Thermoplastic resin composition and molded article

Abstract

Provided is a molded article obtained by using a thermoplastic resin composition that contains a polycarbonate resin having a repeating unit (A) represented by general formula (1) and a repeating unit (B) represented by general formula (2). R1 and R2 each represent a hydrogen atom, a substituted / unsubstituted alkyl group having 1-20 carbon atoms, or a substituted / unsubstituted aryl group. The alkyl groups of R1 and R2 may be bonded to each other to form a ring. R3 and R4 each represent a substituted / unsubstituted alkyl group having 1-20 carbon atoms or a substituted / unsubstituted aryl group. X represents a single bond or a group represented by general formula (3). R6 to R9 each represent a substituted / unsubstituted alkyl group having 1-20 carbon atoms or a substituted / unsubstituted aryl group. R5 represents a hydrogen atom, a substituted / unsubstituted alkyl group having 1-20 carbon atoms, or a substituted / unsubstituted aryl group.

Description

[Technical field]

[0001] The present invention relates to a thermoplastic resin composition having excellent radio wave transmission in the microwave and / or millimeter wave bands as well as excellent heat resistance and flame retardancy, a molded article thereof, and a housing for a communication device having a built-in microwave and / or millimeter wave antenna. The present invention also relates to a communication device using the housing for a communication device. [Background technology]

[0002] Polycarbonate resin has excellent mechanical strength, electrical properties, and transparency, and is used widely as an engineering plastic in a variety of fields, including electrical and electronic equipment and the automotive industry.

[0003] Patent Document 1 proposes a cover for millimeter wave radar that uses a polycarbonate resin made from a bisphenol having a specific substituent group, thereby lowering the dielectric tangent and improving millimeter wave transmittance in the range of 75 GHz to 81 GHz.

[0004] Patent Document 2 discloses a polycarbonate composition and a copolycarbonate having excellent heat resistance and fire resistance, which are produced using two specific types of bisphenols as raw materials.

[0005] Patent Document 3 discloses a polycarbonate having excellent surface hardness, which is produced using a bisphenol different from conventional bisphenol A as a raw material.

[0006] [Patent Document 1] JP 2019-197048 A [Patent Document 2] Japanese Patent Application Publication No. 49-73455 [Patent Document 3] Japanese Patent Application Publication No. 64-69625

[0007] In recent years, high-frequency radio waves such as microwaves and millimeter waves have come to be used in the electrical and electronic equipment and automotive fields, and this has created a demand for materials that have both a low dielectric constant and a low dielectric loss tangent. Particularly in the electrical and electronics fields, there is a demand for low dielectric constant and low dielectric tangent as well as high heat resistance and flame retardancy.

[0008] However, conventional polycarbonate resins made from bisphenol A have been unable to fully meet these demands.

[0009] In recent years, with the increase in the amount of information and communication, there is a strong demand for faster communication speeds in information and communication devices such as notebook computers, tablet terminals, smartphones, and router devices. For high-speed communication, it is preferable to use radio waves in a higher frequency band. Recently, radio waves above 3 GHz, which are classified as the microwave band, have been used. For the next-generation, fifth-generation mobile communication system (5G), the market is expected to take off in the 28 GHz band, which is a higher frequency in the microwave band. Furthermore, it is expected that millimeter wave band radio waves will be used in next-generation communication.

[0010] Accordingly, there is an increasing demand for higher performance for the housings of information and communication devices that are expected to use microwave and / or millimeter wave bands. Radio waves in such high frequency bands have the characteristics of greater transmission loss and poorer permeability through materials than radio waves in lower frequency bands. Therefore, it is desirable for housings used for microwave and / or millimeter wave communication to have better radio wave permeability than ever before.

[0011] The transmission loss depends on the dielectric constant (ε r ) and the dielectric tangent (tan δ) of the dielectric. Therefore, in order to increase the radio wave permeability of the housing, the relative dielectric constant ε r , and the dielectric tangent tan δ must be small.

[0012] Information and communication devices that transmit and receive high-frequency radio waves such as microwaves and / or millimeter waves tend to generate heat. For this reason, it is desirable for materials used in such fields to have not only low dielectric constants and low dielectric loss tangents, but also appropriate heat resistance and flame retardancy, and there is a strong demand for materials that satisfy these conditions. However, conventional materials could not meet all of these requirements.

[0013] Patent Document 1 proposes a cover for a millimeter wave radar in which the dielectric tangent is lowered and millimeter wave transmittance is improved by using a thermoplastic resin composition containing a polycarbonate resin made from a bisphenol having a specific substituent. However, these thermoplastic resin compositions have insufficient heat resistance and flame retardancy for use in information and communication devices such as notebook computers, tablet terminals, smartphones, or router devices.

[0014] Patent Document 2 discloses a polycarbonate copolymer having improved heat resistance and fire resistance, but makes no mention of its dielectric properties.

[0015] On the other hand, in fields where engineering plastics are used, such as in the electrical and electronic equipment sector and the automotive sector, molded products are becoming thinner, smaller, and lighter, and there is a demand for further improvements in the performance of molding materials.

[0016] However, conventional polycarbonate resins made from bisphenol A do not have sufficient surface hardness or alkali resistance to meet these required properties, so there is a demand for the development of polycarbonate resins with high surface hardness and alkali resistance, and several proposals have been made.

[0017] The aforementioned Patent Document 2 discloses a polycarbonate composition and a copolycarbonate having excellent alkali resistance, which are produced using two specific types of bisphenols as raw materials.

[0018] Patent Document 3 discloses a polycarbonate having excellent surface hardness, which is produced using a bisphenol different from conventional bisphenol A as a raw material.

[0019] However, conventional methods have been unable to obtain a polycarbonate resin composition which is excellent in both surface hardness and alkali resistance as well as in heat resistance and impact resistance. Summary of the Invention

[0020] An object of the first aspect of the present invention is to provide a thermoplastic resin composition and molded article having excellent radio wave transmittance in the microwave and / or millimeter wave bands as well as excellent heat resistance and flame retardancy, as well as a housing for a communication device having a built-in microwave and / or millimeter wave antenna, and the communication device.

[0021] The present inventors have discovered that a housing for a communications device with a built-in microwave and / or millimeter wave antenna that meets the above-mentioned objective can be obtained by forming a thermoplastic resin composition containing a polycarbonate resin having two specific types of repeating units, a molded article thereof, and a housing for a communications device with a built-in microwave and / or millimeter wave antenna.

[0022] The first aspect of the present invention resides in the following [1] to

[32] .

[0023] [1] A thermoplastic resin composition comprising a polycarbonate resin having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B') represented by the following general formula (2'):

[0024] [ka]

[0025] In general formula (1), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0026] [ka]

[0027] In the general formula (2'), X' represents a single bond or a methylene group. 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0028] [2] In the general formula (1), R 1 and R 2 is a methyl group, or R 1 and R 2 The thermoplastic resin composition according to [1], wherein the alkyl groups represented by the following formula (1a) or (1b) are bonded to each other to form a ring represented by the following formula (1a) or (1b):

[0029] [ka]

[0030] [3] In the general formula (1), R 3 and R 4 The thermoplastic resin composition according to [1] or [2], wherein

[0031] [4] The thermoplastic resin composition according to any one of [1] to [3], wherein the repeating unit (B') is a repeating unit represented by the following general formula (2A'):

[0032] [ka]

[0033] In general formula (2A'), X' and R 6 ~R 9 has the same meaning as in the above general formula (2').

[0034] [5] The thermoplastic resin composition according to any one of [1] to [4], wherein the repeating unit (B') is a repeating unit represented by the following general formula (2B'):

[0035] [ka]

[0036] In the general formula (2B′), X′ and R 6 ~R 9 has the same meaning as in the above general formula (2').

[0037] [6] In the general formula (2'), R 6 ~R 9 The thermoplastic resin composition according to any one of [1] to [5], wherein

[0038] [7] The thermoplastic resin composition according to any one of [1] to [6], wherein the content ratio of the repeating unit (A) and the repeating unit (B') in the polycarbonate resin is, in terms of molar ratio, repeating unit (A): repeating unit (B') = 1:99 to 99:1.

[0039] [8] The thermoplastic resin composition according to any one of [1] to [7], wherein the sum of the contents of the repeating unit (A) and the repeating unit (B') in the polycarbonate resin is 50 mol % or more in all carbonate structural units of the polycarbonate resin.

[0040] [9] The thermoplastic resin composition according to any one of [1] to [8], wherein the polycarbonate resin has a glass transition temperature of 125° C. or higher.

[0041]

[10] The thermoplastic resin composition according to any one of [1] to [9], wherein the thermoplastic resin composition contains 50 mass % or more of the polycarbonate resin.

[0042]

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

[10] , comprising the polycarbonate resin as a copolymer polycarbonate resin of the repeating unit (A) and the repeating unit (B').

[0043]

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

[10] , comprising the polycarbonate resin as a blend of a polycarbonate resin containing the repeating unit (A) and a polycarbonate resin containing the repeating unit (B').

[0044]

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

[12] , wherein the polycarbonate resin has a viscosity average molecular weight (Mv) in the range of 14,500 to 30,000.

[0045]

[14] The thermoplastic resin composition according to

[13] , wherein the polycarbonate resin has a viscosity average molecular weight (Mv) in the range of 18,000 to 28,000.

[0046]

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

[14] , which has a pencil hardness of H or more as measured by a method in accordance with ISO 15184.

[0047]

[16] A molded article obtained using a thermoplastic resin composition containing a polycarbonate resin having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2):

[0048] [ka]

[0049] In general formula (1), R 1 and R 2R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0050] [ka]

[0051] In the general formula (2), X represents a single bond or a divalent organic group represented by the following general formula (3): 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0052] [ka]

[0053] In general formula (3), R 5 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0054]

[17] In the general formula (1), R 1 and R 2 is a methyl group, or R 1 and R 2 The molded article according to

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

[0055] [ka]

[0056]

[18] In the general formula (1), R 3 and R 4 wherein R is a methyl group.

[0057]

[19] The molded article according to any one of

[16] to

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

[0058] [ka]

[0059] In general formula (2A), X and R 6 ~R 9 has the same meaning as in the above general formula (2).

[0060]

[20] The molded article according to any one of

[16] to

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

[0061] [ka]

[0062] In the general formula (2B), X and R 6 ~R 9 has the same meaning as in the above general formula (2).

[0063]

[21] In the general formula (2), R 6 ~R 9 The molded article according to any one of

[16] to

[20] , wherein

[0064]

[22] In the general formula (3), R 5 wherein R is a hydrogen atom or a methyl group.

[0065]

[23] The molded article according to any one of

[16] to

[22] , wherein the content ratio of the repeating unit (A) and the repeating unit (B) in the polycarbonate resin is, in terms of molar ratio, repeating unit (A): repeating unit (B) = 1:99 to 99:1.

[0066]

[24] The molded article according to any one of

[16] to

[23] , wherein the sum of the contents of the repeating unit (A) and the repeating unit (B) contained in the polycarbonate resin is 50 mol % or more of all carbonate structural units in the polycarbonate resin.

[0067]

[25] The molded article according to any one of

[16] to

[24] , wherein the polycarbonate resin has a glass transition temperature of 125° C. or higher.

[0068]

[26] The molded article according to any one of

[16] to

[25] , wherein the thermoplastic resin composition contains 50 mass% or more of the polycarbonate resin.

[0069]

[27] The molded article according to any one of

[16] to

[26] , which is an extrusion molded article or an injection molded article.

[0070]

[28] The molded article according to

[27] , wherein the extrusion molded article is a sheet or a film.

[0071]

[29] A housing for communication equipment having a built-in microwave and / or millimeter wave antenna, obtained by using the molded article according to any one of

[16] to

[28] .

[0072]

[30] The communications device housing according to

[29] , wherein the antenna is used for radio waves in a frequency band of 3.5 to 30 GHz.

[0073]

[31] The housing for a communications device described in

[29] or

[30] , wherein the communications device is a notebook computer, a tablet terminal, a smartphone, or a router device.

[0074]

[32] A communication device having a built-in microwave and / or millimeter wave antenna, obtained by using the housing for the communication device according to any one of

[29] to

[31] .

[0075] An object of the second aspect of the present invention is to provide a polycarbonate resin composition that has high hardness and excellent alkali resistance, as well as excellent heat resistance and impact resistance.

[0076] The present inventors have found that a polycarbonate resin composition that meets the above-mentioned objectives can be obtained by preparing a polycarbonate resin composition containing carbonate structural units derived from two specific types of aromatic dihydroxy compounds.

