Thermoplastic resin compositions, communication equipment components, and microwave and / or millimeter-wave communication equipment

Abstract

To provide a thermoplastic resin composition which is excellent in surface hardness, heat resistance, initial color tone, impact resistance and low dielectric characteristics.SOLUTION: A thermoplastic resin composition contains a polycarbonate resin. The polycarbonate resin contains a polycarbonate copolymer including a structural unit (a) derived from a 2,2-bis(3-methyl-4-hydroxyphenyl)propane derivative, and a structural unit (b) derived from a 1,1-bis(4-hydroxyphenyl) cyclohexane derivative and / or a structural unit (b) derived from a 1,1-bis(4-hydroxyphenyl)-1-phenylethane derivative, specific viscosity (20°C) of a solution in which 0.7 g of the polycarbonate resin is dissolved in 100 mL of methylene chloride is 0.308 to 0.455, and a viscosity average molecular weight of the polycarbonate resin is 17,300 to 26,400.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin composition excellent in surface hardness, heat resistance, initial color tone, impact resistance, and low dielectric characteristics. The present invention also relates to a communication device member obtained by using this thermoplastic resin composition, and a communication device for microwaves and / or millimeter waves using this communication device member.

Background Art

[0002] Polycarbonate resin is excellent in mechanical strength, electrical properties, transparency, etc., and is widely used in various fields such as the electrical and electronic equipment field and the automotive field as an engineering plastic. In recent years, in these application fields, the thinning, miniaturization, and weight reduction of molded products have progressed, and further performance improvement of the molding material is required. However, conventional polycarbonate resins made from bisphenol A have insufficient surface hardness with respect to these required properties.

[0003]

[0004] <00000�5>Patent Document 1 discloses a polycarbonate polymer excellent in surface hardness, which is produced using a bisphenol having a specific substituent different from conventional bisphenol A as a raw material. However, the polycarbonate polymer of Patent Document 1 had insufficient heat resistance compared to conventional polycarbonate resins made from bisphenol A.

[0005] On the other hand, in the fields of electrical and electronic equipment and automotive, radio waves in high frequency bands such as microwaves and millimeter waves are being used, and accordingly, materials having both a low relative dielectric constant and a low dielectric tangent are required. Especially in the electrical and electronic field, in addition to a low relative dielectric constant and a low dielectric tangent, high heat resistance, good color tone, and less yellowing are required.

[0006] In recent years, with the increase in information communication volume, there has been a strong demand for higher communication speeds in information communication devices such as notebook computers, tablet terminals, smartphones, or router devices. To communicate at high speeds, it is preferable to use radio waves in a higher frequency band, and recently, radio waves exceeding 3 GHz, which are classified in the microwave band, have been used. In the next-generation, fifth-generation mobile communication system (5G), in the microwave band, the market launch in the 28 GHz band, which is a higher frequency, is expected to be promising. Furthermore, it is also assumed that radio waves in the millimeter-wave band will be used in next-generation communication.

[0007] Along with this, there is also an increasing demand for high performance in the members of information communication devices for which the use of the microwave and / or millimeter-wave band is assumed. Such radio waves in a high frequency band have the characteristics of having a larger transmission loss and worse material permeability than radio waves in a lower frequency band. Therefore, it is desired that the device members used for microwave and / or millimeter-wave communication have better radio wave permeability than before.

[0008] The transmission loss is proportional to the square root of the relative permittivity (ε r ) of the dielectric and the dielectric tangent (tanδ) of the dielectric. Therefore, in order to increase the radio wave permeability of the housing, it is necessary to make the relative permittivity ε r and the dielectric tangent tanδ of the material used for the housing small.

[0009] In addition, information communication devices that transmit and receive radio waves in a high frequency band such as microwaves and / or millimeter-waves tend to generate heat. From this, it is desirable that the materials used in such fields have not only a low relative permittivity and a low dielectric tangent but also appropriate heat resistance, and there is a strong demand for materials that satisfy these conditions.

[0010] Furthermore, for the members of information communication devices for which the use of the microwave and / or millimeter-wave band is assumed, or for communication devices incorporating an antenna for microwaves and / or millimeter-waves, it is strongly required that the appearance is good. That is, it is required that the color tone is good and that there is little burning during molding.

[0011] However, conventional materials could not simultaneously meet these requirements.

[0012] Specifically, Patent Document 2 discloses an aromatic polycarbonate resin composition with reduced birefringence and a balanced combination of optical properties and transferability, but makes no mention of color tone or dielectric properties. Furthermore, it does not describe any communication equipment components for microwave and / or millimeter-wave applications, nor any communication equipment using these components. Patent Document 3 proposes a millimeter-wave radar cover in which the dielectric loss tangent is reduced and millimeter-wave transmittance is improved by using a thermoplastic resin composition containing a polycarbonate resin made from bisphenol having a specific substituent. However, these thermoplastic resin compositions have insufficient heat resistance for use as microwave and / or millimeter-wave communication equipment components, and communication equipment using these communication equipment components. Patent Document 4 proposes a thermoplastic resin composition and molded articles thereof, which include a polycarbonate resin having two specific types of repeating units, and which exhibit excellent radio wave transmission in the microwave and / or millimeter wave bands, as well as excellent heat resistance and flame retardancy, and a housing for communication equipment incorporating a microwave and / or millimeter wave antenna. However, there was a lot of discoloration during molding, and the color tone was also unsatisfactory. [Prior art documents] [Patent Documents]

[0013] [Patent Document 1] Japanese Patent Application Publication No. 64-69625 [Patent Document 2] Japanese Patent Publication No. 2003-128906 [Patent Document 3] Japanese Patent Publication No. 2019-197048 [Patent Document 4] International Publication No. 2021 / 039970 [Overview of the project] [Problems that the invention aims to solve]

[0014] The object of the present invention is to provide a thermoplastic resin composition that is excellent in surface hardness, heat resistance, initial color tone, impact resistance, and low dielectric properties. The present invention also aims to provide microwave and / or millimeter-wave communication equipment components obtained using such thermoplastic resin compositions, which have high heat resistance, good color tone, minimal discoloration, and low dielectric properties, and microwave and / or millimeter-wave communication equipment using these communication equipment components. [Means for solving the problem]

[0015] The inventors have discovered that a thermoplastic resin composition comprising a polycarbonate resin having two specific structural units, wherein the polycarbonate resin has a predetermined specific viscosity and viscosity-average molecular weight, and the hydrolyzed product obtained by hydrolyzing the polycarbonate resin contains a certain amount of a specific dihydroxy compound, exhibits excellent surface hardness, heat resistance, initial color tone, and impact resistance, as well as excellent low dielectric properties, thus completing the present invention. The gist of this invention is found in the following [1] to

[15] .

[0016] [1] A thermoplastic resin composition comprising a polycarbonate resin, The polycarbonate resin comprises a structural unit (a) represented by the following formula (11) and a structural unit (b) represented by the following formula (12A) and / or the following formula (12B). The specific viscosity of a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 mL of methylene chloride was measured at 20°C to be 0.308 to 0.455. The viscosity-average molecular weight of the polycarbonate resin is 17,300 to 26,400. A thermoplastic resin composition in which the hydrolyzed polycarbonate resin yields a hydrolyzed product containing dihydroxy compounds represented by the following formulas (13), (14), (15A), and (15B), and the content of the dihydroxy compound represented by the following formula (14) in the hydrolyzed product is 100 ppm to 1,300 ppm relative to the content of the dihydroxy compound represented by the following formula (13).

[0017] [ka]

[0018] (In formula (11), Q represents at least one selected from a single bond, an oxygen atom, a sulfur atom, and a divalent organic group.) In formula (12A), R 11 Each of the terms independently represents an alkyl group with 1 to 4 carbon atoms, and n is an integer from 0 to 3. In formula (12B), W is a methyl group or a phenyl group. In equation (13), Q is the same as Q in equation (11). In equation (14), Q is synonymous with Q in equation (11), and R 12 represents a hydrogen atom or a methyl group. In formula (15A), R 11 R in equation (12A) 11 It is synonymous with [the above]. In equation (15B), W is equivalent to W in equation (12B).

[0019] [2] The thermoplastic resin composition according to [1], wherein Q in formula (11) is represented by the following formula (16).

[0020] [ka]

[0021] (In formula (16), R 13 , R 14 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. * represents a bond to the benzene ring in formula (11).

[0022] [3] In the formula (16), R 13 and R 14 are methyl groups, and the thermoplastic resin composition according to [2].

[0023] [4] The thermoplastic resin composition according to any one of [1] to [3], wherein the structural unit (b) contains a structural unit represented by the formula (12A).

[0024] [5] The thermoplastic resin composition according to [4], wherein the structural unit (a) and the structural unit (b) are contained as a copolymer.

[0025] [6] The thermoplastic resin composition according to any one of [1] to [3], wherein the structural unit (b) contains a structural unit represented by the formula (12B).

[0026] [7] The thermoplastic resin composition according to [6], wherein the structural unit (a) and the structural unit (b) are contained as a blend.

