Polycarbonate Resin

Abstract

Provided is a polycarbonate resin having a constituent unit (I) represented by general formula (1) [in the formula, L1 and L2 each independently represent a divalent linking group selected from an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, an oxyarylene group, and groups obtained by combining two or more thereof, and one or more hydrogen atoms of the linking group may also be substituted with a substituent, and two of the substituents may be bonded together to form a ring structure].

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin, a polycarbonate resin composition containing the resin, a molded article obtained by molding the resin composition, and a method for producing a polycarbonate resin. [Background technology]

[0002] Polycarbonate resins are excellent in heat resistance, mechanical properties, electrical properties, etc., and are widely used, for example, in automobile materials, electrical and electronic equipment materials, various household electrical equipment materials, housing materials, materials for manufacturing parts in other industrial fields, etc. In particular, flame-retardant polycarbonate resins are suitably used as components for office automation and information equipment such as computers, notebook personal computers, mobile phones, printers, and copiers.

[0003] Conventionally, flame retardancy has been imparted to a molded article by blending a halogen-based flame retardant or a phosphorus-based flame retardant into a polycarbonate resin composition containing a polycarbonate resin. However, polycarbonate resin compositions containing halogen-based flame retardants having chlorine or bromine may have problems such as reduced thermal stability and corrosion of the screw of a molding machine or a molding die during molding processing. Also, polycarbonate resin compositions containing phosphorus-based flame retardants may inhibit the high transparency, which is one of the characteristics of polycarbonate resin, or may cause a decrease in impact resistance and heat resistance, so that their applications may be limited. In addition, since molded articles using halogen-based and phosphorus-based flame retardants may cause environmental pollution when the products are disposed of or recovered, there has been a demand in recent years for flame retardancy without using these flame retardants.

[0004] In response to such demands, for example, Patent Document 1 discloses a polycarbonate resin composition having excellent flame retardancy and heat resistance, the polycarbonate resin composition containing a polycarbonate resin having a specific terminal structure and having a viscosity average molecular weight adjusted to a predetermined range, and a stabilizer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-199745 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, there is a high demand for flame retardancy in molding materials, and the polycarbonate resin composition described in Patent Document 1 has room for further improvement in terms of flame retardancy. Therefore, there is a demand for novel polycarbonate resins with better flame retardancy. [Means for solving the problem]

[0007] The present invention provides a polycarbonate resin having specific structural units, and more specifically, provides a polycarbonate resin, a polycarbonate resin composition, a molded article, and a method for producing the polycarbonate resin according to the following aspects [1] to

[11] .

[0008] [1] A polycarbonate resin having a structural unit (I) represented by the following general formula (1): [ka] [In the above formula, L 1 and L 2 are each independently a divalent linking group selected from an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, an oxyarylene group, and a group formed by combining two or more of these, and one or more hydrogen atoms of the linking group may be further substituted with a substituent, and two of the substituents may be bonded to each other to form a ring structure.

[0009] [2] L 1 is a divalent linking group represented by the following general formula (i), and L 2is a divalent linking group represented by the following general formula (ii): [ka] [In the above formula, * indicates the bond position. 1 and R 2 each independently represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 ring carbon atoms, or an arylene group having 6 to 20 ring carbon atoms, in which one or more hydrogen atoms may be further substituted with a substituent, or two of the substituents may be bonded to each other to form a ring structure. p1, q1, p2, and q2 each independently represent an integer of 0 to 10, and r1 and r2 each independently represent 0 or 1, provided that p1+q1 is an integer of 1 or more, and p2+q2 is an integer of 1 or more.

[0010] [3] L 1 is a divalent linking group represented by any one of the following general formulas (i-1) to (i-4), and L 2 is a divalent linking group represented by any one of the following general formulas (ii-1) to (ii-4): [ka] [In the above formula, * indicates the bond position. 1 and R 2 are each independently an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 ring carbon atoms, or an arylene group having 6 to 20 ring carbon atoms, in which one or more hydrogen atoms may be further substituted with a substituent, and two of the substituents may be bonded to each other to form a ring structure. p11, q11, p21, and q21 are each independently an integer of 1 to 10.]

[0011] [4] The polycarbonate resin according to any one of the above [1] to [3], further comprising a structural unit (II) represented by the following general formula (2): [ka] [In the above formula, R a and R b are each independently an alkylene group having 1 to 8 carbon atoms, and R are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 ring carbon atoms. x1 and x2 are each independently an integer of 0 to 10, and n1 and n2 are each independently an integer of 0 to 4. L A is a single bond or a linking group represented by any one of the following formulas (a) to (g). [ka] [In the above formula, * indicates the bond position. c and R d are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. e and R f are each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and m is an integer of 1 to 10.

[0012] [5] The polycarbonate resin according to the above [4], wherein the content ratio of the structural unit (I) to the structural unit (II) [(I) / (II)], in terms of molar ratio, is 0.01 / 99.99 to 99.99 / 0.01. [6] The polycarbonate resin according to any one of the above [1] to [5], wherein the polycarbonate resin has a weight average molecular weight (Mw) of 10,000 to 70,000. [7] The polycarbonate resin according to any one of the above [1] to [6], wherein the polycarbonate resin has a glass transition temperature (Tg) of 100 to 160°C. [8] A polycarbonate resin composition comprising the polycarbonate resin according to any one of the above [1] to [7]. [9] The polycarbonate resin composition according to the above [8], wherein the polycarbonate resin composition is evaluated as V-2 or higher in a flammability test based on the UL94 standard.

[10] A molded article obtained by molding the polycarbonate resin composition according to [8] or [9] above.

[11] A method for producing the polycarbonate resin according to any one of the above [1] to [7], comprising a step of carrying out an ester exchange reaction. Effect of the Invention

[0013] The polycarbonate resin of a preferred embodiment of the present invention has superior flame retardancy, and in a more preferred embodiment, can be used as a material for forming a molded article having a short flaming combustion time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] [Polycarbonate resin] The polycarbonate resin of the present invention has a structural unit (I) represented by the following general formula (1). [ka]

[0015] The polycarbonate resin of the present invention, as represented by the above general formula (1), has a structure having a structural unit (I) containing a triple bond in the main chain, and is therefore considered to have improved flame retardancy, and in particular to have a special effect of shortening the flaming combustion time. In addition, unless otherwise specified, the following embodiments of the polycarbonate resin are described as preferred embodiments from the viewpoint of improving the flame retardancy, particularly the effect of shortening the flaming combustion time.

[0016] In the general formula (I), L 1 and L 2 are each independently a divalent linking group selected from an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, an oxyarylene group, and a group formed by combining two or more of these, and one or more hydrogen atoms of the linking group may be further substituted with a substituent, or two of the substituents may be bonded to each other to form a ring structure. In addition, in the following definition of the preferred number of carbon atoms for each linking group, the number of carbon atoms of any substituent that the linking group may have is not included.

[0017] Examples of the alkylene group include a methylene group (-CH2-), an ethylene group (-CH2CH2-), an ethylidene group (-CH(CH3)-), a trimethylene group (-CH2CH2CH2-), a propylene group (-CH(CH3)CH2-), a propylidene group (-CHCH2(CH3)-), an isopropylidene group (-C(CH3)2-), a tetramethylene group (-CH2CH2CH2CH2-), a 1-methyltrimethylene group (-CH(CH3)CH2CH2-), a 2-methyltrimethylene group (-CH2CH(CH3)CH2-), a butylene group (-C(CH3)2CH2-), and -(CH2) n -(n is an integer of 1 or more, preferably an integer of 1 to 20) and the like. The alkylene group may be a straight-chain alkylene group or a branched-chain alkylene group. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 carbon atoms.