[0077] The gist of the second aspect of the present invention lies in the following

[33] to

[44] .

[0078]

[33] A polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aromatic dihydroxy compound represented by the following general formula (11) and a carbonate structural unit (Y) derived from an aromatic dihydroxy compound represented by the following general formula (12) in a molar ratio of (X) / (Y)=1 / 99 to 99 / 1:

[0079] [ka]

[0080] In general formula (11), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0081] [ka]

[0082] In general formula (12), R 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0083]

[34] The polycarbonate resin composition according to

[33] , comprising the carbonate structural unit (X) and the carbonate structural unit (Y) as a copolymer polycarbonate resin.

[0084]

[35] The polycarbonate resin composition according to

[33] , which is a blend of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Y).

[0085]

[36] The polycarbonate resin composition according to any one of

[33] to

[35] , wherein the polycarbonate resin composition has a viscosity average molecular weight (Mv) in the range of 15,000 to 33,000.

[0086]

[37] The polycarbonate resin composition according to any one of

[33] to

[36] , wherein the polycarbonate resin composition has a pencil hardness of H or more as measured by a method in accordance with ISO 15184.

[0087]

[38] The polycarbonate resin composition according to any one of

[33] to

[37] , wherein the polycarbonate resin composition has a glass transition temperature Tg of 130 to 200°C.

[0088]

[39] The polycarbonate resin composition according to any one of

[33] to

[38] , wherein the carbonate structural unit (X) is a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following general formula (13):

[0089] [ka]

[0090] In general formula (13), R 10 and R 11 R each independently represents a hydrogen atom or a methyl group. 12 and R 13 each independently represents a methyl group or an ethyl group.

[0091]

[40] The polycarbonate resin composition according to any one of

[33] to

[39] , wherein the carbonate structural unit (Y) is a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following general formula (14):

[0092] [ka]

[0093] In general formula (14), R 15 ~R 18 each independently represents a methyl group or an ethyl group.

[0094]

[41] The polycarbonate resin composition according to

[40] , wherein the carbonate structural unit (Y) is a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following general formula (14A):

[0095] [ka]

[0096] In general formula (14A), R 20 ~R 23 each independently represents a methyl group or an ethyl group.

[0097]

[42] An injection-molded article obtained by injection molding the polycarbonate resin composition according to any one of

[33] to

[41] .

[0098]

[43] An extrusion molded product obtained by extrusion molding the polycarbonate resin composition according to any one of

[33] to

[3419] .

[0099]

[44] The extrusion molded product according to

[43] , wherein the extrusion molded product is a sheet or a film.

[0100] An object of the present invention according to a third aspect is to provide a polycarbonate resin composition which is excellent in surface hardness and alkali resistance, as well as in heat resistance, impact resistance and flowability.

[0101] The present inventors have found that a polycarbonate resin composition that meets the above-mentioned objectives can be obtained by preparing a polycarbonate resin composition containing carbonate structural units derived from two specific types of aromatic dihydroxy compounds.

[0102] The gist of the third aspect of the present invention lies in the following

[45] to

[59] .

[0103]

[45] A polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aromatic dihydroxy compound represented by the following general formula (11) and a carbonate structural unit (Z) derived from an aromatic dihydroxy compound represented by the following general formula (21), in a molar ratio of carbonate structural unit (X) / carbonate structural unit (Z) = 1 / 99 to 99 / 1.

[0104] [ka]

[0105] In general formula (11), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0106] [ka]

[0107] In general formula (21), R 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0108]

[46] The polycarbonate resin composition according to

[45] , comprising the carbonate structural unit (X) and the carbonate structural unit (Z) as a copolymer polycarbonate resin.

[0109]

[47] The polycarbonate resin composition according to

[45] , which is a blend of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Z).

[0110]

[48] ​​The polycarbonate resin composition according to any one of

[45] to

[47] , wherein the viscosity average molecular weight (Mv) of the polycarbonate resin in the polycarbonate resin composition is in the range of 16,000 to 30,000.

[0111]

[49] The polycarbonate resin composition according to any one of

[45] to

[48] , wherein the polycarbonate resin composition has a pencil hardness of H or more as measured by a method in accordance with ISO 15184.

[0112]

[50] The polycarbonate resin composition according to any one of

[45] to

[49] , wherein the polycarbonate resin composition has a glass transition temperature Tg of 130 to 200°C.

[0113]

[51] The polycarbonate resin composition according to any one of

[45] to

[50] , wherein the viscosity average molecular weight (Mv) of the polycarbonate resin in the polycarbonate resin composition is in the range of 18,000 to 28,000.

[0114]

[52] The polycarbonate resin composition according to any one of

[45] to

[51] , comprising the carbonate structural unit (X) and the carbonate structural unit (Z) in a molar ratio of carbonate structural unit (X) / carbonate structural unit (Z) of 1 / 99 to 85 / 15.

[0115]

[53] The polycarbonate resin composition according to any one of

[45] to

[52] , wherein the carbonate structural unit (X) is a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following general formula (13):

[0116] [ka]

[0117] In general formula (13), R 10 and R 11 R each independently represents a hydrogen atom or a methyl group. 12 and R 13 each independently represents a methyl group or an ethyl group.

[0118]

[54] The polycarbonate resin composition according to any one of

[45] to

[53] , wherein the carbonate structural unit (Z) is a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following general formula (22):

[0119] [ka]

[0120] In general formula (22), R 31 ~R 34 each independently represents a methyl group or an ethyl group.

[0121]

[55] The polycarbonate resin composition according to

[54] , wherein the carbonate structural unit (Z) is a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following general formula (22A):

[0122] [ka]

[0123] In general formula (22A), R 31 ~R 34 has the same meaning as in the above general formula (22).

[0124]

[56] A molded article obtained from the polycarbonate resin composition according to any one of

[45] to

[55] .

[0125]

[57] An injection-molded article using the polycarbonate resin composition according to any one of

[45] to

[55] .

[0126]

[58] An extrusion molded product using the polycarbonate resin composition according to any one of

[45] to

[55] .

[0127]

[59] The extrusion molded product according to

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

[0128] The molded article of the present invention according to the first aspect and the housing for a communication device having a built-in microwave and / or millimeter wave antenna are excellent in radio wave transmittance in the microwave and / or millimeter wave bands, as well as in heat resistance and flame retardancy, and can therefore be widely used as housings for communication devices having built-in microwave and / or millimeter wave antennas, for example, laptop computers, tablet terminals, smartphones, router devices, etc. Furthermore, it is possible to provide a molded article having excellent impact resistance, and a housing for a communication device having a built-in microwave and / or millimeter wave antenna.

[0129] According to the second aspect of the present invention, it is possible to provide a polycarbonate resin composition which has high hardness and excellent alkali resistance, and also has excellent mechanical strength such as heat resistance and impact resistance.

[0130] According to the third aspect of the present invention, it is possible to provide a polycarbonate resin composition which is excellent in surface hardness and alkali resistance, as well as in heat resistance, impact resistance and flowability.

[0131] The polycarbonate resin compositions of the present invention related to the second and third aspects have such excellent properties and can be widely used as materials for manufacturing parts in automobiles, electrical and electronic devices, and other industrial fields. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0132] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. The present invention is not to be construed as being limited to the embodiments and examples shown below.

[0133] In this specification, unless otherwise specified, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0134] Hereinafter, the present invention relating to the first aspect will be referred to as the "first invention", the present invention relating to the second aspect will be referred to as the "second invention", and the present invention relating to the third aspect will be referred to as the "third invention", and these may be collectively referred to as "the present invention".

[0135] [First Invention] [overview] The molded article of the first invention and the housing for a communication device having a built-in microwave and / or millimeter wave antenna are characterized in that, as described above, they are obtained from a thermoplastic resin composition (hereinafter sometimes referred to as the "thermoplastic resin composition of the present invention") containing a polycarbonate resin having a repeating unit (A) represented by general formula (1) and a repeating unit (B') represented by general formula (2') or a repeating unit (B) represented by general formula (2) (hereinafter sometimes referred to as the "polycarbonate resin of the first invention"). The communications device of the present invention is a communications device with a built-in microwave and / or millimeter wave antenna obtained by using this communications device housing.

[0136] Hereinafter, the components constituting the polycarbonate resin of the first invention and the thermoplastic resin composition of the first invention containing the polycarbonate resin of the first invention will be described in detail.

[0137] [Polycarbonate resin] The polycarbonate resin of the first invention is characterized by having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B') represented by the following general formula (2') or a repeating unit (B) represented by the following general formula (2):

[0138] By using a thermoplastic resin composition containing the polycarbonate resin of the first invention having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B') represented by the following general formula (2') or a repeating unit (B) represented by the following general formula (2), it is possible to impart excellent radio wave transparency in the microwave and / or millimeter wave bands, heat resistance, and flame retardancy to the molded article and casing for communication device of the first invention.

[0139] Hereinafter, "repeating unit (B') or repeating unit (B)" may be expressed as "repeating unit (B'), (B)".

[0140] [ka]

[0141] In general formula (1), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0142] [ka]

[0143] In the general formula (2'), X' represents a single bond or a methylene group. 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0144] [ka]

[0145] In the general formula (2), X represents a single bond or a divalent organic group represented by the following general formula (3): 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0146] [ka]

[0147] In general formula (3), R 5 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0148] The polycarbonate resin of the first invention may be a polycarbonate resin mixture of a polycarbonate resin containing a repeating unit (A) and a polycarbonate resin containing repeating units (B') and (B), or may be a copolymer polycarbonate resin containing the repeating unit (A) and the repeating units (B') and (B). Also, it may be a polycarbonate resin mixture containing a polycarbonate resin containing the repeating unit (A) and / or a polycarbonate resin containing the repeating units (B') and (B), and a copolymer polycarbonate resin containing the repeating unit (A) and the repeating units (B') and (B).

[0149] <Repeating unit (A)> In the general formula (1) representing the repeating unit (A) of the polycarbonate resin of the first invention, R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0150] In general formula (1), R 1 and R 2 From the viewpoint of improving heat resistance, R is a methyl group or 1 and R 2 It is preferable that the alkyl groups of R are bonded to each other to form a ring represented by the following formula (1a) or (1b). From the viewpoint of the balance between heat resistance and fluidity, 1 and R 2 It is particularly preferred that is a methyl group.

[0151] [ka]

[0152] In general formula (1), R 3 and R 4 From the viewpoint of improving flame retardancy and dielectric properties, is preferably a methyl group.

[0153] That is, 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"), which is a repeating unit represented by the following formula (4).

[0154] [ka]

[0155] The polycarbonate resin of the first invention may contain only one type of repeating unit (A), or may contain two or more types.

[0156] <Repeating units (B'), (B)> In the general formula (2') representing the repeating unit (B') of the polycarbonate resin of the present invention, X' represents a single bond or a methylene group.

[0157] In the general formula (2) representing the repeating unit (B) of the polycarbonate resin of the first invention, X represents a single bond or a divalent organic group represented by the following general formula (3). In the general formula (2), X is preferably a single bond or a methylene group from the viewpoint of improving dielectric properties and flame retardancy. 5 is preferably a hydrogen atom.

[0158] [ka]

[0159] In general formula (2'), (2), R 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0160] In general formula (2'), R 6 ~R 9 is preferably a methyl group from the viewpoint of improving heat resistance and flame retardancy.

[0161] In the general formula (2'), R 6 ~R 9 Although there are no restrictions on the substitution position, it is preferably a substitution position represented by the following general formula (2A') or the following general formula (2B'), and from the viewpoint of improving impact resistance, it is particularly preferably a substitution position represented by the following general formula (2A').

[0162] [ka]

[0163] In general formula (2A'), X' and R 6 ~R 9 has the same meaning as in the above general formula (2').

[0164] [ka]

[0165] In the general formula (2B′), X′ and R 6 ~R 9 has the same meaning as in the above general formula (2').

[0166] In the general formula (2), R 6 ~R 9 Although there are no restrictions on the substitution position, it is usually preferably a substitution position represented by the following general formula (2A) or the following general formula (2B), and from the viewpoint of improving impact resistance, it is particularly preferably a substitution position represented by the following general formula (2A).

[0167] [ka]

[0168] In general formula (2A), X, R 6~R 9 has the same meaning as in the above general formula (2).

[0169] [ka]

[0170] In general formula (2B), X, R 6 ~R 9 has the same meaning as in the above general formula (2).