[0027] [8] In the formula (12A), R 11 is a methyl group, and the thermoplastic resin composition according to any one of [1] to [7].

[0028] [9] In the formula (12A), n is 3, and the thermoplastic resin composition according to any one of [1] to [8].

[0029]

[10] The thermoplastic resin composition according to any one of [1] to [9], wherein the structural unit (b) is represented by the following formula (17).

[0030] [Chemical formula]

[0031]

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

[10] , wherein the content of the structural unit (b) contained in the polycarbonate resin is 20 mol% or more based on the sum of the contents of the structural unit (a) and the structural unit (b).

[0032]

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

[11] , wherein the sum of the content ratios of structural unit (a) and structural unit (b) contained in the polycarbonate resin is 80 mol% or more of the total carbonate structural units of the polycarbonate resin.

[0033]

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

[12] , wherein the glass transition temperature of the polycarbonate resin is 125°C or higher.

[0034]

[14] A communication device component obtained using any of the thermoplastic resin compositions described in [1] to

[13] .

[0035]

[15]

[14] A microwave and / or millimeter-wave communication device obtained using the communication device components described above. [Effects of the Invention]

[0036] The thermoplastic resin composition of the present invention exhibits excellent surface hardness, heat resistance, initial color, and impact resistance in molded articles obtained using it, and can therefore be widely used as a material for manufacturing parts in the automotive, electrical and electronic equipment, and other industrial fields.

[0037] Furthermore, because the thermoplastic resin composition of the present invention has excellent low dielectric properties, communication equipment components made from the thermoplastic resin composition of the present invention, and communication equipment using these components, have excellent microwave and / or millimeter-wave band radio wave transmission, high heat resistance, good color tone, and less burning during molding. Therefore, they can be widely used as housings or devices for communication equipment incorporating microwave and / or millimeter-wave antennas, such as notebook computers, tablet terminals, smartphones, or router devices. [Modes for carrying out the invention]

[0038] The present invention will be described in detail below with reference to embodiments and examples. This is not to be interpreted as being limited to the embodiments and examples shown.

[0039] In this specification, unless otherwise specified, "~" means that the numbers before and after it are included as the lower and upper limits.

[0040] [overview] The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising a polycarbonate resin, The polycarbonate resin (hereinafter sometimes referred to as "the polycarbonate resin of the present invention") comprises a structural unit (a) represented by the following formula (11) and a structural unit (b) represented by the following formula (12A) and / or the following formula (12B). The specific viscosity (hereinafter sometimes simply referred to as "specific viscosity") of a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 mL of methylene chloride, measured at 20°C, was 0.308 to 0.455. The viscosity-average molecular weight of the polycarbonate resin is 17,300 to 26,400. The hydrolyzed product obtained by hydrolyzing the polycarbonate resin (hereinafter sometimes referred to as "the hydrolyzed product of the present invention") contains dihydroxy compounds represented by the following formulas (13), (14), (15A), and (15B), and is characterized in that the content ratio of the dihydroxy compound represented by the following formula (14) in the hydrolyzed product is 100 ppm to 1,300 ppm relative to the content of the dihydroxy compound represented by the following formula (13).

[0041] [ka]

[0042] (In formula (11), Q represents at least one selected from a single bond, an oxygen atom, a sulfur atom, and a divalent organic group.) In formula (12A), R 11 Each of the terms independently represents an alkyl group with 1 to 4 carbon atoms, and n is an integer from 0 to 3. In formula (12B), W is a methyl group or a phenyl group. In equation (13), Q is the same as Q in equation (11). In equation (14), Q is synonymous with Q in equation (11), and R 12 represents a hydrogen atom or a methyl group. In formula (15A), R 11 R in equation (12A) 11 It is synonymous with [the above]. In equation (15B), W is equivalent to W in equation (12B).

[0043] In the following, the dihydroxy compound represented by formula (13) will be referred to as "dihydroxy compound (13)", the dihydroxy compound represented by formula (14) will be referred to as "dihydroxy compound (14)", the dihydroxy compound represented by formula (15A) will be referred to as "dihydroxy compound (15A)", and the dihydroxy compound represented by formula (15B) will be referred to as "(15B)", and these may be collectively referred to as "dihydroxy compounds (13) to (15)". Furthermore, the ratio of dihydroxy compound (14) to dihydroxy compound (13) in the hydrolysate of the present invention may be referred to as the "(14) / (13) ratio in the hydrolysate."

[0044] The polycarbonate resin of the present invention, the hydrolysates and dihydroxy compounds (13) to (15) of the present invention, and each component constituting the thermoplastic resin composition of the present invention will be described in detail below.

[0045] [Polycarbonate resin] The polycarbonate resin of the present invention is characterized by having a structural unit (a) represented by the following formula (11) and a structural unit (b) represented by the following formula (12A) and / or the following formula (12B). However, structural unit (b) is different from structural unit (a). The structural unit (a) represented by the following formula (11) and the structural unit (b) represented by the following formula (12A) and / or the following formula (12B) may be included as a copolymer, or as a blend of the respective resins. That is, the polycarbonate resin of the present invention may be a polycarbonate copolymer containing structural unit (a) and structural unit (b), or as a blend of a polycarbonate resin containing structural unit (a) and a polycarbonate resin containing structural unit (b).

[0046] By using a thermoplastic resin composition containing a polycarbonate resin having a structural unit (a) represented by the following formula (11) and a structural unit (b) represented by the following formula (12A) and / or the following formula (12B), and satisfying a predetermined specific viscosity, viscosity-average molecular weight, and (14) / (13) ratio in the hydrolysate, the thermoplastic resin composition of the present invention can be made to have excellent pencil hardness, heat resistance, initial color tone, impact resistance, and low dielectric properties.

[0047] [ka]

[0048] (In formula (11), Q represents at least one selected from a single bond, an oxygen atom, a sulfur atom, and a divalent organic group. In formula (12A), R 11 Each of the elements independently represents an alkyl group having 1 to 4 carbon atoms, and n is an integer from 0 to 3. In formula (12B), W is a methyl group or a phenyl group. )

[0049] The polycarbonate resin of the present invention, having structural unit (a) and structural unit (b), can achieve good pencil hardness, heat resistance, and low dielectric properties. The polycarbonate resin of the present invention may, if necessary, be a copolymerized polycarbonate resin consisting of structural unit (a) and structural unit (b) and other structural unit (c) described later.

[0050] <Structural unit (a)> In formula (11) above, which represents the structural unit (a) of the polycarbonate resin of the present invention, Q represents at least one selected from a single bond, an oxygen atom, a sulfur atom, and a divalent organic group.

[0051] As for the divalent organic group Q, there are no particular restrictions as long as it is conventionally known, and it can be selected and used as appropriate. Specific examples include the organic groups represented by the following formulas (16a) to (16h).

[0052] [ka]

[0053] In formula (16a), R 15 and R 16 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, or an alkoxy group having 1 to 24 carbon atoms, with a monovalent hydrocarbon group having 1 to 24 carbon atoms being preferred. Examples of the above-mentioned monovalent hydrocarbon groups having 1 to 24 carbon atoms include alkyl groups having 1 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, aryl groups having 6 to 24 carbon atoms which may have substituents, and arylalkyl groups having 7 to 24 carbon atoms.

[0054] Examples of alkyl groups having 1 to 24 carbon atoms include linear alkyl groups, branched alkyl groups, and alkyl groups having a partially cyclic structure, but linear alkyl groups are preferred. Examples of such alkyl groups having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group.

[0055] Examples of alkenyl groups having 2 to 24 carbon atoms include linear alkenyl groups, branched alkenyl groups, and alkenyl groups having a partially cyclic structure, but linear alkenyl groups are preferred. Examples of such alkenyl groups having 2 to 24 carbon atoms include vinyl groups, n-propenyl groups, n-butenyl groups, n-pentenyl groups, n-hexenyl groups, n-heptenyl groups, and n-octenyl groups.

[0056] Examples of aryl groups having 6 to 24 carbon atoms include aryl groups that may have substituents such as alkyl groups, phenyl group, naphthyl group, methylphenyl group, dimethylphenyl group, and trimethylphenyl group. Examples of arylalkyl groups having 7 to 24 carbon atoms include the benzyl group.

[0057] Examples of alkoxy groups having 1 to 24 carbon atoms include linear, branched, and partially cyclic alkoxy groups, but linear alkoxy groups are preferred. Specific examples include methoxy, ethoxy, propoxy, and butoxy groups.

[0058] In formula (16b), A 1 is an oxygen atom or NR A This represents R A The above R 15 and R 16 This is the same definition.

[0059] In formula (16c), A 2 This represents a divalent hydrocarbon group having 3 to 18 carbon atoms, such as alkylene groups including propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecynylene, each of which may have further substituents. Examples of substituents include methyl, ethyl, propyl, butyl, pentyl, and phenyl groups. Furthermore, it may have a partially crosslinked structure.

[0060] In formula (16h), A 3 represents an alkylene group having 1 to 7 carbon atoms. Such alkylene groups may be linear, branched, or have a cyclic structure, and examples include methylene, ethylene, propylene, and butylene groups. Furthermore, t represents an integer from 1 to 500, but is preferably 5 to 300, and more preferably 10 to 100.

