic resin composition comprising a polycarbonate resin (P) 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 phosphorus-based flame retardant (C). 【Chemistry 1】 (In general formula (1), R １ and R ２ Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. １ and R ２ The alkyl groups may be bonded to each other to form a ring. ３ and R ４ Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. 【Chemistry 2】 (In general formula (2), R ５ ~R ８ Each of these independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

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 a molar ratio of repeating unit (A):repeating unit (B) = 60:400 to 10:

90.

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

90.

4. The thermoplastic resin composition according to claim 3, wherein the polycarbonate resin (P1) contains 50 to 100% by mass of the polycarbonate copolymer (PA1).

5. The thermoplastic resin composition according to claim 1, wherein the phosphorus-based flame retardant (C) is a condensed phosphate ester and / or a phosphazene compound.

6. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises at least one additive (D) other than the phosphorus-based flame retardant (C).

7. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition further comprises an elastomer (E).

8. In the aforementioned general formula (1), R １ and R ２ are methyl groups, or the alkyl groups of R １ and R ２ are bonded to each other to form a ring represented by the following formula (1a) or (1b), The thermoplastic resin composition according to claim 1. 【Transformation 3】

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

10. 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 4】 (In general formula (2A), R ５ ~R ８ This is equivalent to the expression in the general formula (2) above.

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

12. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition contains 5 parts by mass or more of a polycarbonate resin (P2) that contains 95 mol% or more of a repeating unit (C) represented by the following general formula (3) with respect to 100 parts by mass of the thermoplastic resin. 【Transformation 5】 (In general formula (3), R １０ and R １１ Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group. １０ and R １１ The alkyl groups may be bonded to each other to form a ring. １２ and R １３ Each of these independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted aryl group.

13. The thermoplastic resin composition according to claim 12, wherein the thermoplastic resin composition contains 40 parts by mass or less of the polycarbonate resin (P2) per 100 parts by mass of the thermoplastic resin.

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

15. The thermoplastic resin composition according to claim 1, wherein the evaluation in the UL94 standard vertical combustion test using a 0.75 mm thick test piece prepared using the thermoplastic resin composition is V-0 or V-1.

16. In accordance with ISO 1133, the melting viscosity (melt volume rate (MVR)) measured under conditions of a measurement temperature of 300°C and a load of 11.8 N was 7 cm³. ３ The thermoplastic resin composition according to claim 1, wherein the length is 10 min or more.

17. The thermoplastic resin composition according to claim 1, wherein the DTUL (temperature of deflection under load) measured on an ISO multipurpose test specimen (4 mm thick) under conditions of a load of 1.80 MPa (Method A) in accordance with ISO 75-1 & 2 is 105°C or higher.

18. The notched Charpy impact strength of a 3 mm thick impact resistance test specimen, based on ISO 179-1 and 179-2, at a temperature of 23°C was 6.0 kJ / m². ２ The thermoplastic resin composition according to claim 1.

19. An injection-molded article obtained by injection molding a thermoplastic resin composition according to any one of claims 1 to 18.

20. An extruded article obtained by extruding a thermoplastic resin composition according to any one of claims 1 to 18.

21. The extruded product according to claim 20, wherein the extruded product is a sheet or a film.

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