[0171] It is particularly preferable that the repeating units (B') and (B) are a repeating unit represented by the following general formula (5), which is a repeating unit derived from 4,4-methylenebis(2,6-dimethylphenol) (hereinafter sometimes abbreviated as "TmBPF"), or a repeating unit represented by the following general formula (6), which is a repeating unit derived from 2,2,6,6-tetramethyl-4,4-biphenol (hereinafter sometimes abbreviated as "TmBP"; also referred to as 3,3',5,5'-tetramethyl-1,1'-biphenyl-4,4'-diol).

[0172] [ka]

[0173] The polycarbonate resin of the first invention may contain only one kind of repeating units (B') and (B), or may contain two or more kinds.

[0174] <Repeating unit (A) / Repeating unit (B'), (B)> The content ratio of the repeating unit (A) and the repeating units (B'), (B) in the polycarbonate resin of the first invention is not particularly limited, but the repeating unit (A) / repeating units (B'), (B) (molar ratio) is preferably 1:99 to 99:1, particularly preferably 1:99 to 90:10, particularly preferably 10:90 to 80:20, and of these, preferably 15:85 to 70:30.

[0175] <Other repeating units (C)> The polycarbonate resin of the first invention may contain one or more other repeating units (C) other than the repeating units (A) and the repeating units (B') and (B) within the scope of the first invention. Examples of the other repeating units (C) include repeating units derived from aromatic dihydroxy compounds such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane. Among them, repeating units derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane are preferred.

[0176] In order to reliably obtain the effects of the first invention by containing the repeating unit (A) and the repeating units (B') and (B), the sum of the repeating units (A) and the repeating units (B') and (B) is preferably 40 mol % or more, more preferably 50 mol % or more, even more preferably 60 mol % or more, and particularly preferably 70 mol % or more, with the total carbonate structural units in the polycarbonate resin of the first invention being 100 mol %.

[0177] <Molecular weight of polycarbonate resin> The molecular weight of the polycarbonate resin of the first invention is not particularly limited, but the viscosity average molecular weight (Mv) calculated from the solution viscosity is preferably 14,500 or more. When the viscosity average molecular weight is equal to or more than the above lower limit, the heat resistance and flame retardancy of the thermoplastic resin composition of the first invention, the molded article, and the housing for communication devices are improved, which is preferable. From this viewpoint, the viscosity average molecular weight of the polycarbonate resin of the first invention 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.

[0178] On the other hand, the viscosity average molecular weight (Mv) of the polycarbonate resin of the first invention is preferably 30,000 or less. When the viscosity average molecular weight is the above upper limit or less, the flowability of the thermoplastic resin composition of the first invention containing the polycarbonate resin of the first invention tends to be good, which is preferable. From this viewpoint, the viscosity average molecular weight of the polycarbonate resin of the first invention 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.

[0179] The viscosity average molecular weight (Mv) of polycarbonate resin was calculated by using methylene chloride as a solvent and an Ubbelohde viscometer to determine the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at a temperature of 20°C, and then calculating it using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 This means the value calculated from The intrinsic viscosity (limiting viscosity) [η] is the value calculated by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dL) and using the following formula.

[0180]

number

[0181] The same applies to the viscosity average molecular weight (Mv) in the second and third inventions described below.

[0182] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of the polycarbonate resin of the first invention is not limited, but is preferably 125 to 200°C. If the Tg is 125°C or higher, the heat resistance of the thermoplastic resin composition of the first invention, the molded article, and the housing for communication devices is improved. On the other hand, if the Tg of the polycarbonate resin is 200°C or lower, the flowability of the thermoplastic resin composition of the first invention containing the polycarbonate resin of the first invention is good, and high moldability can be obtained. For this reason, the glass transition temperature (Tg) of the polycarbonate resin of the first invention is preferably 125 to 200°C.

[0183] The Tg of the polycarbonate resin is measured by the method described in the Examples section below.

[0184] <Pencil hardness> The thermoplastic resin composition of the first invention containing the polycarbonate resin of the first invention has high hardness characteristics such that the pencil hardness measured by a method in accordance with ISO 15184 is preferably F or more, more preferably H or more, and particularly preferably 2H or more. The pencil hardness of the thermoplastic resin composition is measured for a molded article made of the thermoplastic resin composition by the method described later in the Examples section.

[0185] <Flame retardancy: 20mm vertical burning test (0.8mmt)> The flame retardancy of the polycarbonate resin of the first invention is preferably such that, when the result of the 20 mm vertical burning test (0.8 mmt) described in the Examples section below is V-2 in the material classification described in UL94, the longest time required for the cotton marker to be ignited by the smoke-generating substance or drops is longest, for example, 10 seconds or more. Moreover, the material classification is more preferably V-1 or V-0, and particularly preferably V-0.

[0186] <Relative permittivity (ε r ), dielectric tangent (tan δ) The polycarbonate resin of the first invention has a relative dielectric constant (ε r ) is preferably 2.60 or less, more preferably 2.55 or less, and particularly preferably 2.50 or less. -3 ) is preferably 4.00 or less, more preferably 3.00 or less, and particularly preferably 2.50 or less. When the relative dielectric constant and the dielectric loss tangent are equal to or less than the above upper limits, the transmittance of microwaves and / or millimeter wave band radio waves becomes good.

[0187] The relative dielectric constant (ε r ) and dielectric tangent (tanδ×10 -3) is measured by cutting out a rectangular film of 70 mm length and 2 mm width from a film of 30 to 250 μm thickness molded using this polycarbonate resin, and after conditioning it for 48 hours under conditions of room temperature of 23° C. and humidity of 50%, using a cavity resonator at a frequency of 10 GHz. Details are as described in the Examples section below.

[0188] <Production method of polycarbonate resin> The polycarbonate resin of the first invention can be produced by a conventionally known polymerization method, and the polymerization method is not particularly limited. Examples of the polymerization method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-phase transesterification method of a prepolymer. Below, a particularly suitable method among these methods will be specifically described.

[0189] (interfacial polymerization method) In the interfacial polymerization method, a dihydroxy compound as a raw material is reacted with a carbonate-forming compound in the presence of an organic solvent and an alkaline aqueous solution that are inert to the reaction, usually at a pH of 9 or higher, and then interfacial polymerization is carried out in the presence of a polymerization catalyst to obtain a polycarbonate resin. If necessary, a molecular weight regulator (terminal terminator) may be present in the reaction system, and an antioxidant may be present to prevent oxidation of the dihydroxy compound as a raw material.

[0190] The organic solvent inert to the reaction is not particularly limited, but examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; and the like. The organic solvent may be used alone or in any combination of two or more in any ratio.

[0191] The alkaline compound contained in the alkaline aqueous solution is not particularly limited, but examples thereof include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogencarbonate. Among these, sodium hydroxide and potassium hydroxide are preferred. The alkaline compounds may be used alone or in any combination of two or more in any ratio.

[0192] Although there is no limitation on the concentration of the alkali compound in the alkaline aqueous solution, the alkali compound concentration is usually 5 to 10 mass % in order to control the pH of the alkaline aqueous solution to 10 to 12. Furthermore, for example, when blowing in phosgene, in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11, it is preferable that the molar ratio of the raw material dihydroxy compound to the alkali compound is usually 1:1.9 or more, preferably 1:2.0 or more, and usually 1:3.2 or less, preferably 1:2.5 or less.

[0193] As the starting dihydroxy compound, at least a dihydroxy compound capable of producing the repeating unit (A) and the repeating units (B') and (B) upon reaction with a carbonate-forming compound is used.

[0194] As the carbonate-forming compound, a carbonyl halide is preferably used. Among them, it is preferable to use phosgene. The method using phosgene is particularly called the phosgene method.

[0195] The polymerization catalyst is not particularly limited, but examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; guanine; and salts of guanidine. The polymerization catalyst may be used alone or in any combination of two or more in any ratio.

[0196] The molecular weight regulator is not particularly limited, but examples thereof include aromatic phenols having a monovalent phenolic hydroxyl group, aliphatic alcohols such as methanol and butanol, mercaptans, phthalic imide, etc. Among these, aromatic phenols are preferred.

[0197] Specific 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, phenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 at the ortho-position, meta-position or para-position, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, 4-(1-adamantyl)phenol, and the like. Of these, pt-butylphenol, p-phenylphenol and p-cumylphenol are preferably used. The molecular weight regulator may be used alone or in any combination of two or more in any ratio.

[0198] The amount of the molecular weight modifier used is not particularly limited, but is, for example, usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the raw material dihydroxy compound.

[0199] The antioxidant is not particularly limited, but examples thereof include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[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]phosphonate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6- triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0200] Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Commercially available products of such phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by BASF, and "Adeka STAB AO-50" and "Adeka STAB AO-60" manufactured by ADEKA.

[0201] The antioxidants may be used alone or in any combination of two or more in any ratio.

[0202] The amount of the antioxidant is not particularly limited, but is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the raw dihydroxy compound. By making the amount of the antioxidant more than the above lower limit, the antioxidant effect is sufficient. The amount of the antioxidant is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the raw dihydroxy compound. By making the amount of the antioxidant less than the above upper limit, gas generation during injection molding can be suppressed.

[0203] In the reaction, the order of mixing the reaction substrate (reaction raw material), reaction solvent (organic solvent), catalyst, additives, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate-forming compound, the molecular weight modifier can be mixed at any time between the reaction of the raw material dihydroxy compound with phosgene (phosgenation) and the start of the polymerization reaction.

[0204] The reaction temperature is not particularly limited, but is preferably 0 to 40° C. The reaction time is not particularly limited, but is preferably several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

[0205] (Melt transesterification method) In the melt transesterification method, for example, a transesterification reaction is carried out between a carbonate ester and a raw material dihydroxy compound. The starting dihydroxy compound is the same as that used in the interfacial polymerization method.

[0206] The carbonate ester may be, for example, a compound represented by the following general formula (I), and examples thereof include aryl carbonates, dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0207] [ka]

[0208] In the above general formula (I), R 101 and R 102 each independently represents an alkyl group, an aryl group, or an arylalkyl group having 1 to 30 carbon atoms. 101 and R 102 When the alkyl group is an alkyl group or an arylalkyl group, it is called a dialkyl carbonate, and when the aryl group is an aryl carbonate, it is called a diaryl carbonate. 101 and R 102 and are preferably both aryl groups, and are more preferably diaryl carbonates represented by the following general formula (II).

[0209] [ka]

[0210] In the above general formula (II), R 103 and R 104 each independently represents a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. p and q each independently represent an integer of 0 to 5.

[0211] Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), bis(4-methylphenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-fluorophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(2,4-difluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, bis(2-nitrophenyl)carbonate, bis(methylsalicylphenyl)carbonate, and diaryl carbonates (which may have a substituent) such as ditolyl carbonate. Among these, diphenyl carbonate is preferred. These carbonate esters can be used alone or in combination of two or more.

[0212] The carbonate ester may be replaced with a dicarboxylic acid or a dicarboxylic acid ester, preferably in an amount of 50 mol % or less, more preferably 30 mol % or less. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, etc. When replaced with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

[0213] The ratio of the starting dihydroxy compound and carbonate ester may be any ratio as long as the desired polycarbonate resin is obtained. However, it is preferable to use the carbonate ester in an excess amount relative to the starting dihydroxy compound when polymerizing with the dihydroxy compound. The amount of the carbonate ester is preferably 1.01 times (molar ratio) or more, more preferably 1.02 times or more, relative to the amount of the dihydroxy compound. By setting the molar ratio to be equal to or more than the above lower limit, the thermal stability of the obtained polycarbonate resin is improved. The amount of carbonate ester is preferably 1.30 times (molar ratio) or less, more preferably 1.20 times or less, relative to the dihydroxy compound. By setting the molar ratio to the above upper limit or less, the reactivity is improved, the productivity of the polycarbonate resin having the desired molecular weight is improved, and the amount of residual carbonate ester in the resin is reduced, so that odor generation during molding or when a molded product is formed can be suppressed, which is preferable.

[0214] When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and a conventionally known one can be used. For example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination as an auxiliary. The transesterification catalyst may be used alone or in any combination of two or more in any ratio.

[0215] In the melt transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 320°C. The pressure during the reaction is not particularly limited, but is usually reduced to 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be carried out under the above-mentioned conditions while removing by-products.

[0216] In the presence of an alkali catalyst, the polycarbonate resin of the present invention is significantly affected by heat history and oxidation, which leads to deterioration of the color. Therefore, it is preferable to select a reaction temperature of 320°C or less and a reduced pressure condition with a lower limit of about 0.05 mmHg to prevent oxygen leakage from the equipment due to excessive reduced pressure.