[0061] Among these, Q is more preferably a single bond or a group represented by the following formula (16), for example, a methylene group, an ethylidene group, or an isopropylidene group. From the viewpoint of improving heat resistance and suppressing scorching, the most preferred is an isopropylidene group (i.e., in the following formula (16), R 13 , R 14 (This is a methyl group.)

[0062] [ka]

[0063] (In formula (16), R 13 , R 14 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. * represents a bond to the benzene ring in formula (11).

[0064] <Structural unit (b)> The structural unit (b) of the polycarbonate resin of the present invention is represented by formula (12A) and / or formula (12B). In the formula (12A), R 11 Each of the terms independently represents an alkyl group with 1 to 4 carbon atoms, and n is an integer from 0 to 3.

[0065] In the formula (12A), R 11 Specific examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and the like.

[0066] Among these, R 11 Preferably, it is a methyl group.

[0067] In formula (12A) above, n is an integer between 0 and 3. n is not particularly limited as long as it is an integer between 0 and 3, but preferably n is 0 or 3, and particularly preferably n is 3.

[0068] In the above formula (12B), W is a methyl group or a phenyl group.

[0069] Among these, W is preferably a methyl group.

[0070] Structural unit (b) may consist only of structural units represented by formula (12A), or only of structural units represented by formula (12B), or may include both structural units represented by structural unit (12A) and structural units represented by structural unit (12B).

[0071] Preferred specific examples of structural unit (b) include structural units represented by the following formulas (17), (18A), and (18B) from the viewpoint of improving color tone.

[0072] [ka]

[0073] The most preferred specific example of structural unit (b) is the structural unit represented by formula (17) above, from the viewpoint of heat resistance and suppression of appearance defects (burning) during molding.

[0074] The structural units (a) and (b) contained in the polycarbonate resin of the present invention may be copolymers or blends of the respective resins. However, if structural unit (b) is a structural unit represented by formula (12A), it is preferable that it be a copolymer, and if structural unit (b) is a structural unit represented by formula (12B), it is preferable that it be a blend.

[0075] <Other structural units (c)> The polycarbonate resin of the present invention may contain one or more other structural units (c) other than structural units (a) and structural unit (b) as a copolymer, to the extent that it does not impair the objectives of the present invention. Examples of other structural units (c) include structural units derived from aromatic dihydroxy compounds such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 4,4'-dihydroxybiphenyl (biphenol), and 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobindan (SBI), but repeating units derived from bisphenol A and biphenol are preferred.

[0076] <Content ratio of structural units (a) and (b)> The polycarbonate resin of the present invention may be any polycarbonate resin having structural unit (a) and structural unit (b), and the content ratio of structural unit (a) and structural unit (b) in the polycarbonate resin of the present invention is not particularly limited. However, it is preferable that the sum of the content ratios of structural unit (a) and structural unit (b) contained in the polycarbonate resin of the present invention be 30 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more, of the total carbonate structural units of the polycarbonate resin.

[0077] Furthermore, while the ratio of structural unit (a) to structural unit (b) is not particularly limited, from the viewpoint of improving heat resistance, it is preferable that structural unit (b) be 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and particularly preferable 20 mol% or more, relative to the sum of the content ratios of structural unit (a) and structural unit (b). On the other hand, from the viewpoint of improving moldability, dielectric properties, and surface hardness, it is preferable that structural unit (b) be 80 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferable 40 mol% or less, relative to the sum of the content ratios of structural unit (a) and structural unit (b).

[0078] <Molecular weight of polycarbonate resin> The molecular weight of the polycarbonate resin of the present invention is not particularly limited, but the viscosity-average molecular weight (Mv) calculated from the solution viscosity is preferably 10,000 to 35,000. By keeping the viscosity-average molecular weight within the above range, the characteristics of the present invention can be effectively brought out. If the viscosity-average molecular weight of the polycarbonate resin is above the lower limit, the pencil hardness and impact resistance of the thermoplastic resin composition of the present invention will be good, which is preferable. Also, if the viscosity-average molecular weight of the polycarbonate resin is below the upper limit, the fluidity of the thermoplastic resin composition of the present invention will be good, which is preferable. From this viewpoint, the viscosity-average molecular weight (Mv) of the polycarbonate resin of the present invention is more preferably 12,000 or more, even more preferably 13,000 or more, and particularly preferably 14,000 or more. Furthermore, it is more preferably 30,000 or less, even more preferably 28,000 or less, and particularly preferably 26,000 or less.

[0079] The viscosity-average molecular weight (Mv) of the polycarbonate resin of the present invention is determined by using methylene chloride as the solvent, and calculating the intrinsic viscosity (intrinsic viscosity) [η] (unit: dL / g) at a temperature of 20°C using an Ubbelohde viscometer, and then using Schnell's viscosity formula, i.e., η = 1.23 × 10⁻¹⁰ -14 Mv 0.813 This refers to the value calculated from [the formula shown]. Furthermore, intrinsic viscosity (intrinsic viscosity) [η] is the value calculated by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dL) and using the following formula.

[0080]

number

[0081] <Glass transition temperature of polycarbonate resin> The glass transition temperature (Tg) of the polycarbonate resin of the present invention is not particularly limited, but it is preferably 125°C or higher. If Tg is 125°C or higher, high heat resistance can be obtained. On the other hand, it is preferable that Tg be 230°C or lower. If Tg is 230°C or lower, good fluidity is obtained, and high moldability can be obtained.

[0082] Furthermore, the Tg of polycarbonate resin is determined by measuring the heat content of a sample of approximately 10 mg of polycarbonate resin using a differential calorimeter at a heating rate of 20°C / min. In accordance with ISO 3146, the extrapolated glass transition onset temperature is determined as the temperature at the intersection of a straight line extending from the low-temperature baseline to the high-temperature side and a tangent line drawn at the point where the slope of the curve representing the stepwise transition of the glass transition is maximum, and this extrapolated glass transition onset temperature is defined as the glass transition temperature (Tg).

[0083] <Method for manufacturing polycarbonate resin> The polycarbonate resin of the present invention can be produced by conventional polymerization methods, and the polymerization method is not particularly limited. Examples of polymerization methods include interfacial polymerization, molten transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Particularly preferred methods among these will be described in detail below.

[0084] (interfacial polymerization method) In the interfacial polymerization method, polycarbonate resin is obtained by reacting a dihydroxy compound and a carbonate-forming compound in the presence of an organic solvent and an alkaline aqueous solution that are inert to the reaction, usually maintaining a pH of 9 or higher, and then carrying out interfacial polymerization in the presence of a polymerization catalyst. A molecular weight modifier (end-terminating agent) may be added to the reaction system as needed, and an antioxidant may be added to prevent oxidation of the dihydroxy compound.

[0085] The organic solvent that is inert to the reaction is not particularly limited, but examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; and so on. One organic solvent may be used, or two or more may be used in any combination and ratio.

[0086] The alkali compounds contained in the alkaline aqueous solution are not particularly limited, but examples include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate, as well as alkaline earth metal compounds. Among these, sodium hydroxide and potassium hydroxide are preferred. Note that one alkali compound may be used, or two or more may be used in any combination and ratio.

[0087] There are no restrictions on the concentration of the alkali compound in the alkaline aqueous solution, but typically, to control the pH of the alkaline aqueous solution to 10-12, the alkali compound concentration is used at 5-10% by mass. Furthermore, for example, when bubbling in phosgene, in order to control the pH of the aqueous phase to 10-12, preferably 10-11, it is preferable to set the molar ratio of the raw material dihydroxy compound to the alkali compound to 1:1.9 or higher, more preferably 1:2.0 or higher, and more preferably 1:3.2 or lower, more preferably 1:2.5 or lower.

[0088] As the starting material dihydroxy compound, at least one dihydroxy compound capable of generating structural unit (a) and structural unit (b) through reaction with a carbonate-forming compound is used.

[0089] Carbonyl halides are preferably used as carbonate-forming compounds, and among these, phosgene is preferred. The method using phosgene is specifically called the phosgene method.

[0090] The polymerization catalyst is not particularly limited, but examples include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; guanine; salts of guanidine; and so on. Note that one polymerization catalyst may be used, or two or more may be used in any combination and ratio.

[0091] Molecular weight modifiers are not particularly limited, but examples include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, etc., but aromatic phenols are preferred among them. Specifically, such aromatic phenols include phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, mn-nonylphenol, pn-nonylphenol Examples include phenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, monoalkylphenols having a linear or branched alkyl group with an average of 12 to 35 carbon atoms in the ortho, meta, or para position, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, 4-(1-adamantyl)phenol, etc. Among these, pt-butylphenol, p-phenylphenol, and p-cumylphenol are preferably used. Furthermore, one molecular weight adjusting agent may be used, or two or more may be used in any combination and ratio.

[0092] The amount of molecular weight adjusting agent used is not particularly limited, but for example, it is usually 0.5 moles or more, preferably 1 mole or more, and usually 50 moles or less, preferably 30 moles or less, per 100 moles of the dihydroxy compound raw material.