[0018] The oxyalkylene group may be an alkylene group having an oxygen atom bonded to one end of the linking portion thereof, and the preferred range of the number of carbon atoms is as described above.

[0019] Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a norbornylene group, an adamantylene group, and a decahydronaphthalenylene group. The cycloalkylene group preferably has 3 to 20 ring carbon atoms, more preferably 5 to 15 ring carbon atoms, and further preferably 5 to 10 ring carbon atoms.

[0020] Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and a terphenylene group. The arylene group preferably has 6 to 20 ring carbon atoms, more preferably 6 to 18 ring carbon atoms, even more preferably 6 to 12 ring carbon atoms, still more preferably 6 to 10 ring carbon atoms, and particularly preferably 6 ring carbon atoms.

[0021] The oxyarylene group includes a group in which an oxygen atom is bonded to one end of the linking portion of the above-mentioned arylene group, and the preferred range of the number of ring carbon atoms is also the same.

[0022] Here, one or more hydrogen atoms of these linking groups may be further substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3), an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3), a thioalkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3), a cycloalkyl group having 3 to 20 ring carbon atoms (preferably 5 to 15, and more preferably 5 to 10), a dialkylamino group having an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3), an amino group, an aryl group having 6 to 20 ring atoms (preferably 6 to 18, more preferably 6 to 12, more preferably 6 to 10, and even more preferably 6), a heteroaryl group having 3 to 20 ring atoms (preferably 5 to 16), a hydroxy group, a cyano group, and a halogen atom. These substituents may be further substituted with other substituents as described above.

[0023] Among these, the substituent that may be substituted on the linking group is preferably a substituent selected from the alkyl group, the alkoxy group, the diarylamino group, the amino group, the aryl group, the heteroaryl, and the hydroxy group, more preferably a substituent selected from the alkyl group and the aryl group, and even more preferably the alkyl group.

[0024] In one embodiment of the present invention, the two substituents may be bonded to each other to form a ring structure, which may be a heterocycle if one of the two bonded substituents contains a heteroatom such as N (nitrogen atom), O (oxygen atom), or S (sulfur atom). Examples of the linking group forming such a ring structure include divalent groups represented by the following general formulas (p-1) to (p-3). [ka]

[0025] In the above formulas (p-1) to (p-3), * indicates a bonding position, and n is an integer of 1 or more, preferably an integer of 1 to 10. L' is each independently a single bond or a divalent linking group. Examples of the linking group include an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, and an oxyarylene group. Specific examples of these linking groups are the same as those described above for L. 1 and L 2 The same as those that can be selected as above are included. However, it is preferable that each L' is independently a single bond, an alkylene group having 1 to 5 carbon atoms (preferably 1 to 3, more preferably 1 to 2, and even more preferably 1), or an arylene group having 6 to 10 ring carbon atoms (preferably 6).

[0026] In addition, L in the general formula (1) 1 and L 2 may be a group formed by combining two or more of these, that is, a divalent linking group formed by combining two or more selected from an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, and an oxyarylene group. As such an embodiment, L 1 is a divalent linking group represented by the following general formula (i), and L 2 is preferably a divalent linking group represented by the following general formula (ii).

[0027] [ka]

[0028] In the above formulas (i) and (ii), * indicates the bonding position. R 1 and R 2 each independently represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 ring carbon atoms, or an arylene group having 6 to 20 ring carbon atoms, in which one or more hydrogen atoms may be further substituted with a substituent, or two of the substituents may be bonded to each other to form a ring structure.

[0029] R 1 and R 2 The alkylene group, the cycloalkylene group, and the arylene group that can be selected as L 1 and L 2 The preferable ranges of the alkylene group, the cycloalkylene group, and the arylene group that can be selected as the alkylene group, the cycloalkylene group, and the arylene group are also the same as those of the alkylene group, the cycloalkylene group, and the arylene group that can be selected as the alkylene group, the cycloalkylene group, and the preferable ranges of the carbon numbers are also the same. The substituents which these groups may have are the same as those described above, and the preferred embodiments are also the same.

[0030] In one embodiment of the present invention, R 1 and R 2 are each independently preferably an alkylene group having 1 to 20 carbon atoms which may have a substituent or an arylene group having 6 to 20 ring carbon atoms which may have a substituent, more preferably an alkylene group having 1 to 20 carbon atoms which may have a substituent, and further preferably an alkylene group having 1 to 20 carbon atoms which has no substituent. The suitable ranges of the carbon numbers of the alkylene group and the arylene group, and the substituents that the alkylene group and the arylene group may have are as described above.

[0031] In the above formulas (i) and (ii), p1, q1, p2, and q2 each independently represent an integer of 0 to 10, and r1 and r2 each independently represent 0 or 1. In addition, p1+q1 are each independently an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, and still more preferably 1. In addition, p2+q2 each independently represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, and still more preferably 1.

[0032] In one embodiment of the present invention, L 1 and L 2 may be the same type of linking group or different types of linking groups. 1 is a methylene group, and L 2 In the case where L is an ethylene group, both are "alkylene groups" and therefore are "same type of linking group". 1 and L 2 are both alkylene groups, L 1 and L 2 are both oxyalkylene groups, L 1 and L 2 are both cycloalkylene groups, L 1 and L 2 are both arylene groups, or L 1 and L 2 and the like may both be oxyalkylene groups. On the other hand, for example, L 1 is a methylene group (alkylene group), and L 2 When is a phenylene group (arylene group), it is considered a "heterogeneous linking group."

[0033] As a more preferred embodiment of the present invention, L 1 is a divalent linking group represented by any one of the following general formulas (i-1) to (i-4), and L 2 is more preferably a divalent linking group represented by any one of the following general formulas (ii-1) to (ii-4).

[0034] [ka]

[0035] In the above formulas (i-1) to (i-4) and (ii-1) to (ii-4), * indicates a bonding position. R 1 and R 2 is the same as defined in the above general formulae (i) and (ii), and preferred embodiments are also the same. p11, q11, p21, and q21 each independently represent an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, even more preferably 1 or 2, and still more preferably 1.

[0036] In one embodiment of the present invention, L 1 is a divalent linking group represented by the above general formula (i-1), and L 2 may be a divalent linking group represented by the above general formula (ii-1), L 1 is a divalent linking group represented by the above general formula (i-2), and L 2 may be a divalent linking group represented by the above general formula (ii-2), L 1 is a divalent linking group represented by the above general formula (i-3), and L 2 may be a divalent linking group represented by the above general formula (ii-3), or L 1 is a divalent linking group represented by the above general formula (i-4), and L 2 may be a divalent linking group represented by the above general formula (ii-4).

[0037] In one embodiment of the present invention, L 1 is a divalent linking group represented by the above general formula (i-1) or (i-3), and L 2 is more preferably a divalent linking group represented by the above general formula (ii-1) or (ii-3), and L 1 is a divalent linking group represented by the above general formula (i-1), and L 2 is a divalent linking group represented by the above general formula (ii-1), or L 1 is a divalent linking group represented by the above general formula (i-3), and L 2is more preferably a divalent linking group represented by the above general formula (ii-3), and L 1 is a divalent linking group represented by the above general formula (i-1), and L 2 is even more preferably a divalent linking group represented by the above general formula (ii-1).