[0217] The reaction can be carried out in either a batch or continuous manner. In the case of a batch reaction, the order of mixing the reaction substrate, reaction solvent, catalyst, additives, etc. is arbitrary as long as the desired polycarbonate resin can be obtained, and an appropriate order may be arbitrarily set.

[0218] In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, any compound that neutralizes the transesterification catalyst may be used. Examples of the catalyst deactivator include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc. The catalyst deactivator may be used alone or in any combination of two or more in any ratio.

[0219] The amount of the catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, and usually 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less, relative to the transesterification catalyst. The amount of the catalyst deactivator used is usually 1 ppm or more, 100 ppm or less, and preferably 50 ppm or less, relative to the polycarbonate resin.

[0220] [Other ingredients] The thermoplastic resin composition of the first invention may contain other components in addition to the polycarbonate resin of the first invention as necessary, as long as the desired physical properties are not significantly impaired. Examples of the other components include resins other than the polycarbonate resin of the first invention, various resin additives, etc. The other components may be contained in one type or in any combination and ratio of two or more types.

[0221] Examples of resins other than the polycarbonate resin of the first invention include the following resins. Thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); Styrenic resins such as polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), and cyclic cycloolefin resin (COP resin); Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU resin); Polymethacrylate resin (PMMA resin); Liquid crystal polymer (LCP), etc.

[0222] The thermoplastic resin composition of the first invention may contain one type of resin other than the polycarbonate resin of the first invention described above, or may contain two or more types in any combination and ratio.

[0223] When the thermoplastic resin composition of the first invention contains a resin other than the polycarbonate resin of the first invention, in order to more effectively obtain the effects of the first invention by including the polycarbonate resin of the first invention, the proportion of the polycarbonate resin of the first invention in all resin components contained in the thermoplastic resin composition of the first invention is preferably 20 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, particularly preferably 50 mass% or more, and most preferably 60 mass% or more.

[0224] Examples of resin additives include heat stabilizers, antioxidants, release agents, ultraviolet absorbers, dyes and pigments, flame retardants, anti-dripping agents, antistatic agents, anti-fogging agents, lubricants, anti-blocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, glass fibers, carbon fibers, inorganic fillers, and organic fibers. The thermoplastic resin composition of the first invention may contain one kind of these resin additives, or may contain two or more kinds in any combination and ratio.

[0225] Including resins and resin additives other than the polycarbonate resin of the first invention, the content of the polycarbonate resin of the first invention in the thermoplastic resin composition of the first invention is preferably 30 mass% or more, more preferably 40 mass% or more, even more preferably 50 mass% or more, particularly preferably 60 mass%, and most preferably 70 to 100 mass%.

[0226] [Method of producing thermoplastic resin composition] There is no limitation on the method for producing the thermoplastic resin composition of the first invention, and a wide variety of known methods for producing thermoplastic resin compositions can be used.Specific examples include a method in which the polycarbonate resin of the first invention and other resins and resin additives used as necessary are melt-kneaded in a mixer such as a Banbury mixer, a roll, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader.

[0227] [Molded products] To produce the molded article of the first invention using the thermoplastic resin composition of the first invention, the thermoplastic resin composition produced as described above may be pelletized and the pellets may be molded by various molding methods to produce a molded article, or the thermoplastic resin composition of the first invention that has been melt-kneaded in an extruder may be directly molded into a molded article without going through the pelletizing process.

[0228] The shape of the molded article of the first invention is not particularly limited and can be appropriately selected depending on the use and purpose of the molded article, and examples thereof include plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-like, box-like, and panel-like shapes. In addition, the molded article may have a three-dimensional shape, for example, an uneven surface or a three-dimensional curved surface. In addition, when used as a sheet, film, plate-like, etc., it may be laminated with other resin sheets to form a multilayer structure.

[0229] The method for forming the molded product is not particularly limited, and any conventionally known molding method can be used. For example, injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multi-layer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, sheet molding, thermoforming, lamination molding, press molding, etc. are included. Among these, injection molding or extrusion molding is particularly preferably used.

[0230] The molding temperature when molding the thermoplastic resin composition of the first invention is preferably 200°C or higher, more preferably 250°C or higher, and most preferably 280°C or higher. By setting the molding temperature to the above lower limit or higher, the flowability is improved and moldability is improved. The molding temperature when molding the thermoplastic resin composition of the first invention is preferably 350°C or lower, particularly preferably 320°C or lower. By setting the molding temperature to the above upper limit or lower, the color tone of the thermoplastic resin composition can be made good.

[0231] When injection molding or extrusion molding is carried out, pigments, dyes, mold release agents, heat stabilizers, etc. may be added appropriately to the thermoplastic resin composition of the first invention within the range that does not impair the object of the present invention.

[0232] <Injection molded products> The thermoplastic resin composition of the first 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 generally used for thermoplastic resins can be used. Examples include ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted and other hollow molding methods, molding methods using a heat-insulating mold, molding methods using a rapidly heated mold, foam molding (including supercritical fluids), insert molding, and IMC (in-mold coating molding) molding. A molding method using a hot runner system can also be used.

[0233] When an injection molding machine or the like is used, the mold temperature is preferably 150°C or less, more preferably 120°C or less, and most preferably 100°C or less. By setting the mold temperature to the above upper limit or less, the cooling time during molding can be shortened, and the manufacturing cycle of molded products can be shortened, thereby improving productivity. When an injection molding machine or the like is used, the mold temperature is preferably 30°C or more, and particularly preferably 50°C or more. Setting the mold temperature to the above lower limit or more is preferable because a uniform molded product can be obtained.

[0234] <Extrusion molding> The thermoplastic resin composition of the first invention can be suitably used as an extrusion molded product by extrusion molding. To produce an extrusion molded product from the thermoplastic resin composition of the first invention, an extrusion molding machine is usually used, although there is no particular limitation. The extrusion molding machine is generally equipped with a T-die, a round die, or the like, and extrusion molded products of various shapes can be obtained. Examples of the extrusion molded product include a sheet, a film, a plate, a tube, a pipe, and the like. Among these, a sheet or a film is preferred.

[0235] The extrusion molded product of the thermoplastic resin composition of the first invention may be laminated on both sides or one side of the extrusion molded product with a hard coat layer for improving adhesion, paintability, and printability, or may be heat-laminated on both sides or one side of the extrusion molded product with a film for improving weather resistance and / or scratch resistance. In addition, the surface may be subjected to a graining process or a semi-transparent or opaque process.

[0236] [Housing for communication devices] The molded article of the first invention obtained using the thermoplastic resin composition of the first invention has excellent radio wave transmittance in the microwave and / or millimeter wave bands, as well as excellent heat resistance and flame retardancy, and is therefore useful as a housing for a communication device having a built-in microwave and / or millimeter wave antenna, for which these properties are strictly required.

[0237] There are no restrictions on the shape, pattern, color, dimensions, etc. of the housing for a communications device incorporating such a microwave and / or millimeter wave antenna, and these can be appropriately selected depending on the application of the housing for a communications device incorporating a microwave and / or millimeter wave antenna.

[0238] In the first invention, microwaves are radio waves with a frequency of 3.0 to 30 GHz, and millimeter waves are radio waves with a frequency of 30 to 300 GHz. Thus, microwaves and / or millimeter waves are radio waves with a frequency of 3.0 to 300 GHz. That is, a communication device with a built-in antenna for microwaves and / or millimeter waves is a communication device with a built-in antenna for transmitting and receiving radio waves with a frequency of 3.0 to 300 GHz. Specific examples of the communication device include a notebook computer, a tablet terminal, a smartphone, or a router device that transmits and receives radio waves with a frequency of 3.0 to 300 GHz.

[0239] The frequency at which the microwave and / or millimeter wave antenna of the communications device housing having the microwave and / or millimeter wave antenna of the first invention transmits and receives is not particularly limited as long as it is 3.0 to 300 GHz, but is more suitable for radio waves in the frequency band of 3.2 to 250 GHz, and even more suitable for radio waves in the frequency band of 3.4 to 200 GHz.

[0240] In particular, the communications device housing having a built-in microwave and / or millimeter wave antenna according to the first aspect of the present invention can be suitably used for radio waves in the frequency band of 3.5 to 30 GHz used in 5G (fifth generation mobile communications system).

[0241] Radio waves in the microwave and / or millimeter wave bands tend to have poor radio wave permeability, and from this perspective, a housing for a communication device incorporating an antenna for transmitting and receiving radio waves in the microwave and / or millimeter wave bands is required to have high radio wave permeability. In addition, since communication devices that transmit and receive microwave and / or millimeter wave band radio waves tend to generate heat, housings for such devices that incorporate antennas that transmit and receive microwave and / or millimeter wave band radio waves are required to have high heat resistance and flame retardancy.

[0242] The polycarbonate resin of the first invention contained in the thermoplastic resin composition of the first invention used for the housing for a communication device having a built-in antenna for transmitting and receiving microwave and / or millimeter wave radio waves of the first invention has a low relative dielectric constant, a low dielectric loss tangent, high heat resistance, and high flame retardancy. Therefore, the thermoplastic resin composition of the first invention containing such a polycarbonate resin of the first invention has a low relative dielectric constant, a low dielectric loss tangent, high heat resistance, and high flame retardancy, and is suitable for use in the housing for a communication device that transmits and receives microwave and / or millimeter wave radio waves.

[0243] Specific examples of the housing for communication devices having a built-in microwave and / or millimeter wave antenna include the housings for notebook computers, tablet terminals, smartphones, router devices, etc. The molded article of the first invention made of the thermoplastic resin composition of the first invention is particularly suitable for these applications.

[0244] [Second Invention] [Polycarbonate resin composition] The polycarbonate resin composition of the second invention contains a carbonate structural unit (X) (hereinafter may be simply referred to as "carbonate structural unit (X)") derived from an aromatic dihydroxy compound represented by the following formula (11) (hereinafter may be simply referred to as "aromatic dihydroxy compound (11)") and a carbonate structural unit (Y) (hereinafter may be simply referred to as "carbonate structural unit (Y)") derived from an aromatic dihydroxy compound represented by the following formula (12) (hereinafter may be simply referred to as "aromatic dihydroxy compound (12)") in a molar ratio of (X) / (Y) = 1 / 99 to 99 / 1. By containing the carbonate structural unit (X) and the carbonate structural unit (Y) in a ratio of (X) / (Y)=1 / 99 to 99 / 1 (molar ratio), the polycarbonate resin composition of the present invention can have significantly improved surface hardness, alkali resistance, heat resistance, and impact strength, and can also have high transparency and hue.

[0245] [ka]

[0246] In general formula (11), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0247] [ka]

[0248] In general formula (12), R 6 ~R 9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0249] The polycarbonate resin composition of the second invention may contain the carbonate structural unit (X) and the carbonate structural unit (Y) in the above (X) / (Y) molar ratio, and there is no particular restriction on the form in which the carbonate structural unit (X) and the carbonate structural unit (Y) are contained. Usually, the carbonate structural unit (X) and the carbonate structural unit (Y) are contained in a polycarbonate resin. That is, the polycarbonate resin composition of the second invention may be a polycarbonate resin mixture of a polycarbonate resin containing a carbonate structural unit (X) and a polycarbonate resin containing a carbonate structural unit (Y), or may contain a copolymer type polycarbonate resin containing both the carbonate structural unit (X) and the carbonate structural unit (Y).

[0250] When the polycarbonate resin composition of the second invention contains a carbonate structural unit (X) and a carbonate structural unit (Y) as a copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Y), the polycarbonate resin composition of the second invention is called a "polycarbonate resin". When the polycarbonate resin composition of the second invention is a mixture of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Y), it is usually called a "polycarbonate resin composition". In the second invention, the term "polycarbonate resin composition" will include the case where the composition is composed of one type of copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Y).

[0251] <General formulas (11), (12)> In the polycarbonate resin composition of the second invention, in the general formula (11), R 1 and R 2 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0252] R 1 and R 2 Specific examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include the following. Methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl; Methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group, methylnonadecyl group; Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group, dimethyloctadecyl group; trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; Ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group; Butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group, etc.

[0253] R is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in the general formula (11). 1 and R 2 may be bonded to each other to form a ring, specific examples of which include those represented by the following general formulas (15) and (16).

[0254] [ka]

[0255] In general formulas (15) and (16), R 3 and R 4 has the same meaning as in general formula (11).

[0256] R 1 and R 2 Specific examples of the substituted or unsubstituted aryl group include a phenyl group, a tolyl group, a 4-methylphenyl group, and a naphthyl group.