[0093] While not particularly limited, examples of antioxidants include hindered phenol-based antioxidants. Specific examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphoate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6- Examples include triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[0094] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Examples of commercially available phenolic antioxidants include BASF's "Irganox 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60."

[0095] Furthermore, one type of antioxidant may be used, or two or more types may be used in any combination and ratio.

[0096] The amount of antioxidant used is not particularly limited, but is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the raw material dihydroxy compound. By using an amount of antioxidant above the lower limit, the antioxidant effect is sufficient. Furthermore, the amount of antioxidant used is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the raw material dihydroxy compound. By using an amount of antioxidant below the upper limit, gas generation during injection molding can be suppressed.

[0097] The order in which the reaction substrate (reaction raw material), reaction solvent (organic solvent), catalyst, additives, etc. are mixed during the reaction is arbitrary as long as the desired polycarbonate resin is obtained, and any appropriate order can be set. For example, when phosgene is used as the carbonate-forming compound, the molecular weight modifier can be mixed at any time between the reaction between the starting material dihydroxy compound and phosgene (phosgenation) and the start of the polymerization reaction.

[0098] The reaction temperature is not particularly limited, but is preferably 0 to 40°C. The reaction time is not particularly limited, but is preferably several minutes (e.g., 10 minutes) to several hours (e.g., 6 hours).

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

[0100] Examples of carbonate esters include compounds represented by the following formula (19), such as aryl carbonates, dialkyl carbonates, biscarbonate forms of dihydroxy compounds, monocarbonate forms of dihydroxy compounds, and carbonate forms of dihydroxy compounds such as cyclic carbonates.

[0101] [ka]

[0102] In the above equation (19), R 17 and R 18 Each of these independently represents an alkyl group, an aryl group, or an arylalkyl group having 1 to 30 carbon atoms. Hereinafter, R 17 and R 18 However, when it is an alkyl group or arylalkyl group, it is sometimes called a dialkyl carbonate, and when it is an aryl group, it is sometimes called a diaryl carbonate. In particular, from the viewpoint of reactivity with dihydroxy compounds, R 17 and R 18 Both are preferably aryl groups, and more preferably diaryl carbonates represented by the following formula (20).

[0103] [ka]

[0104] In the above equation (20), R 19 and R 20 Each of these is independently a halogen atom, a nitro group, a cyano group, a C1-C20 alkyl group, a C1-C20 alkoxycarbonyl group, a C4-C20 cycloalkyl group, or a C6-C20 aryl group, and p and q each independently represent an integer from 0 to 5.

[0105] Examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), diaryl carbonates (which may have substituents) such as bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate, bis(4-fluorophenyl) carbonate, bis(2-chlorophenyl) carbonate, bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, bis(2-nitrophenyl) carbonate, bis(methylsalicylphenyl) carbonate, and ditril carbonate, but diphenyl carbonate is preferred among them. These carbonate esters can be used individually or in combination of two or more.

[0106] Furthermore, the carbonate ester may be substituted with a dicarboxylic acid or dicarboxylic acid ester in an amount of preferably 50 mol% or less, and more preferably 30 mol% or less. Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

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

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

[0109] In the molten transesterification method, the reaction temperature is not particularly limited, but is usually between 100 and 320°C. The reaction pressure is also not particularly limited, but is usually under reduced pressure of 2 mmHg or less. Specifically, the molten polycondensation reaction can be carried out under the above conditions while removing by-products.

[0110] In this case, the polycarbonate resin of the present invention is significantly affected by thermal history and oxidation in the presence of an alkaline catalyst, leading to deterioration of its hue. Therefore, it is preferable to keep the reaction temperature below 320°C and to select reduced pressure conditions with a lower limit of approximately 0.05 mmHg to prevent oxygen leakage from the equipment due to excessive reduced pressure.

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

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

[0113] The amount of catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, relative to the transesterification catalyst, and is also usually 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less. Furthermore, the amount of catalyst deactivator used is usually 1 ppm or more and 100 ppm or less, preferably 50 ppm or less, relative to the polycarbonate resin.

[0114] <Other polycarbonate resins> The polycarbonate resin of the present invention may contain one or more other polycarbonate resins as a blend, as long as the characteristics of the present invention are not impaired. Other polycarbonate resins that may be included in the polycarbonate resin of the present invention include polycarbonate resins having structural units represented by the following formula (21).

[0115] [ka]

[0116] (In the above formula (21), R 21 ~R 24 Each of the following independently represents a hydrogen atom or a methyl group. Z represents a single bond, an oxygen atom, a sulfur atom, or at least one selected from the divalent organic groups represented by the following formulas (22a) to (22h).

[0117] [ka]

[0118] In formula (22a), R 25 and R 26 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, or an alkoxy group having 1 to 24 carbon atoms, with a monovalent hydrocarbon group having 1 to 24 carbon atoms being preferred. Examples of the above-mentioned monovalent hydrocarbon groups having 1 to 24 carbon atoms include alkyl groups having 1 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, aryl groups having 6 to 24 carbon atoms which may have substituents, and arylalkyl groups having 7 to 24 carbon atoms.

[0119] Examples of alkyl groups having 1 to 24 carbon atoms include linear alkyl groups, branched alkyl groups, and alkyl groups having a partially cyclic structure, but linear alkyl groups are preferred. Examples of such alkyl groups having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group.

[0120] Examples of alkenyl groups having 2 to 24 carbon atoms include linear alkenyl groups, branched alkenyl groups, and alkenyl groups having a partially cyclic structure, but linear alkenyl groups are preferred. Examples of such alkenyl groups having 2 to 24 carbon atoms include vinyl groups, n-propenyl groups, n-butenyl groups, n-pentenyl groups, n-hexenyl groups, n-heptenyl groups, and n-octenyl groups.

[0121] Examples of aryl groups having 6 to 24 carbon atoms include aryl groups that may have substituents such as alkyl groups, phenyl group, naphthyl group, methylphenyl group, dimethylphenyl group, and trimethylphenyl group. Examples of arylalkyl groups having 7 to 24 carbon atoms include the benzyl group.

[0122] Examples of alkoxy groups having 1 to 24 carbon atoms include linear, branched, and partially cyclic alkoxy groups, but linear alkoxy groups are preferred. Specific examples include methoxy, ethoxy, propoxy, and butoxy groups.

[0123] In formula (22b), A 4 is an oxygen atom or NR B This represents R B The above R 25 and R 26 This is the same definition.

[0124] In formula (22c), A 5 This represents a divalent hydrocarbon group having 3 to 18 carbon atoms, such as alkylene groups including propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecynylene, each of which may have further substituents. Examples of substituents include methyl, ethyl, propyl, butyl, pentyl, and phenyl groups. Furthermore, it may have a partially crosslinked structure.

[0125] In formula (22h), A 6 represents an alkylene group having 1 to 7 carbon atoms. Such alkylene groups may be linear, branched, or have a cyclic structure, and examples include methylene, ethylene, propylene, and butylene groups. Furthermore, l represents an integer from 1 to 500, with a preference for 5 to 300, and a preference for 10 to 100.

[0126] Among these, Z is more preferably a single bond, an isopropylidene group, or formula (22c), where A 5 It is preferably a divalent hydrocarbon group having 5 carbon atoms and a methyl group as a substituent. Z is most preferably an isopropylidene group.

[0127] <(14) / (13) ratio in hydrolysates> The hydrolyzed product of the present invention, obtained by hydrolyzing the polycarbonate resin of the present invention, contains a dihydroxy compound represented by the following formulas (13) to (15), wherein the content ratio of dihydroxy compound (14) in the hydrolyzed product is 100 ppm to 1,300 ppm relative to the content of dihydroxy compound (13). Having the (14) / (13) ratio in the hydrolyzed product within this range allows for good impact resistance, pencil hardness, and initial color tone of the polycarbonate resin of the present invention.

[0128] [ka]

[0129] (In equation (13), Q is the same as Q in equation (11). In equation (14), Q is the same as Q in equation (11), and R 12 represents a hydrogen atom or a methyl group. In formula (15A), R 11 R in formula (12A) above 11 It is synonymous with [the above]. In equation (15B), W is the same as W in equation (12B).

[0130] The ratio of (14) / (13) in the hydrolyzed polycarbonate resin of the present invention is 100 ppm or more, and more preferably 150 ppm or more, from the viewpoint of improving impact resistance. On the other hand, from the viewpoint of improving initial color tone, the ratio of (14) / (13) in the hydrolyzed polycarbonate resin of the present invention is preferably 1300 ppm or less, and particularly preferably 1200 ppm or less.

[0131] To set the (14) / (13) ratio in the hydrolysate within the above preferred range, for example, this can be achieved by appropriately adjusting the purity of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes referred to as "BPC"), which is the dihydroxy compound (13) that is a raw material for the polycarbonate resin of the present invention, and further appropriately adjusting the amount of catalyst during the production of the polycarbonate resin, pressure, temperature, and the setting conditions at the end of the condensation polymerization reaction.