[0038] It is preferable that the polycarbonate resin of the present invention further contains a structural unit (II) represented by the following general formula (2). [ka]

[0039] In the above formula (2), R a and R b are each independently an alkylene group having 1 to 8 carbon atoms (preferably 1 to 5, more preferably 2 to 3, and even more preferably 2). The alkylene group is, for example, L 1 and L 2 Examples of the alkylene group include the same alkylene groups having 1 to 8 carbon atoms that can be selected as the alkylene group having 1 to 8 carbon atoms.

[0040] Here, x1 and x2 each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and further preferably 0.

[0041] In the above formula (2), R is each independently an alkyl group having 1 to 8 carbon atoms (preferably 1 to 5, more preferably 1 to 3, and even more preferably 1) or an aryl group having 6 to 12 ring carbon atoms (preferably 6 to 10, and more preferably 6). Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, etc. The alkyl group may be a linear alkyl group or a branched alkyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, and a naphthyl group.

[0042] Here, n1 and n2 each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and further preferably 0.

[0043] In the above formula (2), L A is a single bond or a linking group represented by any of the following formulas (a) to (g). [ka]

[0044] In the above formulas (a) to (g), * indicates a bonding position. In addition, R in formula (a) c and R d are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (preferably 1 to 5, more preferably 1 to 3, and even more preferably 1), or an aryl group having 6 to 12 carbon atoms (preferably 6 to 10, and more preferably 6). The alkyl group and the aryl group include the same alkyl group and aryl group that can be selected as R in the above formula (2).

[0045] R in formulas (b) to (d) e and R f are each independently a single bond or an alkylene group having 1 to 4 carbon atoms (preferably 1 to 2, more preferably 1). The alkylene group is, for example, L 1 and L 2 Examples of the alkylene group include the same alkylene groups having 1 to 4 carbon atoms that can be selected as the alkylene group having 1 to 4 carbon atoms.

[0046] In the formula (c), m is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.

[0047] In one embodiment of the present invention, L in the general formula (2) Ais preferably a linking group represented by any one of the above formulas (a) to (d).

[0048] In particular, when x1 and x2 in the general formula (2) are 0, L A is preferably a linking group represented by the above formula (a), formula (c) or formula (d), more preferably a linking group represented by the above formula (a), and R c and R d It is more preferred that the linking group is a methyl group.

[0049] In addition, when x1 and x2 in the general formula (2) are not 0, L A is preferably a linking group represented by the above formula (b).

[0050] In the polycarbonate resin of one embodiment of the present invention, the content of the structural unit (I) is, relative to the total amount (100 mol%) of the structural units of the polycarbonate resin, preferably 0.01 mol% or more, more preferably 0.1 mol% or more, even more preferably 1.0 mol% or more, still more preferably 2.0 mol% or more, particularly preferably 2.5 mol% or more, and is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, still more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0051] In the polycarbonate resin of one embodiment of the present invention, the content of the structural unit (II) is, relative to the total amount (100 mol%) of the structural units of the polycarbonate resin, preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and is preferably 99.99 mol% or less, more preferably 99.9 mol% or less, even more preferably 99.0 mol% or less, still more preferably 98.0 mol% or less, and particularly preferably 97.5 mol% or less.

[0052] The polycarbonate resin of one embodiment of the present invention may contain other structural units in addition to the structural unit (I) and the structural unit (II). However, the total content of the structural units (I) and (II) relative to the total amount (100 mol%) of the structural units of the polycarbonate resin is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, even more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, and particularly preferably 100 mol%.

[0053] In the polycarbonate resin of one embodiment of the present invention, the content ratio of the structural unit (I) to the structural unit (II) [(I) / (II)], in terms of molar ratio, is preferably 0.01 / 99.99 to 99.99 / 0.01, more preferably 0.05 / 99.95 to 50 / 50, even more preferably 0.1 / 99.9 to 20 / 80, still more preferably 0.2 / 99.8 to 10 / 90, still more preferably 0.3 / 99.7 to 7.5 / 92.5, and particularly preferably 0.5 / 99.5 to 5.0 / 95.0.

[0054] The weight average molecular weight (Mw) of the polycarbonate resin of one embodiment of the present invention is preferably 10,000 to 70,000, more preferably 15,000 to 60,000, even more preferably 18,000 to 50,000, and still more preferably 20,000 to 40,000.

[0055] The molecular weight distribution (Mw / Mn) of the polycarbonate resin of one embodiment of the present invention is preferably 5.0 or less, more preferably 3.5 or less, even more preferably 3.0 or less, still more preferably 2.5 or less, and particularly preferably 2.1 or less.

[0056] In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​calculated as standard polystyrene measured by gel permeation chromatography (GPC), and specifically, they mean values ​​measured by the method described in the Examples. The molecular weight distribution means the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) [Mw / Mn].

[0057] The glass transition temperature (Tg) of the polycarbonate resin according to one embodiment of the present invention is preferably 100 to 160°C, more preferably 110 to 150°C, even more preferably 115 to 145°C, and still more preferably 120 to 140°C. In this specification, the glass transition temperature (Tg) is a value measured using a differential scanning calorimeter (DSC), specifically, it means a value measured by the method described in the examples.

[0058] In the polycarbonate resin of one embodiment of the present invention, the thermal decomposition temperature according to the amount of mass reduction is preferably in the following range. Thermal decomposition temperature at which the mass decreases by 1%: preferably 200°C or higher, more preferably 250°C or higher, even more preferably 300°C or higher, and still more preferably 320°C or higher. Thermal decomposition temperature at which the mass decreases by 3%: preferably 230°C or higher, more preferably 280°C or higher, even more preferably 330°C or higher, and still more preferably 350°C or higher. Thermal decomposition temperature at which the mass decreases by 5%: preferably 250°C or higher, more preferably 300°C or higher, even more preferably 350°C or higher, and still more preferably 380°C or higher. Thermal decomposition temperature at which the mass decreases by 10%: preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and still more preferably 420°C or higher. In this specification, the thermal decomposition temperature refers to a value measured using a thermogravimetric and differential thermal analyzer (TG / TDA), specifically, a value measured by the method described in the examples.

[0059] [Method of producing polycarbonate resin] The method for producing the polycarbonate resin of the present invention is not particularly limited, but is preferably a method having a step of carrying out an ester exchange reaction, in which the above-mentioned polycarbonate resin is obtained by carrying out an ester exchange reaction between a diol component, which is a raw material monomer, and a carbonate diester. The diol component, which is a raw material monomer, contains at least a compound (Ia) represented by the following general formula (1a), and preferably further contains a compound (IIa) represented by the following general formula (2a).

[0060] [ka]

[0061] In the above general formula (1a), L 1 and L 2 is the same as defined in the general formula (1), and the preferred embodiments are also as described above. In addition, in the above general formula (2a), R a , R b , R, x1, x2, n1, n2, and L A is the same as defined in the above general formula (2), and the preferred embodiments are also as described above. Compound (Ia) becomes part of the structure of structural unit (I), and compound (IIa) becomes part of the structure of structural unit (II).

[0062] In one embodiment of the present invention, a diol compound other than the above compounds (Ia) and (IIa) may be used as the diol component of the raw material monomer. However, the total content of compound (Ia) and structural unit (IIa) relative to the total amount (100 mol%) of the diol components in the raw material monomers is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, even more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, and particularly preferably 100 mol%.