[0257] R 1 and R 2 Among these, a hydrogen atom, a methyl group, or an ethyl group is preferable, a methyl group is more preferable, and R 1 and R 2 It is preferred that both of these groups are methyl groups.

[0258] In the polycarbonate resin composition of the second invention, 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. By having a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, the surface hardness, alkali resistance, etc. of the polycarbonate resin composition of the second invention can be improved.

[0259] R 3 and R 4Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, a phenyl group, and a tolyl group. Among these, a methyl group is preferable.

[0260] As the aromatic dihydroxy compound (11) according to the second aspect of the present invention, an aromatic dihydroxy compound represented by the following general formula (13) is preferred from the viewpoint of improving surface hardness.

[0261] [ka]

[0262] In general formula (13), R 10 and R 11 R each independently represents a hydrogen atom or a methyl group. 12 and R 13 each independently represents a methyl group or an ethyl group.

[0263] Specific preferred examples of the aromatic dihydroxy compound (11) according to the second invention include 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes abbreviated as "BPC") represented by the following formula (11a), 2,2-bis(2-hydroxy-5-biphenylyl)propane represented by the following formula (11b), 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane represented by the following formula (11c), 4,4-ethylidenebis(2-methylphenol) represented by the following formula (11d), 4,4-(octahydro-4,7-methano-5H-inden-5-ylidene)bis(2-methylphenol) represented by the following formula (11e), and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane represented by the following formula (11f).

[0264] [ka]

[0265] Of these, BPC represented by the above formula (11a) is most preferred.

[0266] The carbonate structural unit (Y) in the second invention has benzene rings of bisphenol linked by methylene groups as in the general formula (12) above, and can improve the impact resistance and other properties of the polycarbonate resin composition of the second invention.

[0267] In the polycarbonate resin composition of the second invention, in the general formula (12), R 6 ~R 9 R each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 6 ~R 9 By containing a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group as R, the surface hardness, alkali resistance, etc. of the polycarbonate resin composition of the second invention can be improved. 6 ~R 9 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0268] As the aromatic dihydroxy compound (12) related to the second invention, an aromatic dihydroxy compound represented by the following general formula (14), in particular an aromatic dihydroxy compound represented by the following general formula (14A) is preferred from the viewpoint of improving surface hardness, impact resistance, and alkali resistance.

[0269] [ka]

[0270] In general formula (14), R 15 ~R 18 each independently represents a methyl group or an ethyl group.

[0271] [ka]

[0272] In general formula (14A), R 20 ~R 23 each independently represents a methyl group or an ethyl group.

[0273] In addition, in the general formula (14A), R 22 , R 23 The substitution position is more preferably the position shown in the following general formula (14B).

[0274] [ka]

[0275] In general formula (14B), R 20 ~R 23 has the same meaning as in general formula (14A).

[0276] Preferred specific examples of the aromatic dihydroxy compound (12) according to the second invention include 4,4-methylenebis(2,6-dimethylphenol) represented by the following formula (12a) (hereinafter, may be abbreviated as "TmBPF"), and 4,4-methylenebis(2,5-dimethylphenol) represented by the following formula (12b) (hereinafter, may be abbreviated as "Bis25X-F").

[0277] [ka]

[0278] <Carbonate structural units (X) and (Y)> The polycarbonate resin composition of the second invention is characterized in that it contains carbonate structural units (X) and carbonate structural units (Y) in a molar ratio of (X) / (Y)=1 / 99 to 99 / 1. By increasing the ratio of the carbonate structural units (Y), heat resistance is further improved, so this ratio is preferably (X) / (Y)=1 / 99 to 85 / 15, more preferably (X) / (Y)=15 / 75 to 65 / 35.

[0279] The polycarbonate resin composition of the second invention may contain only one type of carbonate structural unit (X), or may contain two or more types. That is, it may contain carbonate structural units (X) derived from two or more types of aromatic dihydroxy compounds (11). Also, it may contain only one type of carbonate structural unit (Y), or may contain two or more types. That is, it may contain carbonate structural units (Y) derived from two or more types of aromatic dihydroxy compounds (12).

[0280] The polycarbonate resin composition of the second invention may contain the carbonate structural unit (X) and the carbonate structural unit (Y) in the above (X) / (Y) molar ratio, and may contain any content of each of the carbonate structural units (X) and (Y) within a range that does not impair the characteristics of the polycarbonate resin composition of the second invention. However, in order to reliably obtain the effects of the second invention by containing the carbonate structural unit (X) and the carbonate structural unit (Y), the polycarbonate resin composition of the second invention preferably contains the carbonate structural unit (X) and the carbonate structural unit (Y) in a total amount of 10 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, and particularly preferably 25 to 100 mol% of the carbonate structural units in the polycarbonate resin composition.

[0281] <Other carbonate structural units> The polycarbonate resin composition of the second invention may contain carbonate structural units other than the carbonate structural units (X) and (Y), i.e., carbonate structural units derived from dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (12), within the scope of the object of the second invention.

[0282] Dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (12) include the following. Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl; 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 (hereinafter sometimes abbreviated as "BPA"), 1,1-bis(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(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(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)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethanethane, 1-bis(4-hydroxyphenyl)butane, 2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)hexane, 1-bis(4-hydroxyphenyl)octane, 2-bis(4-hydroxyphenyl)octane, 1-bis(4-hydroxyphenyl)hexane, 2-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 10-bis(4-hydroxyphenyl)decane, and 1-bis(4-hydroxyphenyl)dodecane;1-bis(4-hydroxyphenyl)cyclopentane, 1-bis(4-hydroxyphenyl)cyclohexane, 4-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 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)-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)-3-tert-butyl-cyclohexane, Bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane and 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane; bisphenols containing a cardo structure 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; dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; etc.

[0283] As dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (12), among these, bis(hydroxyaryl)alkanes are preferred, and among these, bis(4-hydroxyphenyl)alkanes are preferred, and in particular, 2,2-bis(4-hydroxyphenyl)propane (BPA) is preferred from the viewpoints of impact resistance and heat resistance.

[0284] The dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (12) may be used alone or in any combination of two or more in any ratio.

[0285] <Molecular weight of polycarbonate resin composition> The molecular weight of the polycarbonate resin composition of the second invention is preferably 15,000 to 33,000 in terms of viscosity average molecular weight (Mv) calculated from the solution viscosity. If the viscosity average molecular weight is equal to or higher than the lower limit, the mechanical properties and alkali resistance of the polycarbonate resin composition of the second invention are good. If the viscosity average molecular weight is equal to or lower than the upper limit, the fluidity of the polycarbonate resin composition of the second invention tends to be sufficient. From this viewpoint, the viscosity average molecular weight (Mv) of the polycarbonate resin composition of the second invention is preferably 16,500 or more, more preferably 18,000 or more. Also, it is preferably 31,500 or less, more preferably 30,000 or less.

[0286] <Pencil hardness> The polycarbonate resin composition of the second invention has high hardness characteristics such that the pencil hardness measured by a method in accordance with ISO 15184 is preferably H or more, and this pencil hardness is more preferably 2H or more. The pencil hardness of the polycarbonate resin composition is measured for a molded article made of the polycarbonate resin composition by the method described later in the Examples section.

[0287] <Glass transition temperature> The polycarbonate resin composition of the second invention preferably has a glass transition temperature Tg of 130 to 200°C. If Tg is 130°C or higher, high heat resistance can be obtained. On the other hand, if Tg is 200°C or lower, good fluidity can be obtained, and high moldability can be obtained. For this reason, the glass transition temperature Tg of the polycarbonate resin composition of the second invention is particularly preferably 130 to 200°C. The Tg of the polycarbonate resin composition is measured by the method described in the Examples section below.

[0288] <Other ingredients> The polycarbonate resin composition of the second invention may contain other components in addition to the polycarbonate resin containing the carbonate structural unit (X) and / or the carbonate structural unit (Y), as necessary, so long as the desired physical properties are not significantly impaired. Examples of the other components include polycarbonate resins that do not contain the carbonate structural unit (X) and the carbonate structural unit (Y), resins other than polycarbonate resins, various resin additives, etc.

[0289] Examples of resin additives include heat stabilizers, antioxidants, release agents, light resistance agents (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, dyes, and pigments. The resin additive may be contained in one type, or in any combination and ratio of two or more types.

[0290] Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; styrene-based resins such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins; and polymethacrylate resins. One type of other resin may be contained, or two or more types may be contained in any combination and ratio.

[0291] [Method for producing polycarbonate resin composition] The polycarbonate resin constituting the polycarbonate resin composition of the second invention can be produced in the same manner as the polycarbonate resin of the first invention described above, except that at least aromatic dihydroxy compound (11) and aromatic dihydroxy compound (12) are used as raw material dihydroxy compounds.

[0292] A copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Y) can be produced by using a raw material dihydroxy compound containing an aromatic dihydroxy compound (11) and an aromatic dihydroxy compound (12). A polycarbonate resin containing the carbonate structural unit (X) or the carbonate structural unit (Y) can be produced by using one of these aromatic dihydroxy compounds.

[0293] [Method of manufacturing molded products] To produce a resin molded article from the polycarbonate resin composition of the second invention, a conventional extruder or injection molding machine is used.

[0294] The molding temperature when molding the polycarbonate resin composition of the second invention is preferably 200°C or higher, more preferably 250°C or higher, and most preferably 280°C or higher. Also, it is preferably 350°C or lower, and particularly preferably 320°C or lower. If the molding temperature is too low, the melt viscosity increases, the flowability decreases, and moldability may decrease. If the molding temperature is too high, the polycarbonate resin composition may become discolored, and the color tone of the obtained molded product may also deteriorate, which is not preferable.

[0295] When injection molding or extrusion molding is carried out, pigments, dyes, mold release agents, heat stabilizers, etc. may be added appropriately to the polycarbonate resin composition of the second invention within the range that does not impair the object of the second invention.

[0296] <Injection molded products> To produce an injection-molded article from the polycarbonate resin composition of the second invention, a conventional injection molding machine is used.

[0297] When using an injection molding machine or the like, the mold temperature is preferably 150°C or less, more preferably 120°C or less, and most preferably 100°C or less. Also, it is preferably 30°C or more, and particularly preferably 50°C or more. If the mold temperature is too high, it is necessary to extend the cooling time during molding, which may lengthen the production cycle of the molded product and reduce productivity. If the mold temperature is too low, the melt viscosity of the polycarbonate resin composition becomes too high, which may make it impossible to obtain a uniform molded product, and problems such as unevenness on the surface of the molded product may occur, which is not preferable.

[0298] <Extrusion molding> To produce an extrusion molded product from the polycarbonate resin composition of the second invention, a normal extrusion molding machine is used. The extrusion molding machine is generally equipped with a T-die, a round die, or the like, and can produce extrusion molded products of various shapes. Examples of the extrusion molded products include sheets, films, plates, tubes, pipes, and the like. Among these, sheets or films are preferred.

[0299] The extrusion molded product of the polycarbonate resin composition of the second invention may be laminated on both sides or one side of the extrusion molded product with a hard coat layer for improving adhesion, paintability, and printability, or may be heat-laminated on both sides or one side of the extrusion molded product with a film for improving weather resistance and / or scratch resistance. In addition, the surface may be subjected to a graining process or a semi-transparent or opaque process.

[0300] Molded articles of the polycarbonate resin composition of the second invention can be used in buildings, vehicles, electrical and electronic devices, machinery, and various other fields.

[0301] [Third Invention] [Polycarbonate resin composition] The polycarbonate resin composition of the third invention contains a carbonate structural unit (X) (hereinafter may be simply referred to as "carbonate structural unit (X)") derived from an aromatic dihydroxy compound represented by the following general formula (11) (hereinafter may be simply referred to as "aromatic dihydroxy compound (11)") and a carbonate structural unit (Z) (hereinafter may be simply referred to as "carbonate structural unit (Z)") derived from an aromatic dihydroxy compound represented by the following general formula (21) (hereinafter may be simply referred to as "aromatic dihydroxy compound (21)") in a molar ratio of carbonate structural unit (X) / carbonate structural unit (Z) (hereinafter may be simply referred to as "(X) / (Z)") = 1 / 99 to 99 / 1. By containing the carbonate structural unit (X) and the carbonate structural unit (Z) in a ratio of (X) / (Z) = 1 / 99 to 99 / 1 (molar ratio), the polycarbonate resin composition of the third invention can have significantly improved surface hardness, alkali resistance, heat resistance, impact strength, and fluidity, and can also have high transparency and hue.