[0132] <Analytical methods for dihydroxy compounds (13)-(15) in hydrolysates> The content of dihydroxy compounds (13) to (15) in the hydrolysate of the present invention can be analyzed as follows.

[0133] Dissolve 0.5 g of polycarbonate resin in 5 mL of methylene chloride, then add 45 mL of methanol and 5 mL of 25% by mass sodium hydroxide aqueous solution, and stir at 70°C for 30 minutes to hydrolyze (methylene chloride solution). After that, add 6 N hydrochloric acid to this methylene chloride solution to adjust the pH of the solution to about 2, and adjust the volume to 100 mL with pure water. Next, 20 μL of the prepared methylene chloride solution is injected into a liquid chromatograph, and the content of dihydroxy compound (13), dihydroxy compound (14), dihydroxy compound (15A), and dihydroxy compound (15B) is measured (in ppm), and these are recorded as the content of each dihydroxy compound. The liquid chromatography and measurement conditions are as follows: Liquid chromatography: Shimadzu LC-10AD Column: YMC PACK ODS-AM M-307-3 4.6mm ID × 75mm L Detector: UV280nm Eluent: (A) 0.05% trifluoroacetic acid aqueous solution (B) methanol Gradient conditions: 0 minutes (B=40%), 25 minutes (B-95%) Flow rate: 1.0mL / min Column temperature: 40℃ Injection volume: 20μL The proportion of dihydroxy compound (14) is calculated from the peak area of ​​each component, based on a calibration curve created using BPC, which is dihydroxy compound (13).

[0134] Although there may be some errors depending on the column's degradation status and manufacturing date, under these conditions, dihydroxy compounds (13), such as BPC, are detected at around 12.2 minutes, dihydroxy compounds (14) at around 15.0 minutes, and dihydroxy compounds (15A), such as BP-TMC, at around 17.6 minutes.

[0135] As described above, the content of the dihydroxy compound (14) in the hydrolysate of the present invention is achieved by appropriately adjusting the purity of BPC, which is the dihydroxy compound (13) that serves as a raw material for the polycarbonate resin of the present invention, and further adjusting the manufacturing conditions of the polycarbonate resin.

[0136] <Identification of dihydroxy compounds (14) in hydrolysates> The structure of the dihydroxy compound (14) in the hydrolysate of the present invention is identified by the above analytical method, and when a peak derived from a specific structure is detected, the analytical solution is separated, and the separated sample is... 1 H-NMR, 13 The analysis was performed using 13C-NMR, two-dimensional NMR, mass spectrometry (MS), and infrared absorption spectroscopy (IR spectroscopy). Furthermore, the identification of the structure can be confirmed by observing a signal originating from the carboxylic acid in the IR spectrum and by LC-MS analysis.

[0137] <Specific viscosity of polycarbonate resin> The specific viscosity of a solution prepared by dissolving 0.7 g of the polycarbonate resin of the present invention in 100 mL of methylene chloride, measured at 20°C, is 0.308 to 0.455. If the specific viscosity of the polycarbonate resin of the present invention is above the lower limit mentioned above, the polycarbonate resin of the present invention will have good impact resistance and heat resistance, which is preferable. Furthermore, if the viscosity-average molecular weight is below the upper limit mentioned above, the initial color tone and fluidity of the polycarbonate resin of the present invention will be good, which is preferable. From these viewpoints, the specific viscosity of the polycarbonate resin of the present invention is preferably 0.309 or higher, more preferably 0.311 or higher, even more preferably 0.313 or higher, and also preferably 0.452 or lower, more preferably 0.450 or lower, and even more preferably 0.449 or lower.

[0138] <Initial color tones of polycarbonate resin> The polycarbonate resin of the present invention exhibits excellent initial color tone. The initial color tone of the polycarbonate resin of the present invention is typically 20 or less in terms of the YI value (Yellow Index value) of the polycarbonate resin pellets, preferably 15 or less, more preferably 14 or less, particularly preferably 13 or less, and most preferably 10 or less. The initial color tone of polycarbonate resin can be reduced by setting the (14) / (13) ratio in the hydrolysate of the polycarbonate resin to an appropriate value.

[0139] The initial color tone of polycarbonate resin can be evaluated by measuring the YI value (Yellow Index value) in the reflected light of the pellet, in accordance with ASTM D1925. Specifically, a Konica Minolta CM-5 spectrophotometer is used, with a measurement diameter of 30 mm and SCE selected as the measurement conditions. A calibration glass CM-A212 for petri dish measurement is fitted into the measurement section, and a zero calibration box CM-A124 is placed over it to perform zero calibration, followed by white calibration using the built-in white calibration plate. Measurements were taken using a white calibration plate CM-A210, and it was confirmed that L* was 99.40±0.05, a* was 0.03±0.01, b* was -0.43±0.01, and YI was -0.58±0.01. Pellet measurements were taken by filling a cylindrical glass container with an inner diameter of 30 mm and a height of 50 mm with pellets to a depth of approximately 40 mm. The process of removing the pellets from the glass container and measuring again was repeated twice, and the average of the three measured values ​​was used. A smaller YI value indicates less yellowing of the resin and better color tone.

[0140] <Pencil hardness of polycarbonate resin> The polycarbonate resin of the present invention has high hardness properties such that its pencil hardness, measured by a method compliant with ISO 15184, is preferably HB or higher, and more preferably H or higher. The pencil hardness of polycarbonate resin is measured using a pencil hardness tester with a load of 750g on a polycarbonate resin test piece measuring 3mm thick, 25mm long, and 25mm wide. This test piece can be obtained by injection molding using an injection molding machine.

[0141] <Impact resistance of polycarbonate resin> Regarding the impact resistance of the polycarbonate resin of the present invention, in the Izod notch-free impact test described in the Examples section below, it is preferable that the number of breaks in the five test pieces is one or less, and it is more preferable that none of them break.

[0142] <Appearance of the polycarbonate resin plate> The frequency of discoloration that occurs during the molding of the polycarbonate resin of the present invention can be evaluated by visually observing the appearance of 30 injection-molded plates and counting the number of plates on which black foreign matter (discoloration) has occurred when evaluating the yellow index (YI) value of the injection-molded product. Of the 30 plates injection-molded from the polycarbonate resin of the present invention, the number of plates exhibiting black foreign matter (burning) is preferably 15 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 3 or less.

[0143] <Relative dielectric constant of polycarbonate resin (ε r ), dielectric loss tangent (tanδ) > The polycarbonate resin of the present invention is not particularly limited, but the relative permittivity (ε) measured at a temperature of 23°C and a frequency of 10GHz is not limited. r ) is 2.45 or less, and the dielectric loss tangent (tanδ) is 3.00 × 10⁻¹⁰ -13 The following is preferable: When the relative permittivity and dielectric loss tangent are within this range, the transmission of radio waves in the high-frequency band becomes good. Furthermore, the relative permittivity (ε) of polycarbonate resin r The dielectric loss tangent (tanδ) and the dielectric loss tangent (tanδ) can be measured using a cavity resonator at a frequency of 10 GHz after cutting a strip of film 70 mm long and 2 mm wide from a film with a thickness of 40 to 150 μm obtained by hot-press molding of polycarbonate resin, and conditioned for 48 hours at room temperature of 23°C and humidity of 50%.

[0144] [Thermoplastic resin composition] The thermoplastic resin composition of the present invention is characterized by containing the polycarbonate resin of the present invention as described above. The thermoplastic resin composition of the present invention may contain other components in addition to the polycarbonate resin of the present invention as described above, as necessary, provided that the desired physical properties are not significantly impaired. Examples of other components include resins other than the polycarbonate resin of the present invention, various resin additives, and so on. The other components may be present as a single component, or as two or more components in any combination and ratio.

[0145] <Other resins> Examples of resins other than the polycarbonate resin of the present invention include, Thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate resin (PTT resin), and polybutylene terephthalate resin (PBT resin); Styrene-based resins such as polystyrene resin (PS resin), high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), and cyclic cycloolefin resin (COP resin); Polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin); polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); liquid crystal polymer (LCP) These are some examples. Furthermore, the other resins may be present in any single form, or in any combination and ratio of two or more forms.

[0146] <Seed resin additive> Examples of resin additives that may be contained in the thermoplastic resin composition of the present invention include heat stabilizers, antioxidants, mold release agents, lightfastness agents (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, dyes, pigments, and the like. Note that the composition may contain only one resin additive, or two or more additives in any combination and ratio.

[0147] <Polycarbonate resin content> The thermoplastic resin composition of the present invention may contain one of the resins or resin additives other than the polycarbonate resin of the present invention described above, and may contain two or more in any combination and ratio.

[0148] Furthermore, if the thermoplastic resin composition of the present invention contains resins or resin additives other than the polycarbonate resin of the present invention, in order to more effectively obtain the effects of the present invention by including the polycarbonate resin of the present invention, it is preferable that the proportion of the polycarbonate resin of the present invention in the total resin components contained in the thermoplastic resin composition of the present invention be 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 70% by mass or more.