[0063] In one embodiment of the present invention, the blend ratio of compound (Ia) to compound (IIa) [(Ia) / (IIa)], in molar ratio, is preferably 0.01 / 99.99 to 99.99 / 0.01, more preferably 0.05 / 99.95 to 50 / 50, even more preferably 0.1 / 99.9 to 20 / 80, even more preferably 0.2 / 99.8 to 10 / 90, still more preferably 0.3 / 99.7 to 7.5 / 92.5, and particularly preferably 0.5 / 99.5 to 5.0 / 95.0.

[0064] Examples of the carbonate diester include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. Among these, diphenyl carbonate is preferred from the viewpoints of reactivity and purity. These carbonic acid diesters may be used alone or in combination of two or more kinds.

[0065] The amount of the carbonic acid diester to be added is preferably 1.01 to 1.30 mol, more preferably 1.01 to 1.20 mol, and even more preferably 1.01 to 1.10 mol, per mol of the diol component.

[0066] In the transesterification reaction, it is preferable to use a transesterification catalyst. Examples of the transesterification catalyst include organic acid salts, carbonates, oxides, hydroxides, hydrides, and alkoxides of metals selected from alkali metals and alkaline earth metals, as well as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate, zirconium acetate, and titanium tetrabutoxide. These transesterification catalysts may be used alone or in combination of two or more kinds.

[0067] The amount of the transesterification catalyst used is preferably 1×10 -9 ~1×10 -3 mole, more preferably 1×10 -7 ~1×10 -4 It is a mole.

[0068] Specific reaction conditions for the ester exchange reaction are preferably a reaction temperature of 120 to 260° C. (preferably 180 to 260° C.) and a reaction time of 0.1 to 5 hours (preferably 0.5 to 3 hours). Next, while increasing the degree of vacuum in the reaction system, the reaction temperature is raised to react the diol compound with other monomers, and finally, it is preferable to carry out a polycondensation reaction at a temperature of 200 to 350°C under a reduced pressure of 1 mmHg or less for 0.05 to 2 hours. Such a reaction may be carried out in a continuous or batch manner. The reaction apparatus used in carrying out the above reaction may be a vertical type equipped with an anchor-type impeller, a Max Blend impeller, a helical ribbon-type impeller, or the like, or may be a horizontal type equipped with a paddle impeller, a lattice impeller, a spectacle impeller, or the like, or an extruder type equipped with a screw. In addition, it is preferable to use a reaction apparatus in which these types are appropriately combined in consideration of the viscosity of the polymer.

[0069] In the method for producing a polycarbonate resin according to one embodiment of the present invention, the catalyst may be removed or deactivated after completion of the polymerization reaction, from the viewpoint of maintaining thermal stability and hydrolytic stability.

[0070] After the catalyst is deactivated, a step of removing low boiling point compounds from the resin by volatilization may be performed at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350° C. In this step, a horizontal device equipped with stirring blades having excellent surface renewal ability, such as paddle blades, lattice blades, and spectacle blades, or a thin film evaporator is preferably used.

[0071] Since it is desirable that the resin thus obtained contains as little foreign matter as possible, the molten raw material and the catalyst liquid may be filtered. The mesh of the filter used for filtration is preferably 5 μm or less, more preferably 1 μm or less.

[0072] The polycarbonate resin obtained in this step may be made into flakes and adjusted to a polycarbonate resin composition. In addition, if necessary, the polycarbonate resin may be isolated based on a known method, and then the polycarbonate resin composition may be made into pellets by, for example, a known strand-type cold cut method (a method in which a polycarbonate resin composition that has been melted once is molded into a strand shape, cooled, and then cut into a predetermined shape to form pellets), an air hot cut method (a method in which a polycarbonate resin composition that has been melted once is cut into pellets in the air without coming into contact with water), or an underwater hot cut method (a method in which a polycarbonate resin composition that has been melted once is cut in water and simultaneously cooled to form pellets). The resulting pellets of the polycarbonate resin composition are preferably dried, as necessary, using a method such as a hot air drying oven, a vacuum drying oven, or a dehumidifying drying oven.

[0073] The polycarbonate resin thus obtained may contain impurities such as phenolic compounds that may be produced as by-products during production, and diol components or carbonate diesters that remain unreacted. The impurities such as phenolic compounds and carbonic acid diesters can cause a decrease in strength and odor when molded into a molded article, so it is preferable that the content of these compounds is as small as possible.

[0074] The content of residual phenolic compounds is preferably 3000 ppm by mass or less, more preferably 2000 ppm by mass or less, more preferably 1000 ppm by mass or less, even more preferably 800 ppm by mass or less, still more preferably 500 ppm by mass or less, and particularly preferably 300 ppm by mass or less, relative to 100% by mass of the polycarbonate resin. The content of the remaining diol component is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 100 ppm by mass or less, and still more preferably 10 ppm by mass or less, based on 100% by mass of the polycarbonate resin. The content of the remaining carbonate diester is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 100 ppm by mass or less, and still more preferably 10 ppm by mass or less, based on 100% by mass of the polycarbonate resin.

[0075] The contents of the phenolic compound, the diol component and the carbonic acid diester may be reduced to an undetectable level, but from the viewpoint of productivity, they may be contained in small amounts within a range that does not impair the effect. Also, a small amount can improve the plasticity of the resin when it is melted.

[0076] The content of each of the remaining phenolic compounds, diol components, or carbonate diesters may be, for example, 0.01 ppm by mass or more, 0.1 ppm by mass or more, or 1 ppm by mass or more, relative to 100% by mass of the polycarbonate resin.

[0077] The contents of the phenolic compound, the diol component and the carbonate diester in the polycarbonate resin can be adjusted to be within the above ranges by appropriately adjusting the polycondensation conditions and the settings of the apparatus, and can also be adjusted by the conditions of the extrusion step after the polycondensation.

[0078] [Polycarbonate resin composition] The polycarbonate resin composition of the present invention (hereinafter, also simply referred to as "resin composition") contains the polycarbonate resin of one embodiment of the present invention described above. In the resin composition of one embodiment of the present invention, the content of the polycarbonate resin of the above-mentioned one embodiment of the present invention is usually 30 to 100 mass%, preferably 50 to 100 mass%, more preferably 60 to 100 mass%, even more preferably 70 to 100 mass%, and still more preferably 80 to 100 mass%, relative to the total amount (100 mass%) of the resin composition.

[0079] The polycarbonate resin composition according to one embodiment of the present invention may contain resins other than the polycarbonate resin of the present invention, as long as the effects of the present invention are not impaired. Examples of such other resins include thermoplastic polyester resins such as polycarbonate resins other than the polycarbonate resin of the present invention, 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), and methyl methacrylate-styrene copolymer (MS resin); and core / shell type elastomers such as methyl methacrylate-acrylic rubber-styrene copolymer (MAS). Examples of suitable resins include elastomers such as cyclic cycloolefin resins (COP resins), cyclic cycloolefin (COP) copolymer resins, polyethylene resins (PE resins), and polypropylene resins (PP resins); polyamide resins (PA resins); polyimide resins (PI resins); polyetherimide resins (PEI resins); polyurethane resins (PU resins); polyphenylene ether resins (PPE resins); polyphenylene sulfide resins (PPS resins); polysulfone resins (PSU resins); polymethacrylate resins (PMMA resins); and polycaprolactones. These other resins may be contained alone or in combination of two or more kinds.