[0302] [ka]

[0303] In general formula (11), R 1 and R 2 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 2 The alkyl groups in R may be bonded to each other to form a ring. 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0304] [ka]

[0305] In general formula (21), R 6 ~R9 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0306] The polycarbonate resin composition of the third invention may contain the carbonate structural unit (X) and the carbonate structural unit (Z) in a molar ratio of (X) / (Z)=1 / 99 to 99 / 1, and there is no particular limitation on the form in which the carbonate structural unit (X) and the carbonate structural unit (Z) are contained. Usually, the carbonate structural unit (X) and the carbonate structural unit (Z) are contained in the polycarbonate resin.

[0307] The polycarbonate resin composition of the third invention may be a polycarbonate resin mixture of a polycarbonate resin containing a carbonate structural unit (X) and a polycarbonate resin containing a carbonate structural unit (Z), or may contain a copolymer type polycarbonate resin containing both the carbonate structural unit (X) and the carbonate structural unit (Z). The polycarbonate resin composition of the third invention may be a mixture of a polycarbonate resin containing the carbonate structural unit (X) and / or the carbonate structural unit (Z) and a copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Z), or may further contain a polycarbonate resin containing neither the carbonate structural unit (X) nor the carbonate structural unit (Z).

[0308] When the polycarbonate resin composition of the third invention contains a carbonate structural unit (X) and a carbonate structural unit (Z) as a copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Z), the polycarbonate resin composition of the third invention is called a "polycarbonate resin". When the polycarbonate resin composition of the third invention is a mixture of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Z), it is usually called a "polycarbonate resin composition". The same applies to the above-mentioned other content forms.

[0309] In the third invention, the term "polycarbonate resin composition" will include the case where the composition is composed of one type of copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Z).

[0310] <General formula (11), (21)> The general formula (11), the aromatic dihydroxy compound (11), and the carbonate structural unit (X) in the polycarbonate resin composition of the third invention are the same as the general formula (11), the aromatic dihydroxy compound (11), and the carbonate structural unit (X) in the polycarbonate resin composition of the second invention, and the preferred ones are also the same.

[0311] In the polycarbonate resin composition of the third invention, the carbonate structural unit (Z) has two benzene rings linked together by a single bond as represented by the general formula (21) above, thereby making it possible to improve impact resistance.

[0312] In the polycarbonate resin composition of the third invention, 6 ~R 9 R each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 6 ~R 9 By containing a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group as R, the surface hardness, alkali resistance, etc. of the polycarbonate resin composition of the third invention can be improved. 6 ~R 9 Specific examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or the substituted or unsubstituted aryl group include R 3 ,R 4Specific examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or the substituted or unsubstituted aryl group include those exemplified above, but a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0313] As the aromatic dihydroxy compound (21) related to the third invention, an aromatic dihydroxy compound represented by the following general formula (22), particularly an aromatic dihydroxy compound represented by the following general formula (22A) is preferred from the viewpoint of improving surface hardness, impact resistance, and alkali resistance.

[0314] [ka]

[0315] In general formula (22), R 31 ~R 34 each independently represents a methyl group or an ethyl group.

[0316] [ka]

[0317] In general formula (22A), R 31 ~R 34 has the same meaning as in the above general formula (22).

[0318] In addition, in the general formula (22A), R 33 , R 34 The substitution position is more preferably the position shown in the following general formula (22B).

[0319] [ka]

[0320] In general formula (22B), R 31 ~R 34 has the same meaning as in formula (22A).

[0321] A preferred specific example of the aromatic dihydroxy compound (21) according to the third invention includes 2,2,6,6-tetramethyl-4,4-biphenol (hereinafter sometimes abbreviated as "TmBP" and also referred to as 3,3',5,5'-tetramethyl-1,1'-biphenyl-4,4'-diol) represented by the following formula (23).

[0322] [ka]

[0323] <Carbonate structural units (X) and (Z)> The polycarbonate resin composition of the third invention is characterized in that it contains carbonate structural units (X) and carbonate structural units (Z) in a molar ratio of (X) / (Z)=1 / 99 to 99 / 1. By increasing the ratio of the carbonate structural units (Z), heat resistance is further improved, so this ratio is preferably (X) / (Z)=1 / 99 to 95 / 5, more preferably (X) / (Z)=5 / 95 to 90 / 10.

[0324] The molar ratio of the carbonate structural unit (X) and the carbonate structural unit (Z) contained in the polycarbonate resin composition of the third invention is determined by dissolving the polycarbonate resin composition in deuterated chloroform. 1 It can be calculated by measuring H-NMR. Specifically, a polycarbonate resin in deuterated chloroform solution is prepared so that the polycarbonate resin concentration is 50 mg / mL, and measurement is performed at 30°C, with a relaxation time of 6 seconds and an accumulation count of 128.

[0325] The proportions of the carbonate structural unit (X), the carbonate structural unit (Z) and other carbonate structural units described below contained in the polycarbonate resin composition of the third invention can also be calculated from the charge composition ratio of the dihydroxy compound during the production of the polycarbonate resin. In the examples shown below, the proportions are determined from the charge composition ratio.

[0326] The polycarbonate resin composition of the third invention may contain only one type of carbonate structural unit (X), or may contain two or more types. That is, it may contain carbonate structural units (X) derived from two or more types of aromatic dihydroxy compounds (11). Also, it may contain only one type of carbonate structural unit (Z), or may contain two or more types. That is, it may contain carbonate structural units (Z) derived from two or more types of aromatic dihydroxy compounds (21).

[0327] The polycarbonate resin composition of the third invention may contain the carbonate structural unit (X) and the carbonate structural unit (Z) in the above (X) / (Z) molar ratio, and may contain any content of each of the carbonate structural units (X) and (Z) within a range that does not impair the characteristics of the polycarbonate resin composition of the third invention. However, in order to reliably obtain the effects of the third invention by containing the carbonate structural unit (X) and the carbonate structural unit (Z), the polycarbonate resin composition of the third invention preferably contains the carbonate structural unit (X) and the carbonate structural unit (Z) in a total amount of 20 mol% or more, preferably 40 mol% or more, more preferably 60 mol% or more, and particularly preferably 60 to 100 mol% of the carbonate structural units in the polycarbonate resin composition.

[0328] <Other carbonate structural units> The polycarbonate resin composition of the third invention may contain carbonate structural units other than the carbonate structural units (X) and (Z), i.e., carbonate structural units derived from dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (21), within the scope of the third invention.

[0329] Dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (21) include the following. Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl; 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 (hereinafter sometimes abbreviated as "BPA"), 1,1-bis(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(4-hydroxy-3,5-dimethylphenyl)propane (hereinafter sometimes abbreviated as "TmBPA"), 2,2-bis(3-cyano It is also called 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, and bis(4-hydroxy-3,5-dimethylphenyl)methane (4,4-methylenebis(2,6-dimethylphenol) (hereinafter sometimes abbreviated as "TmBPF").), bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethanethane, 1-bis(4-hydroxyphenyl)butane, 2-bis(4-hydroxyphenyl)butane bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1-bis(4-hydroxyphenyl)octane, 2-bis(4-hydroxyphenyl)octane, 1-bis(4-hydroxyphenyl)hexane, 2-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 10-bis(4-hydroxyphenyl)decane, and 1-bis(4-hydroxyphenyl)dodecane; 1-bis(4-hydroxyphenyl)cyclopentane, 1-bis(4-hydroxyphenyl)cyclohexane, 4-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 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)-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)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane and other bis(hydroxyaryl)cycloalkanes; 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, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, etc.

[0330] As dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (21), among these, bis(hydroxyaryl)alkanes are preferred, and among these, bis(4-hydroxyphenyl)alkanes are preferred. In particular, from the viewpoints of impact resistance and heat resistance, 2,2-bis(4-hydroxyphenyl)propane (BPA) or bis(4-hydroxy-3,5-dimethylphenyl)methane (4,4-methylenebis(2,6-dimethylphenol) (TmBPF)) is preferred, and from the viewpoint of dielectric properties, TmBPF is preferred.

[0331] The dihydroxy compounds other than the aromatic dihydroxy compounds (11) and (21) may be used alone or in any combination of two or more in any ratio.

[0332] <Molecular weight of polycarbonate resin> The molecular weight of the polycarbonate resin in the polycarbonate resin composition of the third invention is not particularly limited, but the viscosity average molecular weight (Mv) calculated from the solution viscosity is preferably 16,000 or more. When the viscosity average molecular weight is the above lower limit or more, it is preferable because the mechanical properties and alkali resistance of the polycarbonate resin composition of the third invention are improved. From this viewpoint, the viscosity average molecular weight of the polycarbonate resin is more preferably 17,000 or more, even more preferably 18,000 or more, and particularly preferably 18,500 or more. The viscosity average molecular weight (Mv) of the polycarbonate resin in the polycarbonate resin composition of the third invention is preferably 30,000 or less. When the viscosity average molecular weight is the above upper limit or less, the flowability of the polycarbonate resin composition of the third invention tends to be good, which is preferable. From this viewpoint, the viscosity average molecular weight of the polycarbonate resin is more preferably 29,000 or less, even more preferably 28,000 or less, and particularly preferably 27,000 or less.

[0333] <Pencil hardness> The polycarbonate resin composition of the third invention has high hardness characteristics such that the pencil hardness measured by a method in accordance with ISO 15184 is not particularly limited, but is preferably H or higher, and more preferably 2H or higher. The pencil hardness of the polycarbonate resin composition is measured for a molded article made of the polycarbonate resin composition by the method described later in the Examples section.

[0334] <Glass transition temperature> The polycarbonate resin composition of the third invention preferably has a glass transition temperature Tg of 130 to 200°C. If Tg is 130°C or higher, high heat resistance can be obtained. On the other hand, if Tg is 200°C or lower, good fluidity can be obtained, and high moldability can be obtained. For this reason, the glass transition temperature Tg of the polycarbonate resin composition of the third invention is preferably 130 to 200°C. The Tg of the polycarbonate resin composition is measured by the method described in the Examples section below.

[0335] <Other ingredients> The polycarbonate resin composition of the third invention may contain other components in addition to the polycarbonate resin containing the carbonate structural unit (X) and / or the carbonate structural unit (Z), as necessary, so long as the desired physical properties are not significantly impaired. Examples of the other components include polycarbonate resins that do not contain the carbonate structural unit (X) and the carbonate structural unit (Z), resins other than polycarbonate resins, various resin additives, etc.

[0336] In order to reliably obtain the effects of the third invention by containing a polycarbonate resin containing the carbonate structural units (X) and the carbonate structural units (Z), the polycarbonate resin composition of the third invention preferably contains the carbonate structural units (X) and the carbonate structural units (Z) in a total amount of 65 mass% or more, particularly 70 mass% or more, and even more particularly 75 mass% or more, based on 100 mass% of the polycarbonate resin composition.

[0337] In order to effectively bring out the features of the third invention, the content of the polycarbonate resin in the polycarbonate resin composition of the third invention is preferably 80 mass% or more, more preferably 85 mass% or more, and particularly preferably 90 mass% or more, relative to 100 mass% of the polycarbonate resin composition of the third invention.

[0338] Examples of resin additives include heat stabilizers, antioxidants, release agents, light resistance agents (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, dyes, and pigments. The resin additive may be contained in one type, or in any combination and ratio of two or more types.

[0339] Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; styrene-based resins such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins; and polymethacrylate resins. One type of other resin may be contained, or two or more types may be contained in any combination and ratio.

[0340] [Manufacturing method of polycarbonate resin] The polycarbonate resin constituting the polycarbonate resin composition of the third invention can be produced in the same manner as the polycarbonate resin of the first invention described above, except that at least aromatic dihydroxy compound (11) and aromatic dihydroxy compound (21) are used as raw material dihydroxy compounds.

[0341] A copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Z) can be produced by using a raw material dihydroxy compound containing an aromatic dihydroxy compound (11) and an aromatic dihydroxy compound (21). A polycarbonate resin containing the carbonate structural unit (X) or the carbonate structural unit (Z) can be produced by using one of these aromatic dihydroxy compounds.

[0342] [Manufacturing method of polycarbonate resin molded products] To produce a polycarbonate resin molded article from the polycarbonate resin composition of the third invention, a conventional extruder or injection molding machine is used.

[0343] The molding temperature when molding the polycarbonate resin composition of the third invention is preferably 200°C or higher, more preferably 250°C or higher, and most preferably 280°C or higher. By setting the molding temperature to the above lower limit or higher, the flowability is improved and moldability is improved. The molding temperature when molding the polycarbonate resin composition of the third invention is preferably 350°C or lower, particularly preferably 320°C or lower. By setting the molding temperature to the above upper limit or lower, the color tone of the polycarbonate resin composition can be made good.