[0149] <Initial color tone of thermoplastic resin composition> The thermoplastic resin composition of the present invention exhibits excellent initial color tone. The initial color tone of the thermoplastic resin composition of the present invention is preferably 30 or less in terms of the YI value (Yellow Index value) of the pellets of the thermoplastic resin composition, more preferably 25 or less, and particularly preferably 20 or less.

[0150] [Communication equipment components] The thermoplastic resin composition of the present invention exhibits excellent radio wave transmission in the microwave and / or millimeter wave bands, good color tone, minimal discoloration, and excellent heat resistance. Therefore, it is useful as a component for microwave and / or millimeter wave communication equipment where these properties are strictly required.

[0151] There are no restrictions on the shape, pattern, color, dimensions, etc., of such microwave and / or millimeter-wave communication equipment components, and they can be appropriately selected according to the application of the microwave and / or millimeter-wave communication equipment components. Applications include, for example, enclosures for communication equipment incorporating microwave and / or millimeter-wave antennas such as laptop computers, tablet devices, smartphones, or router devices; modules for in-vehicle millimeter-wave radar used in automatic brake control systems, inter-vehicle distance control systems, pedestrian accident reduction steering systems, unintended acceleration suppression systems, pedal misapplication acceleration suppression systems, approaching vehicle warning systems, lane keeping assist systems, rear-end collision prevention warning systems, parking assist systems, vehicle surrounding obstacle warning systems, etc.; platform monitoring / level crossing obstacle detection systems, in-train content transmission systems, tram / railway collision avoidance systems, runway foreign object detection systems, etc. Examples include: millimeter-wave radar modules for railways and aircraft used in various applications; millimeter-wave radar modules for traffic infrastructure such as intersection monitoring devices and elevator monitoring devices; millimeter-wave radar modules for various security devices; millimeter-wave radar modules for medical and nursing care applications such as child and elderly monitoring systems; millimeter-wave radar modules for various information content transmission applications; antenna substrate materials for base station substrates, router substrates, server substrates, CPU substrates, etc.; and various antenna components such as monopole antennas, dipole antennas, patch antennas, whip antennas, loop antennas, and slot antennas.

[0152] In this 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. Therefore, microwaves and / or millimeter waves are radio waves with a frequency of 3.0 to 300 GHz. In other words, a communication device that incorporates a microwave and / or millimeter wave antenna is a communication device that incorporates an antenna that transmits and receives radio waves with a frequency of 3.0 to 300 GHz. Specific examples of such communication devices include laptop computers, tablet terminals, smartphones, or router devices that transmit and receive radio waves with a frequency of 3.0 to 300 GHz.

[0153] The microwave and / or millimeter-wave antenna of the microwave and / or millimeter-wave communication equipment component of the present invention is not particularly limited as long as it is between 3.0 and 300 GHz, but is more suitable for radio waves in the 3.2 to 250 GHz frequency band, and even more suitable for radio waves in the 3.4 to 200 GHz frequency band. In particular, the microwave and / or millimeter-wave communication equipment components of the present invention can be suitably used for radio waves in the 3.5 to 30 GHz frequency band used in 5G (fifth-generation mobile communication systems).

[0154] Radio waves in the microwave and / or millimeter-wave bands tend to have poor radio wave penetration. From this perspective, enclosures for communication equipment that house antennas for transmitting and receiving radio waves in the microwave and / or millimeter-wave bands are required to have high radio wave penetration. Furthermore, since communication equipment that transmits and receives microwave and / or millimeter-wave radio waves tends to generate heat, high heat resistance is required for the enclosures of communication equipment that house antennas that transmit and receive microwave and / or millimeter-wave radio waves.

[0155] The polycarbonate resin contained in the thermoplastic resin composition of the present invention, used in microwave and / or millimeter-wave communication equipment components of the present invention, possesses excellent dielectric properties, good heat resistance, good color tone, and minimal discoloration. Therefore, the thermoplastic resin composition of the present invention, including such polycarbonate resin, reflects these characteristics, exhibiting excellent radio wave transmission in the microwave and / or millimeter-wave band, high heat resistance, and a good appearance. As such, it is suitable for use in communication equipment components that transmit and receive radio waves in the microwave and / or millimeter-wave band, where these properties are strictly required.

[0156] Specific examples of communication equipment components for microwave and / or millimeter-wave devices include casings for communication equipment that incorporate microwave and / or millimeter-wave antennas, such as notebook computers, tablet terminals, smartphones, or router devices, as well as antenna substrate materials such as base station substrates, router substrates, server substrates, and CPU substrates. The thermoplastic resin composition of the present invention is particularly suitable for these applications.

[0157] <Manufacturing method for communication equipment components> There are no particular limitations on the method for processing the thermoplastic resin composition of the present invention into the communication equipment component of the present invention, but examples include injection molding, injection compression molding, extrusion molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, sheet molding, thermoforming, lamination molding, and press molding. Of these, injection molding or extrusion molding is particularly preferred.

[0158] The molding temperature when molding the thermoplastic resin composition of the present invention is not particularly limited, but is preferably 200°C or higher, more preferably 250°C or higher, and most preferably 280°C or higher. By setting the molding temperature above the lower limit, fluidity is improved and moldability is enhanced. Furthermore, the molding temperature when molding the thermoplastic resin composition of the present invention is preferably 350°C or lower, and particularly preferably 320°C or lower. By setting the molding temperature below the upper limit, the appearance of the communication equipment components can be improved.

[0159] When performing molding, pigments, dye release agents, heat stabilizers, etc., can be appropriately added to the thermoplastic resin composition of the present invention, as long as they do not impair the objectives of the present invention. [Examples]

[0160] The present invention will be described in more detail below based on examples. However, the present invention is not limited to the following examples.

[0161] The physical properties of the polycarbonate resins obtained in the following examples and comparative examples were evaluated by the method described below.

[0162] [1] Viscosity average molecular weight (Mv) Polycarbonate resin was dissolved in methylene chloride (concentration 7.0 g / L), and the intrinsic viscosity (intrinsic viscosity) [η] (unit dL / g) at 20°C was determined using an Ubbelohde viscosity tube (manufactured by Moritomo Rika Kogyo Co., Ltd.). The viscosity-average molecular weight (Mv) was then calculated from Schnell's viscosity formula (see below). η = 1.23 × 10 -4 Mv 0.83

[0163] [2]Specific viscosity The specific viscosity of a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 mL of methylene chloride was measured at 20°C using an Ubbelohde viscous tube (manufactured by Moritomo Rika Kogyo Co., Ltd.).

[0164] [3] Glass transition temperature (Tg) Using a differential calorimeter (SII DSC6220), approximately 10 mg of polycarbonate resin sample was heated at a heating rate of 20°C / min, and the heat content was measured. In accordance with ISO 3146, the extrapolated glass transition onset temperature was determined as the temperature at the intersection of a straight line extending from the low-temperature baseline to the high-temperature side and a tangent line drawn at the point where the slope of the curve representing the stepwise transition of the glass transition is maximum. This extrapolated glass transition onset temperature was defined as the glass transition temperature (Tg).

[0165] [4] Surface hardness (pencil hardness) Using a small injection molding machine (Shinko Cellbic C, Mobile Co., Ltd.), polycarbonate resin plates with a thickness of 3 mm, a length of 25 mm, and a width of 25 mm were molded under the cylinder and mold temperature conditions described in Tables 1 and 2 to obtain test specimens. The pencil hardness of these test specimens was measured using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) with a load of 750 g, in accordance with ISO 15184.

[0166] [5] Initial color of pellets The initial color tone of the polycarbonate resin was evaluated by measuring the YI value (Yellow Index value) in the reflected light of the pellet, in accordance with ASTM D1925. Specifically, a Konica Minolta CM-5 spectrophotometer was used, with a measurement diameter of 30 mm and SCE selected as the measurement conditions. A calibration glass CM-A212 for petri dish measurement was fitted into the measurement section, and a zero calibration box CM-A124 was placed over it to perform zero calibration, followed by white calibration using the built-in white calibration plate. Measurements were performed using a white calibration plate CM-A210, confirming that L* was 99.40±0.05, a* was 0.03±0.01, b* was -0.43±0.01, and YI was -0.58±0.01. Pellet measurements were performed by filling a cylindrical glass container with an inner diameter of 30 mm and a height of 50 mm with pellets to a depth of approximately 40 mm. The process of removing the pellets from the glass container and measuring again was repeated twice, and the average of the three measured values ​​was used.

[0167] [6] Impact resistance Using a small injection molding machine (Shinko Cellbic C, Mobile Co., Ltd.), polycarbonate resin plates with a thickness of 3.2 mm, a length of 53.5 mm, and a width of 12.7 mm were molded to obtain test specimens. In accordance with JIS K-7110, five test specimens were subjected to an Izod impact test without notches using a 60 kg hammer, and the number of breaks among the five specimens was determined.