[0080] As the polycarbonate resin other than the polycarbonate resin of the present invention, an aromatic polycarbonate resin is preferable. Examples of monomers that can be used as raw materials for aromatic polycarbonate resins include the following aromatic dihydroxy compounds. Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene; Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl; dihydroxynaphthalenes such as 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, and 1,3-bis(4-hydroxyphenoxy)benzene; 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenyl 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethan, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylemethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethan, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, bis(hydroxyaryl)alkanes such as 1,1-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, and 1,1-bis(4-hydroxyphenyl)dodecane; 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl) - bis(hydroxyaryl)cycloalkanes such as 3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, and 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane; Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene; Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; Dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; and the like. Of these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred, with 2,2-bis(4-hydroxyphenyl)propane (ie, bisphenol A) being particularly preferred from the standpoint of marketability. The aromatic dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0081] In the resin composition according to one embodiment of the present invention, when the resin composition contains the polycarbonate resin of the present invention as a main component, the content of the other resin relative to 100 parts by mass of the total amount of the polycarbonate resin of the present invention contained in the resin composition may be 0 to 100 parts by mass, 0 to 50 parts by mass, 0 to 20 parts by mass, 0 to 10 parts by mass, 0 to 5 parts by mass, or 0 to 1 part by mass. On the other hand, when the resin composition contains other resins as main components, the content of the polycarbonate resin of the present invention relative to 100 parts by mass of the total amount of the other resins contained in the resin composition may be 0.01 to 100 parts by mass, 0.05 to 70 parts by mass, 0.10 to 50 parts by mass, 0.30 to 40 parts by mass, 0.50 to 30 parts by mass, 0.70 to 20 parts by mass, or 1.0 to 10 parts by mass.

[0082] The resin composition according to one embodiment of the present invention may contain, in addition to the polycarbonate resin (α) of the present invention, a polycarbonate resin (β) having the structural unit (II) represented by the general formula (2) as another resin. The content ratio [(α) / (β)] of the polycarbonate resin (α) to the polycarbonate resin (β) in the resin composition is, in mass ratio, preferably 0.01 / 99.99 to 99.99 / 0.01, more preferably 0.05 / 99.95 to 50 / 50, even more preferably 0.1 / 99.9 to 20 / 80, still more preferably 0.2 / 99.8 to 10 / 90, still more preferably 0.3 / 99.7 to 7.5 / 92.5, and particularly preferably 0.5 / 99.5 to 5.0 / 95.0.

[0083] Furthermore, the resin composition according to one embodiment of the present invention may further contain various additives within a range that does not impair the effects of the present invention. Such various additives are appropriately selected depending on the application. For example, it is preferable to contain a heat stabilizer, an antioxidant, a flame retardant, a flame retardant assistant, an ultraviolet absorber, a release agent, a colorant, etc., and further, if necessary, an antistatic agent, a fluorescent brightener, an antifogging agent, a flow improver, a plasticizer, a dispersant, an antibacterial agent, etc. may be contained.

[0084] <Heat stabilizer> Examples of the heat stabilizer used in one embodiment of the present invention include phenol-based heat stabilizers, phosphorus-based heat stabilizers, and sulfur-based heat stabilizers. Specific examples of the heat stabilizer include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 10 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

[0085] It is also preferable to use at least one selected from the group consisting of (a) a phosphite compound in which at least one ester in the molecule is esterified with phenol and / or a phenol having at least one alkyl group having 1 to 25 carbon atoms, (b) phosphorous acid, and (c) tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-di-phosphonite. Examples of the phosphite compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonyl phenyl)phosphite, trisnonylphenyl phosphite, tris(octylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, trinonyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, bis(2,4-di-t-butylphenyl) phosphite, pentaerythritol phosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, diphenyl pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-ethylphenyl)pentaerythritol diphosphite, and the like.

[0086] As the organic phosphite compound, commercially available products may be used, and examples thereof include "ADKASTAB 1178", "ADKASTAB 2112", and "ADKASTAB HP-10" manufactured by Adeka Corporation (product names, the same applies below); "JP-351", "JP-360", and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd.; and "IRGAFOS 168" manufactured by BASF.

[0087] Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, and 2-ethylphenyldiphenyl phosphate.

[0088] These heat stabilizers may be used alone or in combination of two or more kinds. In the resin composition of one embodiment of the present invention, the content of the heat stabilizer is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.7 parts by mass, and even more preferably 0.03 to 0.5 parts by mass, per 100 parts by mass of the polycarbonate resin contained in the resin composition.

[0089] <Antioxidants> Examples of the antioxidant used in one embodiment of the present invention include phenol-based antioxidants, hindered phenol-based antioxidants, bisphenol-based antioxidants, and polyphenol-based antioxidants. Specific examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-butylidene bis-(3-methyl-6-t-butylphenol), triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3”,5,5',5”-hexa-t-butyl-a,a',a”-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octyl) 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, and the like. As the phenol-based antioxidant, commercially available products may be used, such as "Irganox 1010" and "Irganox 1076" manufactured by BASF (registered trademark, the same below), and "ADK STAB AO-50" and "ADK STAB AO-60" manufactured by Adeka Corporation (registered trademark, the same below).

[0090] These antioxidants may be used alone or in combination of two or more kinds. In the resin composition according to one embodiment of the present invention, the content of the antioxidant is preferably 0.001 to 1 part by mass, and more preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the polycarbonate resin contained in the resin composition.

[0091] <Flame retardants> Examples of flame retardants used in one embodiment of the present invention include organic metal salt-based flame retardants, phosphorus-based flame retardants, silicone-based flame retardants, etc., and specific examples include the flame retardants (flame retardant compositions) described in paragraphs

[0085] to

[0093] of JP2016-183422A, the contents of which are incorporated herein by reference. Among these, the flame retardant used in one embodiment of the present invention preferably contains an organic sulfonic acid metal salt. Examples of the organic sulfonic acid metal salt used as the flame retardant include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts, and as the metal salt, alkali metal salts and alkaline earth metal salts are preferred. Examples of alkali metals constituting the metal salt include sodium, lithium, potassium, rubidium, and cesium, and examples of alkaline earth metals constituting the metal salt include calcium and strontium. Among these, from the viewpoint of providing a molding material for a molded body that can effectively promote the formation of a carbonized layer during combustion and maintain high transparency, a preferred metal constituting the organic sulfonate metal salt used in one embodiment of the present invention is an alkali metal selected from sodium, potassium, rubidium, and cesium, and more preferably sodium or potassium.

[0092] As the aliphatic sulfonate, a fluoroalkane-sulfonic acid metal salt is preferable, and a perfluoroalkane-sulfonic acid metal salt is more preferable. Specific examples thereof include sodium perfluorobutane-sulfonate, potassium perfluorobutane-sulfonate, sodium perfluoroethane-sulfonate, and potassium perfluoroethane-sulfonate. The carbon number of the fluoroalkylsulfonic acid metal salt is preferably 1 to 8, and more preferably 2 to 4, from the viewpoint of using it as a molding material for a molded article that can maintain high transparency.

[0093] As the aromatic sulfonate metal salt, an aromatic sulfonate alkali metal salt is preferable, and specific examples thereof include sodium 3,4-dichlorobenzenesulfonate, sodium 2,4,5-trichlorobenzenesulfonate, sodium benzenesulfonate, sodium diphenylsulfone-3-sulfonic acid, potassium diphenylsulfone-3-sulfonic acid, sodium 4,4'-dibromodiphenyl-sulfone-3-sulfonic acid, potassium 4,4'-dibromophenyl-sulfone-3-sulfonic acid, disodium diphenylsulfone-3,3'-disulfonic acid, dipotassium diphenylsulfone-3,3'-disulfonic acid, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, potassium p-toluenesulfonate, and potassium p-styrenesulfonate.