[0344] When injection molding or extrusion molding is carried out, pigments, dyes, mold release agents, heat stabilizers, etc. may be added appropriately to the polycarbonate resin composition of the third invention within the range that does not impair the object of the present invention.

[0345] [Molded products] The polycarbonate resin composition of the third invention can be suitably used as a molded product by thermal processing such as injection molding and extrusion molding. There is no limitation on the shape, pattern, color, size, etc. of such a polycarbonate resin molded product, and it can be appropriately selected according to the application of the molded product. For example, various shapes such as plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, annular, circular, elliptical, polygonal, irregular, hollow, frame-like, box-like, panel-like, and special shapes can be mentioned. In addition, it may be a three-dimensional shape having an uneven surface or a three-dimensional curved surface.

[0346] <Injection molded products> The polycarbonate resin composition of the third 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 generally used for thermoplastic resins can be used. Examples include ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted and other hollow molding methods, molding methods using a heat-insulating mold, molding methods using a rapidly heated mold, foam molding (including supercritical fluids), insert molding, and IMC (in-mold coating molding) molding. A molding method using a hot runner system can also be used.

[0347] When an injection molding machine or the like is used, the mold temperature is preferably 150°C or less, more preferably 120°C or less, and most preferably 100°C or less. By setting the mold temperature to the above upper limit or less, the cooling time during molding can be shortened, and the manufacturing cycle of molded products can be shortened, thereby improving productivity. When an injection molding machine or the like is used, the mold temperature is preferably 30°C or more, and particularly preferably 50°C or more. Setting the mold temperature to the above lower limit or more is preferable because a uniform molded product can be obtained.

[0348] <Extrusion molding> The polycarbonate resin composition of the third invention can be suitably used as an extrusion molded product by extrusion molding. To produce an extrusion molded product from the polycarbonate resin composition of the third invention, an extrusion molding machine is usually used, although there is no particular limitation. The extrusion molding machine is generally equipped with a T-die, a round die, or the like, and can produce extrusion molded products of various shapes. Examples of the extrusion molded product include a sheet, a film, a plate, a tube, a pipe, and the like. Among these, a sheet or a film is preferred.

[0349] The extrusion molded product of the polycarbonate resin composition of the third invention may be laminated on both sides or one side with a hard coat layer for improving adhesion, paintability, and printability, or a film for improving weather resistance and / or scratch resistance may be heat laminated on both sides or one side of the extrusion molded product. In addition, the surface may be subjected to a graining process, a semi-transparent or opaque process, or the like.

[0350] <Application> Molded articles of the polycarbonate resin composition of the third invention can be used as parts for, for example, various automobile members, electrical and electronic devices, information terminal devices, OA devices, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and sundries, lighting equipment, etc. Among these, the molded article of the present invention has excellent surface hardness and alkali resistance, and excellent heat resistance, impact resistance, and flowability, and is therefore particularly suitable for use in parts for electrical and electronic devices, information terminal devices, OA devices, home appliances, etc., and can be particularly suitable for use as a molding material for the housings of electrical and electronic devices, information terminal devices, OA devices, automobile interior parts, and home appliances. EXAMPLES

[0351] The present invention will now be described in more detail with reference to examples. The present invention is not limited to the following examples.

[0352] The physical properties of the polycarbonate resins obtained in the following Examples and Comparative Examples were evaluated by the following methods.

[0353] (1)Surface hardness: Pencil hardness Using a small injection molding machine (Shinko Selvic C, Mobile, Inc.), polycarbonate resin plates with a thickness of 3 mm, length of 25 mm, and width of 25 mm were molded to obtain test pieces under the conditions of cylinder temperature and mold temperature shown in Tables 1 and 2. The pencil hardness of the test pieces was measured at a load of 750 g using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with ISO 15184.

[0354] (2) Fluidity: Viscosity average molecular weight (Mv) The 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 viscosity tube (manufactured by Moritomo Rika Kogyo Co., Ltd.), and the viscosity average molecular weight (Mv) was calculated using Schnell's viscosity formula (formula below). η = 1.23 × 10 -4 Mv 0.83

[0355] (3) Heat resistance: glass transition temperature (Tg) Using a differential scanning calorimeter (DSC6220 manufactured by SII), about 10 mg of a polycarbonate resin sample was heated at a heating rate of 20°C / min to measure the calorific value, and the extrapolated glass transition onset temperature was determined according to JIS K7121, which is the temperature at the intersection of a straight line extending the low-temperature side baseline to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change in the glass transition is maximum. The extrapolated glass transition temperature was designated as the glass transition temperature (Tg).

[0356] (4) Impact resistance: Izod impact strength Using a small injection molding machine (Shinko Selvic C, Mobile Co., Ltd.), polycarbonate resin plates with a thickness of 3.2 mm, length of 53.5 mm, and width of 12.7 mm were molded to obtain test pieces under the conditions of cylinder temperature and mold temperature shown in Tables 1 and 2. In accordance with JIS K-7110, the test pieces were subjected to an impact test five times using a 60 kg hammer, and the number of breaks was compared.

[0357] (5) Alkali resistance Using a small injection molding machine (Shinko Selvic C, Mobile, Inc.), a polycarbonate resin plate 3 mm thick, 25 mm long, and 25 mm wide was molded to obtain a test piece under the cylinder temperature and mold temperature conditions shown in Tables 1 and 2. The test piece was immersed in a 25% by mass NaOH aqueous solution filled in a petri dish at 50°C for 92 hours, then removed and washed with water. If the test piece was unchanged from before the test, it was rated as "S", if it was slightly whitened, it was rated as "A", if it was whitened, it was rated as "B", and if it was significantly whitened, it was rated as "C".

[0358] (6) Flame retardancy: 20mm vertical flame test (0.8mmt) The polycarbonate resin pellets were dried at 120°C for 4 hours, and then molded into combustion test specimens measuring 125 mm x 13 mm x 0.8 mm thick using an injection molding machine (Sumitomo Heavy Industries, Ltd., "SE100") at a cylinder temperature of 300°C and a mold temperature of 80°C. The obtained test pieces for the combustion test were subjected to a 20 mm vertical combustion test in accordance with UL94 (October 29, 1996, 5th edition). The flammability test results were classified into V-0, V-1, V-2, and non-conforming according to the material classification described in UL94. If the classification result was V-2, the time required for the smoke or drops to ignite the cotton tag was recorded and compared.

[0359] (7) Dielectric properties: Dielectric constant (ε r ) · Dielectric tangent (tan δ) Polycarbonate resin that had been vacuum dried at 80°C for 5 hours was molded into a film shape using a heat press molding machine to produce a film with a thickness of 40 to 150 μm. The molding conditions for the heat press molding machine were appropriately adjusted to a temperature of 150 to 250°C and a pressure of 10 to 15 MPa. From this film, a strip of film with a length of 70 mm and a width of 2 mm was cut out and conditioned for 48 hours under conditions of room temperature of 23°C and humidity of 50%. After that, the relative dielectric constant (ε r ) and dielectric tangent (tanδ×10-3 ) was measured.

[0360] [Example 1] A raw material mixture was prepared by adding 23.34 g (about 0.091 mol) of 4,4-methylenebis(2,6-dimethylphenol) (TmBPF) (manufactured by Tokyo Chemical Industry Co., Ltd.), 93.37 g (about 0.364 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) (manufactured by Honshu Chemical Co., Ltd.), 99.97 g (about 0.467 mol) of diphenyl carbonate (DPC), and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst to a glass reactor having a capacity of 150 ml and equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device.

[0361] Next, the pressure in the glass reactor was reduced to about 50 Pa (0.38 Torr), and then the operation of returning the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. After the nitrogen replacement, the temperature outside the reactor was set to 220°C, and the temperature inside the reactor was gradually raised to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) in absolute pressure over 40 minutes while distilling off phenol by-produced by the oligomerization reaction of the dihydroxy compound and DPC inside the reactor.

[0362] Next, the pressure in the reactor was kept at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. Thereafter, the temperature outside the reactor was raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 40 minutes, and the distilled phenol was removed from the system. Furthermore, the temperature outside the reactor was raised to 285°C, and the absolute pressure inside the reactor was reduced to 30 Pa (about 0.2 Torr), and a polycondensation reaction was carried out. The polycondensation reaction was terminated when the agitator of the reactor reached a predetermined stirring power.

[0363] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then the gauge pressure was increased to 0.2 MPa. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor to obtain strand-shaped polycarbonate resin, which was then pelletized using a rotary cutter. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Table 1.

[0364] [Example 2] The procedure described in Example 1 was repeated except that the raw material mixture was prepared by adding 46.69 g (approximately 0.182 mol) of TmBPF (manufactured by Tokyo Chemical Industry Co., Ltd.), 70.02 g (approximately 0.273 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 99.97 g (approximately 0.467 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 5 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 1 and 3.

[0365] [Example 3] The procedure described in Example 1 was repeated except that the raw material mixture was prepared by adding 93.37 g (approximately 0.364 mol) of TmBPF (manufactured by Tokyo Chemical Industry Co., Ltd.), 23.34 g (approximately 0.091 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 99.97 g (approximately 0.467 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 8 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 1 and 3.

[0366] [Example 4] The procedure described in Example 1 was repeated except that the raw material mixture was prepared by adding 11.67 g (approximately 0.046 mol) of TmBPF (manufactured by Tokyo Chemical Industry Co., Ltd.), 105.04 g (approximately 0.410 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 99.97 g (approximately 0.467 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 8 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Table 1.

[0367] [Example 5] The procedure described in Example 1 was repeated except that the raw material mixture was prepared by adding 46.68 g (approximately 0.182 mol) of TmBPF (manufactured by Tokyo Chemical Industry Co., Ltd.), 70.03 g (approximately 0.273 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 99.97 g (approximately 0.467 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 5 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Table 1.

[0368] [Example 6] A raw material mixture was prepared by adding 27.96 g (about 0.115 mol) of 2,2,6,6-tetramethyl-4,4-biphenol (TmBP) (manufactured by Tokyo Chemical Industry Co., Ltd.), 88.75 g (about 0.3462 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) (manufactured by Honshu Chemical Co., Ltd.), 103.33 g (about 0.482 mol) of diphenyl carbonate (DPC), and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst to a glass reactor having a capacity of 150 ml and equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device.

[0369] Next, the pressure in the glass reactor was reduced to about 50 Pa (0.38 Torr), and then the operation of returning the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. After the nitrogen replacement, the temperature outside the reactor was set to 220°C, and the temperature inside the reactor was gradually raised to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) in absolute pressure over 40 minutes while distilling off phenol by-produced by the oligomerization reaction of the dihydroxy compound and DPC inside the reactor.

[0370] Next, the pressure in the reactor was kept at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. Thereafter, the temperature outside the reactor was raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 40 minutes, and the distilled phenol was removed from the system. Furthermore, the temperature outside the reactor was raised to 285°C, and the absolute pressure inside the reactor was reduced to 30 Pa (about 0.2 Torr), and a polycondensation reaction was carried out. The polycondensation reaction was terminated when the agitator of the reactor reached a predetermined stirring power.

[0371] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then the gauge pressure was increased to 0.2 MPa. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor to obtain strand-shaped polycarbonate resin, which was then pelletized using a rotary cutter. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Table 1.

[0372] [Example 7] The procedure of Example 6 was repeated except that the raw material mixture was prepared by adding 45.12 g (approximately 0.186 mol) of TmBP (manufactured by Tokyo Chemical Industry Co., Ltd.), 71.59 g (approximately 0.279 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 103.90 g (approximately 0.485 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 3.2 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 1 and 3.

[0373] [Example 8] The procedure described in Example 6 was repeated except that the raw material mixture was prepared by adding 11.09 g (approximately 0.046 mol) of TmBP (manufactured by Tokyo Chemical Industry Co., Ltd.), 93.88 g (approximately 0.366 mol) of BPC (manufactured by Honshu Chemical Industry Co., Ltd.), 11.74 g (approximately 0.046 mol) of 4,4-methylenebis(2,6-dimethylphenol) (TmBPF) (manufactured by Tokyo Chemical Industry Co., Ltd.), 101.50 g (approximately 0.474 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 3 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Table 1.