[0168] [7] (14) / (13) ratio in hydrolysates 0.5 g of the sample was dissolved in 5 mL of methylene chloride, then 45 mL of methanol and 5 mL of 25% by mass sodium hydroxide aqueous solution were added, and the mixture was stirred at 70°C for 30 minutes to hydrolyze it (methylene chloride solution). Subsequently, 6 N hydrochloric acid was added to this methylene chloride solution to adjust the pH to approximately 2, and the volume was adjusted to 100 mL with pure water. Next, 20 μL of the prepared methylene chloride solution was injected into a liquid chromatograph under the following conditions, and the content of dihydroxy compounds (13) to (15) was measured. Based on this, the ratio of the content of dihydroxy compound (14) to the content of dihydroxy compound (13) was calculated in ppm. The liquid chromatography and measurement conditions are as follows: Liquid chromatography: Shimadzu LC-10AD Column: YMC PACK ODS-AM M-307-3 4.6mm ID × 75mm L Detector: UV280nm Eluent: (A) 0.05% trifluoroacetic acid aqueous solution (B) methanol Gradient conditions: 0 minutes (B=40%), 25 minutes (B-95%) Flow rate: 1.0mL / min Column temperature: 40℃ The content of dihydroxy compound (14) was calculated from the peak area of ​​each component based on a calibration curve created using dihydroxy compound (13), 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC). Under these conditions, dihydroxy compound (13), BPC, was detected at approximately 12.2 minutes, dihydroxy compound (14) at approximately 15.0 minutes, and dihydroxy compound (15A), 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol, showed a peak at approximately 17.6 minutes.

[0169] [8] Plate color Polycarbonate resin pellets were vacuum-dried at 90°C for more than 5 hours. The dried polycarbonate resin pellets were supplied to an injection molding machine (J75EII model, manufactured by Japan Steel Works, Ltd.), and the process of molding plate-shaped injection molded pieces (60 mm wide x 60 mm long x 3 mm thick) was repeated under conditions of a final cylinder temperature of 300°C and a molding cycle of approximately 30 seconds. The yellow index (YI) value of transmitted light in the thickness direction of the injection molded pieces obtained from the 10th to 40th shots was measured using a Konica Minolta CM-5 spectrophotometer in accordance with ASTM D1925. The plates obtained from the aforementioned injection molding were placed in a measurement chamber, and the YI value of the transmitted light was measured. A smaller YI value indicates less yellowness and better quality. Note that the color tone of the plates is unstable immediately after molding, so the color tone was measured more than one day after molding. In addition, plates used for comparison were stored under the same conditions, and the values ​​measured at the same time were used.

[0170] [9] Number of plates with defective appearance The 30 injection-molded plates described in [8] above were visually inspected, and the number of plates with black foreign matter (burn marks) was counted.

[0171]

[10] Dielectric properties: Relative permittivity (ε r ) · Dielectric loss tangent (tanδ) Polycarbonate resin, vacuum-dried at 80°C for 5 hours, was formed into a film using a hot press molding machine to produce films with a thickness of 40-150 μm. The molding conditions of the hot press molding machine were adjusted as appropriate within the range of temperature 150-250°C and pressure 10-15 MPa. Strips of film measuring 70 mm in length and 2 mm in width were cut from this film and conditioned for 48 hours under conditions of room temperature 23°C and humidity 50%. The relative permittivity (ε) was then measured at a frequency of 10 GHz using a cavity resonator (CP-531, manufactured by Kanto Applied Electronics Development Co., Ltd.) and a series network analyzer (E8361A PNA, manufactured by Keysight Technologies). r ) and dielectric loss tangent (tanδ × 10 -3 ) was measured.

[0172] [Manufacturing Examples 1-15: Manufacturing Examples of Polycarbonate Resin] Examples of manufacturing processes for polycarbonate resins, specifically PC(A1) to PC(A10), PC(B1), PC(B2), and PC(C1) to PC(C3), are shown.

[0173] [Manufacturing Example 1] A raw material mixture was prepared by adding 89.59 g (approximately 0.350 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) (manufactured by Honshu Chemical Co., Ltd.), 27.12 g (0.087 mol) of 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (BP-TMC) (manufactured by Honshu Chemical Co., Ltd.), 96.39 g (approximately 0.450 mol) of diphenyl carbonate (DPC), and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds, to a 150 ml glass reactor equipped with a reactor stirrer, reactor heater, and reactor pressure regulator.

[0174] Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the pressure was restored to atmospheric pressure with nitrogen. This process was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purging, the external temperature of the reactor was raised to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. While distilling off the phenol produced as a by-product by the oligomerization reaction of the dihydroxy compound and DPC taking place inside the reactor, the pressure inside the reactor was reduced from an absolute pressure of 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) over 40 minutes.

[0175] Next, the reactor pressure was maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off the phenol. After that, the external temperature of the reactor was raised to 250°C, and the internal pressure of the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes to remove the distilled phenol from the system. Furthermore, the external temperature of the reactor was raised to 285°C, and the internal pressure of the reactor was reduced to 30 Pa (approximately 0.2 Torr) to carry out the polycondensation reaction. The polycondensation reaction was terminated when the reactor stirrer reached a predetermined stirring power.

[0176] Next, the reactor was repressurized to an absolute pressure of 101.3 kPa using nitrogen, and then increased to a gauge pressure of 0.2 MPa. The polycarbonate resin was then extracted in strand form from the bottom of the reactor tank, and after obtaining the strand-shaped polycarbonate resin, it was pelletized using a rotary cutter. The polycarbonate resin PC(A1) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0177] [Manufacturing Example 2] The process was carried out using the method described in Production Example 1, except that a raw material mixture was prepared by adding 89.59 parts (approximately 0.350 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 27.12 parts (approximately 0.087 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 98.73 parts (approximately 0.461 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(A2) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0178] [Manufacturing Example 3] Except for setting the stirring power at the end of the reaction to a higher value than in Production Example 1, the procedure was carried out in the same manner as described in Production Example 1. The polycarbonate resin PC(A3) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0179] [Manufacturing Example 4] Except for setting the stirring power at the end of the reaction to a higher level than in Production Examples 1 and 3, the procedure was carried out in the same manner as described in Production Example 1. The polycarbonate resin PC(A4) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0180] [Manufacturing Example 5] The process was carried out in the same manner as described in Production Example 1, except that a raw material mixture was prepared by adding 89.59 parts (approximately 0.350 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 27.12 parts (approximately 0.087 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 95.92 parts (approximately 0.448 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 6.0 μmol per mole of total dihydroxy compounds. The polycarbonate resin PC(A5) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0181] [Manufacturing Example 6] The process was carried out using the method described in Production Example 1, except that a raw material mixture was prepared by adding 89.59 parts (approximately 0.350 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 27.12 parts (approximately 0.087 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 95.92 parts (approximately 0.448 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 10.0 μmol per mole of total dihydroxy compounds. The polycarbonate resin PC(A6) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0182] [Manufacturing Example 7] The process was carried out in the same manner as described in Production Example 1, except that a raw material mixture was prepared by adding 64.57 parts (approximately 0.252 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 52.14 parts (approximately 0.168 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 94.62 parts (approximately 0.442 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 2.0 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(A7) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0183] [Manufacturing Example 8] The process was carried out using the method described in Production Example 1, except that a raw material mixture was prepared by adding 64.57 parts (approximately 0.252 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 52.14 parts (approximately 0.168 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 92.64 parts (approximately 0.432 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(A8) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1A.

[0184] [Manufacturing Example 9] The process was carried out using the method described in Production Example 1, except that a raw material mixture was prepared by adding 58.36 parts (approximately 0.228 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 58.36 parts (approximately 0.188 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 93.93 parts (approximately 0.438 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(A9) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0185] [Manufacturing Example 10] The process was carried out in the same manner as described in Production Example 1, except that a raw material mixture was prepared by adding 52.78 parts (approximately 0.206 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 63.93 parts (approximately 0.206 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 91.31 parts (approximately 0.426 mol) of DPC, and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 2.0 μmol per mole of total dihydroxy compounds. The polycarbonate resin PC(A10) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0186] [Manufacturing Example 11] The process was carried out in the same manner as described in Production Example 1, except that a raw material mixture was prepared by adding 54.72 parts (approximately 0.214 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 61.99 parts (approximately 0.214 mol) of 4,4'-(1-phenylethylidene)diphenol (hereinafter sometimes abbreviated as BP-AP) (manufactured by Honshu Chemical Co., Ltd.), 93.75 parts (approximately 0.438 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(A11) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0187] [Manufacturing Example 12] The process was carried out in the same manner as described in Production Example 1, except that a raw material mixture was prepared by adding 100.00 parts (approximately 0.390 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 86.91 parts (approximately 0.406 mol) of DPC, and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(B1) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0188] [Manufacturing Example 13] The process was carried out in the same manner as described in Production Example 1, except that a raw material mixture was prepared by adding 100.00 parts (approximately 0.390 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 86.08 parts (approximately 0.402 mol) of DPC, and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(B2) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0189] [Manufacturing Example 14] The process was carried out using the method described in Production Example 1, except that a raw material mixture was prepared by adding 116.71 parts (approximately 0.402 mol) of BP-AP (manufactured by Honshu Chemical Co., Ltd.), 89.12 parts (approximately 0.416 mol) of DPC, and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 0.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(B3) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0190] [Manufacturing Example 15] The process was carried out in the same manner as described in Production Example 1, except that a raw material mixture was prepared by adding 89.59 parts (approximately 0.350 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 27.12 parts (approximately 0.087 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 98.26 parts (approximately 0.459 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mol of total dihydroxy compounds. The polycarbonate resin PC(C1) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0191] [Manufacturing Example 16] The process was carried out using the method described in Production Example 1, except that a raw material mixture was prepared by adding 89.59 parts (approximately 0.350 mol) of BPC (manufactured by Honshu Chemical Co., Ltd.), 27.12 parts (approximately 0.087 mol) of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 95.74 parts (approximately 0.447 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 8.0 μmol per mole of total dihydroxy compounds. The polycarbonate resin PC(C2) obtained in this manner was subjected to each evaluation using the procedure described above. The results are shown in Table 1B.