[0094] As the organic sulfonate metal salt, particularly from the viewpoint of using it as a molding material for a molded article with improved transparency, potassium salt of diphenylsulfone-3-sulfonic acid, potassium salt of p-toluenesulfonic acid, potassium salt of p-styrenesulfonic acid, or potassium salt of dodecylbenzenesulfonic acid is preferred, and potassium salt of diphenylsulfone-3-sulfonic acid is more preferred.

[0095] These flame retardants may be used alone or in combination of two or more kinds. In the resin composition of one embodiment of the present invention, the content of the flame retardant is preferably 0.005 to 0.2 parts by mass, more preferably 0.01 to 0.15 parts by mass, and even more preferably 0.03 to 0.12 parts by mass, per 100 parts by mass of the polycarbonate resin contained in the resin composition. In addition, when the resin composition of one embodiment of the present invention contains a flame retardant, the content of the flame retardant other than the metal organic sulfonate is preferably 0.1 part by mass or less, more preferably 0.01 part by mass or less, and even more preferably 0.001 part by mass or less, per 100 parts by mass of the metal organic sulfonate.

[0096] The resin composition of the present invention may be substantially free of a flame retardant, and the content of the flame retardant in the resin composition is preferably less than 0.005 parts by mass, more preferably less than 0.001 parts by mass, and even more preferably less than 0.0001 parts by mass, per 100 parts by mass of the polycarbonate resin contained in the resin composition.

[0097] <Flame retardant synergist> Examples of the flame retardant auxiliary used in one embodiment of the present invention include silicone compounds, and from the viewpoint of providing a molding material for a molded article that has good dispersibility in the resin composition and can improve transparency and flame retardancy, silicone compounds having a phenyl group in the molecule are preferred. The weight average molecular weight (Mw) of the silicone compound is preferably 450 to 5,000, more preferably 750 to 4,000, even more preferably 1,000 to 3,000, and still more preferably 1,500 to 2,500. If the weight average molecular weight is 450 or more, the productivity is improved and the flame retardancy can be further improved. If the weight average molecular weight is 5000 or less, the decrease in dispersibility in the resin composition can be effectively suppressed, and the flame retardancy and mechanical properties can be maintained at a good level.

[0098] These flame retardant auxiliaries may be used alone or in combination of two or more kinds. In the resin composition according to one embodiment of the present invention, the content of the flame retardant auxiliary is preferably 0.1 to 7.5 parts by mass, and more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the polycarbonate resin contained in the resin composition.

[0099] <Ultraviolet absorbing agent> Examples of the ultraviolet absorber used in one embodiment of the present invention include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, hindered amine compounds, and phenyl salicylate compounds. Among these, the ultraviolet absorbent is preferably an organic ultraviolet absorbent, and more preferably a benzotriazole-based compound or a benzophenone-based compound.

[0100] Examples of benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-t-butyl-phenyl)-5-chlorobenzotriazole. benzotriazole, 2-(2'-hydroxy-3',5'-di-t-amyl)-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-phenol, -2-yl]-5-(octyloxy)phenol, 2,2'-(1,4-phenylene)bis[4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl)-methylene]-propanediol acid dimethyl ester, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylmethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(t-butyl)phenol phenol, 2,4-di-t-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol], [methyl-3-[3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate, and the like. Among these, the benzotriazole-based compound is preferably 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole or 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol].

[0101] Examples of benzophenone compounds include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, and 2,2',4,4'-tetrahydroxy-benzophenone.

[0102] Examples of the phenyl salicylate compounds include phenyl salicylate, 4-t-butyl-phenyl salicylate, and the like. Examples of triazine compounds include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, and the like. Examples of the hindered amine compounds include bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate.

[0103] These ultraviolet absorbents may be used alone or in combination of two or more kinds. In the resin composition according to one embodiment of the present invention, the content of the ultraviolet absorber is preferably 0.01 to 3 parts by mass, and more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the polycarbonate resin contained in the resin composition.

[0104] <Release agent> Examples of the release agent used in one embodiment of the present invention include aliphatic carboxylic acids, carboxylic acid esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane compounds.

[0105] Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic mono-, di- or tri-carboxylic acids, of which mono- or di-valent saturated or unsaturated aliphatic carboxylic acids having 6 to 36 carbon atoms are preferred, and mono-valent saturated aliphatic carboxylic acids having 6 to 36 carbon atoms are more preferred. The aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralinic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid.

[0106] Examples of the aliphatic carboxylic acid constituting the carboxylate ester include the same as those described above, and examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols, preferably monohydric or polyhydric saturated alcohols having 1 to 30 carbon atoms, and more preferably monohydric or polyhydric aliphatic saturated alcohols having 1 to 30 carbon atoms. The aliphatic saturated alcohol also includes alicyclic saturated alcohol, in which at least one hydrogen atom may be substituted with a substituent such as a fluorine atom or an aryl group. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. The carboxylic acid ester may contain an aliphatic carboxylic acid and / or an alcohol as an impurity, and may be a mixture of a plurality of compounds. Specific examples of the carboxylate ester include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0107] Examples of the aliphatic hydrocarbon compound include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. The aliphatic hydrocarbon compounds also include alicyclic hydrocarbons. These aliphatic hydrocarbon compounds may also be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferred, and paraffin wax or polyethylene wax is more preferred.

[0108] As the polysiloxane compound, polysiloxane-based silicone oils are preferred, and examples thereof include dimethyl silicone oil, phenyl methyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

[0109] These release agents may be used alone or in combination of two or more kinds. In the resin composition according to one embodiment of the present invention, the content of the release agent is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the polycarbonate resin contained in the resin composition.

[0110] <Coloring agent> Examples of the colorant used in one embodiment of the present invention include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium-cobalt green, cobalt green, cobalt blue, copper-chromium black, and copper-iron black; chromate pigments such as yellow lead and molybdate orange; and ferrocyanide pigments such as iron blue. Examples of organic pigments or organic dyes include phthalocyanine-based dyes and pigments such as copper phthalocyanine blue and copper phthalocyanine green (hereinafter, dyes or pigments are also referred to as "dyes and pigments"); azo-based dyes and pigments such as nickel azo yellow; condensed polycyclic dyes and pigments such as thioindigo-based, perinone-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, and quinophthalone-based; quinoline-based, anthraquinone-based, heterocyclic, and methyl-based dyes and pigments, and the like. Among these, from the viewpoint of thermal stability, one or more selected from titanium oxide, carbon black, cyanine dyes and pigments, quinoline dyes and pigments, anthraquinone dyes and pigments, and phthalocyanine dyes and pigments are preferred. In addition, the colorant used in one embodiment of the present invention may be a master batch made of a polystyrene-based resin, a polycarbonate-based resin, an acrylic-based resin, or the like, from the viewpoints of improving handling properties during extrusion and improving dispersibility in the resin composition.

[0111] These colorants may be used alone or in combination of two or more kinds. In the resin composition of one embodiment of the present invention, the content of the colorant is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polycarbonate resin contained in the resin composition.

[0112] <Physical properties of polycarbonate resin composition> The polycarbonate resin composition of the present invention has superior flame retardancy, and in a more preferred embodiment, can be used as a material for forming a molded article having a short flaming combustion time. Specifically, the polycarbonate resin composition is preferably evaluated as V-2 or higher in a flammability test based on the UL94 standard, more preferably V-1 or higher, and even more preferably V-0. In this specification, the flammability test based on the UL94 standard refers to values ​​measured in accordance with the method described in the examples below.