[0374] [Example 9] The procedure described in Example 6 was repeated except that the raw material mixture was prepared by adding 22.31 g (approximately 0.092 mol) of TmBP (manufactured by Tokyo Chemical Industry Co., Ltd.), 70.80 g (approximately 0.276 mol) of BPC (manufactured by Honshu Chemical Industry Co., Ltd.), 23.60 g (approximately 0.092 mol) of TmBPF (manufactured by Tokyo Chemical Industry Co., Ltd.), 102.06 g (approximately 0.476 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 3 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the evaluations according to the procedures described above. The results are shown in Table 1.

[0375] [Example 10] The procedure of Example 1 was repeated except that a raw material mixture was prepared by adding 71.51 g (approximately 0.265 mol) of 4,4-ethylidenebis(2,6-dimethylphenol) (TmBPE), 45.20 g (approximately 0.176 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 96.79 g (approximately 0.452 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 5 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the evaluations according to the procedures described above. The results are shown in Table 3.

[0376] [Comparative Example 1] A raw material mixture was prepared by adding 116.71 g (approximately 0.455 mol) of TmBPF (manufactured by Tokyo Chemical Industry Co., Ltd.), 99.48 g (approximately 0.464 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst so that the amount of cesium carbonate was 5 μmol per 1 mol of the total dihydroxy compounds.

[0377] Next, the pressure in the glass reactor was reduced to about 50 Pa (0.38 Torr), and then the operation of returning the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. After the nitrogen replacement, the temperature outside the reactor was set to 220°C, and the temperature inside the reactor was gradually raised to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) in absolute pressure over 40 minutes while distilling off phenol by-produced by the oligomerization reaction of the dihydroxy compound and DPC inside the reactor.

[0378] Next, the pressure inside the reactor was kept at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. Thereafter, the temperature outside the reactor was raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute pressure over 40 minutes, and the distilled phenol was removed from the system. Furthermore, when the temperature outside the reactor was raised to 285°C, crystallization of the reaction solution occurred, making it difficult to continue the reaction, so the reaction was stopped. In this Comparative Example 1, since only TmBPF was used, crystallization proceeded and a polymer could not be obtained, so the above-mentioned evaluations were not performed.

[0379] [Comparative Example 2] The procedure described in Example 1 was repeated except that a raw material mixture was prepared using 61.73 g (approximately 0.241 mol) of TmBPF (Tokyo Chemical Industry Co., Ltd.), 54.98 g (approximately 0.241 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter, sometimes abbreviated as "BPA"), 108.34 g (approximately 0.506 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 3 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the evaluations according to the procedures described above. The results are shown in Table 2.

[0380] [Comparative Example 3] The procedure of Example 1 was repeated except that the raw material mixture was prepared by adding 100.00 g (approximately 0.390 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 86.08 g (approximately 0.402 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 4.5 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 2 and 3.

[0381] [Comparative Example 4] The procedure of Example 1 was repeated except that the raw material mixture was prepared by adding 116.71 g (approximately 0.511 mol) of BPA, 117.18 g (approximately 0.547 mol) of DPC, and a 0.04 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 0.5 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 2 and 3.

[0382] [Comparative Example 5] The procedure described in Example 1 was repeated, except that a raw material mixture was prepared by adding 116.71 g (approximately 0.410 mol) of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (hereinafter sometimes abbreviated as "TmBPA") (manufactured by Honshu Chemical Co., Ltd.), 88.79 g (approximately 0.414 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 5 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 2 and 3.

[0383] [Comparative Example 6] The procedure described in Example 1 was repeated except that the raw material mixture was prepared by adding 25.34 g (approximately 0.089 mol) of TmBPA (manufactured by Honshu Chemical Co., Ltd.), 91.37 g (approximately 0.356 mol) of TmBPF (manufactured by Tokyo Chemical Industry Co., Ltd.), 97.83 g (approximately 0.457 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 8 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the evaluations according to the procedures described above. The results are shown in Table 2.

[0384] [Comparative Example 7] The procedure described in Example 1 was repeated except that a raw material mixture was prepared by adding 61.38 g (approximately 0.216 mol) of TmBPA (manufactured by Honshu Chemical Co., Ltd.), 55.33 g (approximately 0.216 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 95.71 g (approximately 0.447 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 2 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 2 and 3.

[0385] [Comparative Example 8] The procedure of Example 1 was repeated except that the raw material mixture was prepared by adding 54.98 g (approximately 0.241 mol) of BPA (manufactured by Honshu Chemical Co., Ltd.), 61.73 g (approximately 0.241 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 107.82 g (approximately 0.503 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst such that the amount of cesium carbonate was 3 μmol per 1 mol of the total dihydroxy compounds. The polycarbonate resin thus obtained was subjected to the various evaluations according to the procedures described above. The results are shown in Tables 2 and 3.

[0386] [Table 1]

[0387] [Table 2]

[0388] [Table 3]

[0389] [Consideration] From the above results, the following can be seen: Examples 1 to 4 and Examples 7 to 9 have good impact resistance since there was no break in the five-time impact test. Comparative Example 4 has good impact resistance, but the pencil hardness and alkali resistance are inferior to Examples 1 to 4 and Examples 7 to 9. Comparative Example 2 also has good impact resistance, but the alkali resistance and pencil hardness are inferior to Examples 1 to 4 and Examples 7 to 9. Although Examples 5 and 6 do not exhibit the same impact resistance as Examples 1 to 4 and Examples 7 to 9, they have very high pencil hardness and good alkali resistance. Comparative Examples 2 and 4 have good impact resistance, but are inferior to Examples 5 and 6 in pencil hardness. In Comparative Example 1, crystallization occurs during polymerization, making it difficult to obtain a polymer. Comparative Example 3 has good pencil hardness, but is inferior in impact resistance to Examples 1 to 9, and also has poor heat resistance due to its low Tg. Comparative Examples 5 and 7 are good in pencil hardness and alkali resistance, but are significantly inferior in impact resistance to Examples 1-9. Comparative Example 6 has good alkali resistance, but is inferior to Examples 1-9 in pencil hardness and impact resistance.

[0390] In addition, the polycarbonate resins of Examples 2 and 3 having the repeating unit (A) (derived from BPC) and the repeating units (B') and (B) (derived from TmBPF) are superior in relative dielectric constant and dielectric dissipation factor compared to Comparative Example 4, and superior in heat resistance, relative dielectric constant and dielectric dissipation factor compared to Comparative Example 8. Although the dielectric properties and heat resistance are at the same level as Comparative Example 7, the flame retardancy is remarkably superior. Examples 7 and 10 are superior in heat resistance, flame retardancy, and impact resistance compared to Comparative Example 3, are superior in heat resistance, dielectric properties, and flame retardancy compared to Comparative Example 4, and are significantly superior in flame retardancy and impact resistance compared to Comparative Example 5. Examples 7 and 10 are superior in flame retardancy and impact resistance compared to Comparative Example 7. Examples 7 and 10 are superior in heat resistance, dielectric properties, and flame retardancy compared to Comparative Example 8. Comparative Example 1 was difficult to mold because it crystallized, and therefore could not be used as a housing for a communication device incorporating a microwave and / or millimeter wave antenna.

[0391] Moreover, Examples 1 to 10 can be injection molded without any problems using a general injection molding machine, and are excellent in flowability and moldability.

[0392] From the above, it can be seen that the polycarbonate resins of Examples 1 to 10, which are the polycarbonate resin compositions of the present invention, are superior in both surface hardness and alkali resistance, and are also superior in heat resistance, impact resistance, and fluidity, compared to the polycarbonate resins of Comparative Examples 1 to 8. Moreover, it can be seen that the polycarbonate resins of Examples 2 and 3, which are the polycarbonate resins of the first invention, are resins having excellent dielectric properties, as well as excellent heat resistance and flame retardancy, and are suitable for use as housings for communication devices having built-in microwave and / or millimeter wave antennas.

[0393] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2019-157059 filed on August 29, 2019, Japanese Patent Application No. 2020-101649 filed on June 11, 2020, and Japanese Patent Application No. 2020-122968 filed on July 17, 2020, and is incorporated by reference in its entirety.

Claims

1. A thermoplastic resin composition comprising a polycarbonate resin having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B') represented by the following general formula (2A'). 【Chemistry 1】 In general formula (1), R １ and R ２ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. １ and R ２ The alkyl groups in R may be bonded to each other to form a ring. ３ and R ４ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 【Chemistry 2】 In the general formula (2A'), X' represents a single bond or a methylene group. ６ ~R ９ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

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

3. In the general formula (1), R ３ and R ４ The thermoplastic resin composition according to claim 1 or 2, wherein is a methyl group.

4. In the general formula (2A'), R ６ ~R ９ The thermoplastic resin composition according to any one of claims 1 to 3, wherein is a methyl group.

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the content ratio of the repeating unit (A) and the repeating unit (B') in the polycarbonate resin is, in terms of molar ratio, repeating unit (A): repeating unit (B') = 1:99 to 99:

1.

6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the sum of the contents of the repeating unit (A) and the repeating unit (B') contained in the polycarbonate resin is 50 mol% or more of all carbonate structural units in the polycarbonate resin.

7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the polycarbonate resin has a glass transition temperature of 125°C or higher.

8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the thermoplastic resin composition contains 50% by mass or more of the polycarbonate resin.

9. The thermoplastic resin composition according to any one of claims 1 to 8, comprising the polycarbonate resin as a copolymer polycarbonate resin of the repeating unit (A) and the repeating unit (B').

10. The thermoplastic resin composition according to any one of claims 1 to 8, comprising a polycarbonate resin containing the repeating unit (A) and a polycarbonate resin containing the repeating unit (B').

11. The thermoplastic resin composition according to any one of claims 1 to 10, wherein the viscosity average molecular weight (Mv) of the polycarbonate resin is in the range of 14,500 to 30,000.

12. The thermoplastic resin composition according to claim 11, wherein the viscosity average molecular weight (Mv) of the polycarbonate resin is in the range of 18,000 to 28,000.

13. The thermoplastic resin composition according to any one of claims 1 to 12, having a pencil hardness of H or more as measured by a method in accordance with ISO 15184.

14. A molded article obtained using a thermoplastic resin composition containing a polycarbonate resin having a repeating unit (A) represented by the following general formula (1) and a repeating unit (B) represented by the following general formula (2A). 【Chemistry 4】 In general formula (1), R １ and R ２ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. １ and R ２ The alkyl groups in R may be bonded to each other to form a ring. ３ and R ４ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 【Chemistry 5】 In the general formula (2A), X represents a single bond or a divalent organic group represented by the following general formula (3): ６ ~R ９ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 【Chemistry 6】 In general formula (3), R ５ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

15. In the general formula (1), R １ and R ２ is a methyl group, or R １ and R ２ The molded article according to claim 14, wherein the alkyl groups represented by the following formula (1a) or (1b) are bonded to each other to form a ring represented by the following formula (1a) or (1b): 【Chemistry 7】

16. In the general formula (1), R ３ and R ４ The molded article according to claim 14 or 15, wherein is a methyl group.

17. In the general formula (2A), R ６ ~R ９ The molded article according to any one of claims 14 to 16, wherein is a methyl group.

18. In the general formula (3), R ５ The molded article according to any one of claims 14 to 17, wherein is a hydrogen atom or a methyl group.

19. The molded article according to any one of claims 14 to 18, wherein the content ratio of the repeating unit (A) and the repeating unit (B) in the polycarbonate resin is, in terms of molar ratio, repeating unit (A): repeating unit (B) = 1:99 to 99:

1.

20. The molded article according to any one of claims 14 to 19, wherein the sum of the contents of the repeating unit (A) and the repeating unit (B) contained in the polycarbonate resin is 50 mol% or more of all carbonate structural units of the polycarbonate resin.

21. The molded article according to any one of claims 14 to 20, wherein the polycarbonate resin has a glass transition temperature of 125°C or higher.

22. The molded article according to any one of claims 14 to 21, wherein the thermoplastic resin composition contains 50% by mass or more of the polycarbonate resin.

23. The molded article according to any one of claims 14 to 22, wherein the molded article is an extrusion molded article or an injection molded article.

24. 24. The article of claim 23, wherein the extruded article is a sheet or film.

25. A housing for communication equipment having a built-in microwave and / or millimeter wave antenna, obtained by using the molded article according to any one of claims 14 to 24.

26. 26. The communications device housing according to claim 25, wherein the antenna is used for radio waves in a frequency band of 3.5 to 30 GHz.

27. The communications device housing according to claim 25 or 26, wherein the communications device is a notebook computer, a tablet terminal, a smartphone, or a router device.

28. A communication device having a built-in microwave and / or millimeter wave antenna, obtained by using the housing for communication device according to any one of claims 25 to 27.

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