[0192] [Manufacturing Example 17] 64.57 parts (about 0.252 mol) of BPC (manufactured by Honshu Chemical Industry Co., Ltd.), 52.14 parts (about 0.168 mol) of BP-TMC (manufactured by Honshu Chemical Industry Co., Ltd.), 94.89 parts (about 0.443 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst were added so that the amount of cesium carbonate was 1.5 μmol per 1 mol of all dihydroxy compounds to prepare a raw material mixture, and then the procedure was carried out in the same manner as described in Production Example 1. [[ID=?]] For the polycarbonate resin PC(C3) thus obtained, each evaluation was carried out according to the above procedure. The results are shown in Table 1B.

[0193] [Production Example 18] 46.69 g (about 0.182 mol) of 4,4-methylenebis(2,6-dimethylphenol) (TmBPF) (manufactured by Tokyo Chemical Industry Co., Ltd.), 70.02 g (about 0.273 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) (manufactured by Honshu Chemical Industry Co., Ltd.), 99.97 g (about 0.467 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst were added so that the amount of cesium carbonate was 5 μmol per 1 mol of all dihydroxy compounds to prepare a raw material mixture, and then the procedure was carried out in the same manner as described in Production Example 1 to obtain a polycarbonate resin PC(C4).

[0194]

Table 1

[0195] [Production Examples 19, 20, 21: Production Examples of Thermoplastic Resin Compositions] Production examples of PC(A12), PC(A13), and PC(A14), which are thermoplastic resin compositions, are shown. The respective components described in Table 1A and 1B above and Table 2 below were blended at the ratios (mass ratios) described in Table 3 below, mixed in a tumbler for 20 minutes, and then supplied to a φ30 mm twin-screw extruder (TEX30α) manufactured by Japan Steel Works, Ltd. equipped with 1 vent, kneaded under the conditions of a screw rotation speed of 160 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 260°C, and the molten resin extruded in a strand shape was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of thermoplastic resin compositions PC(A12), PC(A13), and PC(A14).

[0196] [Table 2][[ID=…]] [[ID=…]] [[ID=…]] [[ID=…]] [[ID=…]]

[0197] [[ID=…]] [[ID=…]] [Table 3][[ID=…]] [[ID=…]] [[ID=…]] [[ID=…]] [[ID=…]]

[0198] [[ID=…]] [Examples 1 to 14, Comparative Examples 1 to 4][[ID=…]] Regarding PC(A1) to PC(A14), PC(B2), and PC(C1) to PC(C3) obtained by the above method, the results of evaluating the glass transition temperature, surface hardness, initial color tone of the pellets, and impact resistance, together with the measurement results of the viscosity average molecular weight, specific viscosity, and (14) / (13) ratio in the hydrolyzate, are shown in Tables 4A and 4B below.[[ID=…]] [[ID=…]]

[0199] [[ID=…]] [[ID=…]] [[ID=…]] [Table 4][[ID=…]] [[ID=…]] [[ID=…]] [[ID=…]]

[0200] [[ID=…]] From Tables 4A and 4B, it can be seen that the polycarbonate resin of the present invention containing structural unit (a) and structural unit (b) and satisfying the specific viscosity, viscosity average molecular weight, and (14) / (13) ratio defined in the present invention has a high glass transition temperature, excellent heat resistance, high surface hardness, and also excellent initial color tone and impact resistance.[[ID=…]] On the other hand, in Comparative Example 1 which does not contain structural unit (b) and the (14) / (13) ratio in the hydrolyzate is outside the scope of the present invention, the glass transition temperature is low, the heat resistance is poor, and the impact resistance is also bad. Even when containing the polycarbonate resin of the present invention, Comparative Example 2, whose specific viscosity is outside the specified range of the present invention, exhibits significantly inferior impact resistance. In Comparative Example 3, where the specific viscosity and the (14) / (13) ratio in the hydrolysate are outside the specified range of the present invention, the initial color tone is significantly inferior. Comparative Example 4, in which the specific viscosity and viscosity-average molecular weight are outside the range specified by the present invention, exhibits inferior impact resistance.

[0201] [Example 15, Comparative Examples 5, 6] Table 5 below shows the results of evaluations of the glass transition temperature, plate color, plate appearance, and dielectric properties of PC(A3), PC(B2), and PC(C4) obtained by the method described above.

[0202] [Table 5]

[0203] Table 5 shows that the polycarbonate resin of Example 15, which contains structural units (a) and (b) and satisfies the specific viscosity, viscosity-average molecular weight, and (14) / (13) ratio in the hydrolysate as defined in the present invention, has a higher glass transition temperature and thus higher heat resistance, as well as superior dielectric properties, compared to the polycarbonate resin of Comparative Example 5. Furthermore, the polycarbonate resin of the present invention in Example 15 has significantly superior plate color and appearance compared to the polycarbonate resin of Comparative Example 6. From the above, it can be seen that the polycarbonate resin of Example 15, which is the polycarbonate resin of the present invention, has superior dielectric properties, heat resistance, and color tone compared to the polycarbonate resins of Comparative Examples 5 and 6, and also exhibits fewer appearance abnormalities during molding, making it suitable for use as a component in microwave and / or millimeter-wave communication equipment.

Claims

1. A thermoplastic resin composition containing polycarbonate resin, The polycarbonate resin comprises a structural unit (a) represented by the following formula (11) and a structural unit (b) represented by the following formula (12A) and / or the following formula (12B). The ratio of structural unit (a) to structural unit (b) is such that structural unit (b) is 20 mol% or more and 50 mol% or less of the sum of the content ratios of structural unit (a) and structural unit (b). The proportion of the polycarbonate resin in the total resin components contained in the thermoplastic resin composition is 30% by mass or more. The specific viscosity of a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 mL of methylene chloride was measured at 20°C to be between 0.308 and 0.

455. The viscosity-average molecular weight of the polycarbonate resin is 17,300 to 26,400. A thermoplastic resin composition in which the hydrolyzed polycarbonate resin yields a hydrolyzed product containing dihydroxy compounds represented by the following formulas (13), (14), (15A), and (15B), and the content of the dihydroxy compound represented by the following formula (14) in the hydrolyzed product is 100 ppm to 1,300 ppm relative to the content of the dihydroxy compound represented by the following formula (13). 【Chemistry 1】 (In equation (11), Q is expressed by the following equation (16). In formula (12A), R １１ Each of the terms independently represents an alkyl group having 1 to 4 carbon atoms, and n is an integer from 0 to 3. In formula (12B), W is a methyl group or a phenyl group. In equation (13), Q is the same as Q in equation (11). In equation (14), Q is the same as Q in equation (11), and R １２ represents a hydrogen atom or a methyl group. In formula (15A), R １１ R in equation (12A) １１ It is synonymous with [the above]. In equation (15B), W is equivalent to W in equation (12B). 【Chemistry 2】 (In formula (16), R13 and R14 are methyl groups. * represents the bond to the benzene ring in formula (11).)

2. The thermoplastic resin composition according to claim 1, wherein the structural unit (b) includes a structural unit represented by formula (12A).

3. The thermoplastic resin composition according to claim 2, wherein the structural unit (a) and structural unit (b) are included as a copolymer.

4. The thermoplastic resin composition according to claim 1, wherein the structural unit (b) includes a structural unit represented by formula (12B).

5. The thermoplastic resin composition according to claim 4, wherein the structural unit (a) and structural unit (b) are included as a blend.

6. In the formula (12A), R １１ The thermoplastic resin composition according to claim 1, wherein is a methyl group.

7. The thermoplastic resin composition according to claim 1, wherein n is 3 in formula (12A).

8. The thermoplastic resin composition according to claim 1, wherein the structural unit (b) is represented by the following formula (17). 【Transformation 3】

9. The thermoplastic resin composition according to claim 1, wherein the sum of the content ratios of structural unit (a) and structural unit (b) contained in the polycarbonate resin is 80 mol% or more of the total carbonate structural units of the polycarbonate resin.

10. The thermoplastic resin composition according to claim 1, wherein the glass transition temperature of the polycarbonate resin is 125°C or higher.

11. A communication device component obtained using the thermoplastic resin composition described in any one of claims 1 to 10.

12. A microwave and / or millimeter-wave communication device obtained using the communication device component described in claim 11.

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