[0113] Furthermore, with respect to the polycarbonate resin composition of one embodiment of the present invention, the flaming combustion time measured in accordance with the method described in the Examples below is preferably 20 seconds or less, more preferably 16 seconds or less, even more preferably 13 seconds or less, still more preferably 10 seconds or less, and particularly preferably 0 second.

[0114] <Molded products> The molded article of the present invention is obtained by molding the polycarbonate resin composition according to one embodiment of the present invention described above. In the molded article according to one embodiment of the present invention, the shape, pattern, color, size, etc. can be appropriately selected depending on the application of the molded article. The molded article according to one embodiment of the present invention may be, for example, electric and electronic devices, OA (Office Automation) equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and miscellaneous goods, parts for lighting equipment and the like, parts for various household electrical appliances and the like, housings, containers, covers, storage parts, cases for electrical appliances, covers and cases for lighting equipment, and the like. Examples of electrical and electronic equipment include personal computers, game consoles, television receivers, display devices such as liquid crystal displays and plasma display devices, printers, copy machines, scanners, fax machines, electronic organizers and personal digital assistants (PDAs), electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, drives and readers for recording media, mice, numeric keypads, various music players, portable radios and audio players, etc. Further examples of molded articles include illuminated signs, liquid crystal backlights, lighting displays, traffic signs, signboards, screens, reflectors, meter parts and other automobile parts, toys, ornaments, and the like.

[0115] The method for producing the molded article of one embodiment of the present invention is not particularly limited, and any molding method generally used for polycarbonate resin compositions can be used, such as injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted or other hollow molding, molding using a heat-insulating mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, etc. A molding method using a hot runner system can also be used. EXAMPLES

[0116] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The values ​​in the examples were measured using the following methods or devices.

[0117] (1) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn) A calibration curve was created using standard polystyrene (manufactured by Tosoh Corporation, product name "PStQuick MP-M") with a known molecular weight (molecular weight distribution = 1) under the following measurement conditions using GPC (gel permeation chromatography). The elution time and molecular weight value of each peak from the measured standard polystyrene were plotted, and a calibration curve was obtained by approximating using a cubic equation. [Measurement conditions] Equipment: Tosoh Corporation, product name "HLC-8320GPC" Columns: Guard column (TSKguardcolumn SuperMPHZ-M) x 1, analytical column (TSKgel SuperMultiporeHZ-M) x 3 Solvent: Chloroform (HPLC grade) ·Injection volume; 10μL ·Sample concentration; 0.2w / v% Solvent flow rate: 0.35ml / min ·Measurement temperature: 40℃ Detector: RI Then, based on the obtained calibration curve, the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in terms of polystyrene from the following formula, and the molecular weight distribution (Mw / Mn) was calculated. [Calculation formula] Mw = Σ(W i ×M i ) / Σ(W i ) Mn = Σ(N i ×M i ) / Σ(N i ) Molecular weight distribution=Mw / Mn (In the above formula, i is the i-th division point when dividing the molecular weight M, W i is the i-th weight, N i is the number of i-th molecules, M i represents the i-th molecular weight. Also, the molecular weight M represents the molecular weight in polystyrene equivalent at the same elution time on the calibration curve.)

[0118] (2) Glass transition temperature (Tg) Measurements were performed using a differential scanning calorimeter (DSC) (product name "DSC-7000", manufactured by Hitachi High-Tech Science Corporation). The measurement sample was prepared by weighing 7 to 12 mg of test piece into an AI autosampler sample container (RDC aluminum pan, cylindrical container with diameter 6.8 mm and height 2.5 mm) and sealing the top of the sample container with the AI ​​autosampler cover. The measurements were performed under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and 10.0 mg of sapphire was used as a standard material in the reference cell. The measurement sample adjusted to 30°C was heated to 220°C at 10°C / min, then cooled to 30°C at 10°C / min. After that, the sample was heated again to 270°C at 10°C / min and measured.

[0119] (3) Measurement method of thermal decomposition temperature The measurements were performed using a thermogravimetry / differential thermal analyzer (TG / TDA) (product name "TGDTA7300", manufactured by Hitachi High-Tech Science Corporation). The measurement sample was prepared by weighing a 2 mg test piece into a platinum pan (Pt open-type sample container, a cylindrical container with a diameter of 5.2 mm and a height of 2.5 mm). The measurement was performed in a nitrogen atmosphere (nitrogen flow rate: 250 ml / min), and 0.00519 g of α-alumina was used as a reference material in the reference cell. The measurement sample was adjusted to 30°C and heated to 550°C at 10°C / min for measurement.

[0120] (4) Content of structural units The content ratio of the constituent units derived from each raw material monomer in each polycarbonate resin in Table 1 is as follows: 1 The abundance ratio of 1H belonging to each raw material monomer was measured based on the H-NMR measurement conditions and calculated. ( 1 H-NMR measurement conditions) Equipment: JNM-ECA500 (500MHz), manufactured by JEOL Ltd. Measurement mode: 1 H-NMR Solvent: CDCl3 (deuterated chloroform) Internal standard: Tetramethylsilane

[0121] The structures of the raw material compounds used in the examples are shown below together with their abbreviations. [ka]

[0122] Example 1 The raw material monomers were 2BD-2EO (1.44 g, 8.27 mmol), BPA (68.56 g, 300.32 mmol), and DPC (68.09 g, 317.85 mmol). The catalyst was cesium carbonate (CsCO3, 1 × 10 per 1 mol of 2BD-2EO and BPA). -6 (mol) was precisely weighed into a 300 mL four-neck flask and dried under reduced pressure at room temperature for 1 hour under vacuum. After that, the atmosphere in the reactor was replaced with nitrogen three times to make the inside of the reactor under nitrogen atmosphere. The four-neck flask was equipped with a stirrer and a distillation apparatus, and heated to 195° C. under a nitrogen atmosphere at a pressure of 101.3 kPa. After confirming complete dissolution of the raw material monomers after heating, the pressure in the reactor was reduced to 27 kPa, and stirring was continued for 80 minutes. The temperature was then increased to 200° C. at a rate of 30° C. / h and maintained at 200° C. for 20 minutes to allow the reaction to proceed, after which the pressure inside the reactor was reduced to 24 kPa and stirring was carried out for 10 minutes. Then, the temperature was increased to 210° C. at a rate of 60° C. / h, the pressure inside the reactor was reduced to 20 kPa, and the mixture was stirred for 10 minutes. The temperature was increased to 220° C. at a rate of 60° C. / h, the pressure inside the reactor was reduced to 14 Pa, and stirring was continued for 10 minutes. The pressure was then further reduced to 7 kPa, and stirring was continued for 10 minutes. Then, the temperature was increased to 230° C. at a rate of 60° C. / h, the pressure inside the reactor was reduced to 1 kPa or less, and the mixture was stirred for 110 minutes to terminate the reaction. After the reaction was completed, nitrogen was introduced into the reactor to return it to normal pressure, and a polycarbonate resin (PC resin-1) was obtained.

[0123] Example 2 A polycarbonate resin (PC resin-2) was obtained in the same manner as in Example 1, except that 2BD (1.42 g, 16.50 mmol), BPA (68.56 g, 300.32 mmol) and DPC (69.93 g, 326.44 mmol) were used as raw material monomers.

[0124] Comparative Example 1 A polycarbonate resin (PC resin-3) was obtained in the same manner as in Example 1, except that PAE-NAP (0.71 g, 2.90 mmol), BPA (68.56 g, 300.32 mmol) and DPC (68.09 g, 317.85 mmol) were used as raw material monomers.

[0125] Comparative Example 2 A commercially available BPA polycarbonate (manufactured by Mitsubishi Engineering Plastics Corporation, product name "Iupilon H-4000") was used as polycarbonate resin (PC resin-4).

[0126] The resulting polycarbonate resins (PC resin-1) to (PC resin-4) were measured for their physical properties according to the above-mentioned measuring methods, and were also subjected to the following flame retardancy test. The results are shown in Table 1. <Flame retardancy test> The polycarbonate resins (PC resin-1) to (PC resin-4) obtained above were each injection molded in an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name "SE50DUZ") under conditions of a cylinder temperature of 300°C and a mold temperature of 120°C to produce test pieces with a length of 12.5 mm, a width of 125 mm, and a thickness of 2 mm. Note that for PC resin-1 and PC resin-4 in Example 1 and Comparative Example 2, test pieces with a length of 12.5 mm, a width of 125 mm, and a thickness of 1 mm were separately produced by injection molding under the same conditions as above. Five of each of these test pieces were produced. Then, the 2 mm thick test piece and the 1 mm thick test piece (only Example 1 and Comparative Example 2) were evaluated for flame retardancy based on a method conforming to Underwriters Laboratories' Subject 94 (UL94). Specifically, five test pieces were prepared and classified into "V-0", "V-1", "V-2" and "Not Compliant (NG)" in order of flame retardancy. In addition, the flaming burning time (unit: seconds), which is the burning time of the one that burned the most among the five test pieces, was also measured.

[0127] [Table 1]

[0128] From Table 1, PC resins 1 and 2 obtained in Examples 1 and 2 have excellent flame retardancy, and in particular, the flaming combustion time is short. On the other hand, PC resin 3 obtained in Comparative Example 1 showed good results in the flammability test based on UL94, but the flaming combustion time was long, and there is room for improvement in the flame retardancy. Moreover, PC resin 4 in Comparative Example 2 showed poor flame retardancy.

[0129] Example 3 (1) Synthesis of Polymer B (Homo-2BD-2EO PC) The raw material monomers were 2BD-2EO (63.00 g, 361.7 mmol), DPC (79.80 g, 372.50 mmol), and the catalyst was zinc acetate (Zn(Oac)2, 3 × 10 per mol of 2BD-2EO). -6 The reaction mixture was dried under reduced pressure at room temperature for 1 hour under vacuum, and then replaced with nitrogen three times to place the reaction mixture under a nitrogen atmosphere. The reactor was placed in a 300 mL reactor equipped with a stirrer and a distillation device under a nitrogen atmosphere of 101.3 kPa and heated to 185 ° C. 10 minutes after the start of heating, complete dissolution of the raw materials was confirmed, and then the degree of vacuum was adjusted to 27 kPa. Stirring was then performed for 140 minutes under the same conditions. The degree of vacuum was then adjusted to 24 kPa, and stirring was performed for 60 minutes. The degree of vacuum was then adjusted to 20 kPa, and stirring was performed for 20 minutes. The degree of vacuum was then adjusted to 14 Pa, and stirring was performed for 10 minutes. The degree of vacuum was then adjusted to 7 kPa, and stirring was performed for 30 minutes. The degree of vacuum was then adjusted to 1 kPa or less, and stirring was performed for another 110 minutes. After the reaction was completed, nitrogen was introduced into the reactor to return to normal pressure, and polymer B (Homo-2BD-2EO PC), which is a polycarbonate resin, was obtained. The Mw of the obtained polymer B was 16600 and Mn was 5500. (2) Preparation of polycarbonate resin composition Using a resin mixing device, Labo Plastomill (Toyo Seiki Seisakusho Co., Ltd., model: 4M150), the mixer part was heated to 280°C and rotated at 30 rpm. Next, 44.29 g of Iupilon H4000 (Mw and Mn are as shown in Table 1), a polycarbonate resin using bisphenol A as a raw material and manufactured by Mitsubishi Engineering Plastics, and 0.70 g of Homo-2BD-2EO PC obtained in (1) above as polymer B were added into the mixer, and the mixture was stirred and mixed for 120 seconds to obtain a polycarbonate resin composition. (3) Measurement of physical properties of polycarbonate resin composition The physical properties of the obtained polycarbonate resin were measured according to the above-mentioned measuring method, and the results are shown in Table 2. In addition, a test piece of 12.5 mm length × 125 mm width × 2 mm thickness was prepared by injection molding under the same conditions as the above-mentioned flame retardancy test, and the flame retardancy test (UL94) was performed using the test piece according to the same procedure as above. The result was V-0, and the flaming burning time was 5 seconds.

[0130] [Table 2]

Claims

1. A polycarbonate resin having a structural unit (I) represented by the following general formula (1): 【Chemistry 1】 [In the above formula, L 1 is a divalent linking group represented by any one of the following general formulas (i-1), (i-2) and (i-4): L 2 is a divalent linking group represented by any one of the following general formulas (ii-1), (ii-2) and (ii-4). 【Chemistry 2】 [In the above formula, * indicates a bonding position. R 1 and R 2 are each independently an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 ring carbon atoms, or an arylene group having 6 to 20 ring carbon atoms, in which one or more hydrogen atoms may be further substituted with a substituent, and two such substituents may be bonded to each other to form a ring structure. p11, q11, p21, and q21 are each independently an integer of 1 to 10.]

2. The polycarbonate resin according to claim 1, further comprising a structural unit (II) represented by the following general formula (2): 【Chemistry 3】 [In the above formula, R ａ and R ｂ are each independently an alkylene group having 1 to 8 carbon atoms, and R is each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 ring carbon atoms. x1 and x2 are each independently an integer of 0 to 10, and n1 and n2 are each independently an integer of 0 to 4. L Ａ is a single bond or a linking group represented by any one of the following formulas (a) to (g). 【Chemistry 4】 [In the above formula, * indicates the bond position. ｃ and R ｄ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ｅ and R ｆ are each independently a single bond or an alkylene group having 1 to 4 carbon atoms, and m is an integer of 1 to 10.

3. 3. The polycarbonate resin according to claim 2, wherein the content ratio of the structural unit (I) to the structural unit (II) [(I) / (II)] is, in molar ratio, 0.01 / 99.99 to 99.99 / 0.

01.

4. The polycarbonate resin according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) of the polycarbonate resin is 10,000 to 70,000.

5. The polycarbonate resin according to any one of claims 1 to 4, wherein the polycarbonate resin has a glass transition temperature (Tg) of 100 to 160°C.

6. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 5.

7. The polycarbonate resin composition according to claim 6, wherein the polycarbonate resin composition is evaluated as V-2 or higher in a flammability test based on the UL94 standard.

8. A molded article obtained by molding the polycarbonate resin composition according to claim 6 or 7.

9. A method for producing a polycarbonate resin having a structural unit (I) represented by the following general formula (1), comprising a step of carrying out an ester exchange reaction: 【Chemistry 5】 [In the above formula, L 1 and L 2 are each independently a divalent linking group selected from an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, an oxyarylene group, and a group formed by combining two or more of these, and one or more hydrogen atoms of the linking group may be further substituted with a substituent, and two of the substituents may be bonded to each other to form a ring structure.]

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