JP2021191817A - Polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition excellent in heat resistance, mechanical strength and molding processing ability, and comprising a low dielectric constant and a low dielectric tangent.SOLUTION: There is provided a polycarbonate resin composition including a polycarbonate resin including: a repeating unit (A) expressed by the following formula (1); and a repeating unit (B) expressed by the following formula (2). A ratio of a sum of a repeating unit (C) which is included in the repeating unit (B) and is expressed by the following formula (3), and a repeating unit (D) which is expressed by the following formula (4) and included in the repeating unit (B), is 40 mol% or more.SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate resin composition having excellent heat resistance, mechanical strength, and molding processability, as well as a low relative permittivity and a low dielectric loss tangent. The present invention also relates to a molded product using this polycarbonate resin composition and a cover for a millimeter wave radar.

Polycarbonate resin is excellent in mechanical strength, heat resistance, electrical characteristics, transparency, etc., and is widely used as an engineering plastic in various fields.

In recent years, high frequency band radio waves have come to be used in the fields of electrical and electronic equipment and automobiles, and along with this, materials having a low relative permittivity and a low dielectric loss tangent are required. However, the conventional polycarbonate resin made from bisphenol A could not sufficiently satisfy these requirements.

It can be expected that the relative permittivity can be lowered by using a polycarbonate resin made from an aliphatic diol, but there is a problem that the heat resistance is lowered.

Patent Document 1 discloses a polycarbonate copolymer having improved optical properties and heat resistance by copolymerizing a cyclic acetal-based diol, which is an aliphatic diol, and an aromatic-based diol. Further, Patent Document 2 discloses a polycarbonate copolymer having a low photoelastic constant and improved thermal stability by copolymerizing a cyclic acetal-based diol, which is an aliphatic diol, with an aromatic-based diol. Has been done.

Patent Document 3 proposes a cover for a millimeter wave radar having a reduced dielectric loss tangent and improved millimeter wave transmission by using a polycarbonate resin made from bisphenol having a specific substituent.

Japanese Unexamined Patent Publication No. 9-268225 International Publication No. 2012/0693965 Japanese Unexamined Patent Publication No. 2019-197048

With the increase in the amount of information communication in recent years, there is a strong demand for increasing the communication speed of information communication devices such as mobile phones. It is preferable to use radio waves in a high frequency band for high-speed communication, and the market for next-generation (5G) communication is expected to rise in the 28 GHz band.

The use of such high frequency bands is expected to be used not only in communication such as mobile phones but also in a wide range of fields. For example, in in-vehicle applications, social infrastructure applications, medical / nursing care applications, the frequency of millimeter-wave radar is increasing for the purpose of increasing the distance to a detectable object and improving the maximum resolution.

In addition, there is an increasing demand for higher performance in the housings of information communication equipment that are expected to use high frequency bands. Radio waves in the high frequency band have a larger transmission loss than radio waves in the lower frequency band, and are characterized by poor material permeability. Therefore, it is desired that the housing used for high-frequency communication has better radio wave transmission than before.

The transmission loss is proportional to the square root of the relative permittivity (ε _r ) of the dielectric and the dielectric loss tangent (tan δ) of the dielectric. Therefore, in order to improve the radio wave transmitting of the housing, it is necessary to be small relative dielectric constant of the material used for housing epsilon _r, and dielectric loss tangent tan [delta.

Further, it is desirable that the material used in such a field not only has a low relative permittivity and a low dielectric loss tangent, but also has appropriate heat resistance, mechanical strength, and molding processability, and these conditions are satisfied. There is a strong demand for materials that meet these requirements. However, conventional materials have not been able to meet these requirements.

Patent Document 1 discloses a polycarbonate copolymer having improved heat resistance, but does not mention any dielectric properties. Further, Patent Document 2 discloses a polycarbonate copolymer having improved thermal stability, but does not mention any dielectric property.

Patent Document 3 proposes a cover for a millimeter-wave radar in which the dielectric loss tangent is lowered and the millimeter-wave permeability is improved by using a polycarbonate resin made from bisphenol having a specific substituent. No significant improvement in the relative permittivity was observed as compared with the polycarbonate resin made from A as a raw material.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a polycarbonate resin composition having excellent heat resistance, mechanical strength, and molding processability, as well as a low relative permittivity and a low dielectric loss tangent. And.

As a result of diligent research to solve the above problems, the present inventor has found that a polycarbonate resin composition containing two specific repeating units can be used to obtain a polycarbonate resin composition that meets the above object. , The present invention has been completed.

That is, the gist of the present invention lies in the following [1] to [17].

[1] A polycarbonate resin composition containing a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), the repeating unit. Polycarbonate resin in which the sum of the ratio of the repeating unit (C) represented by the following formula (3) and the ratio of the repeating unit (D) represented by the following formula (4) contained in (B) is 40 mol% or more. Composition.

[In the formula (1), W ¹ is an organic group containing a cyclic structure and may contain a hetero atom. R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, may contain a hetero atom, or may be bonded to ^{W 1 to form a ring.}
In the formula (2), R ^{5 to} R ⁸ are independent groups having a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group having 6 to 12 carbon atoms including an aryl group, and W ² is a group. , A single bond, an oxygen atom, a sulfur atom, and at least one selected from a divalent organic group.
In formula (3), R ⁹ and R ¹⁰ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or groups having 6 to 12 carbon atoms including an aryl group, and R ¹¹ and R are R 11 and R, respectively. ^{Reference numeral 12} is an alkyl group having 1 to 10 carbon atoms independently, or a group having 6 to 12 carbon atoms including an aryl group.
In the formula (4), R ^{13 to} R ¹⁶ are independent alkyl groups having 1 to 10 carbon atoms or groups having 6 to 12 carbon atoms including an aryl group. ]

[2] The polycarbonate resin composition according to [1], wherein the amount of terminal hydroxyl groups measured by a colorimetric method using a titanium tetrachloride / acetic acid method is 100 to 2,500 ppm.

[3] The polycarbonate resin composition according to [1] or [2], wherein the amount of residual phenol is 250 ppm or less.

[4] The polycarbonate resin composition according to any one of [1] to [3], ^{wherein W 1} in the formula (1) is selected from the following formula (5) or (6).

[In formula (6), R ¹⁷ and R ¹⁸ each independently have a hydrogen atom, a group containing a hetero atom, a group containing a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom containing an aryl group. Represents a group of 6-12. ]

[5] The polycarbonate resin composition according to any one of [1] to [4], ^{wherein R 9} and R ¹⁰ in the formula (3) are independently hydrogen atoms or methyl groups, respectively.

[6] The polycarbonate resin composition according to any one of [1] to [5], ^{wherein R 13 to} R ¹⁶ in the formula (4) are methyl groups.

[7] The polycarbonate resin composition according to any one of [1] to [6], ^{wherein R 9} and R ¹⁰ in the formula (3) are methyl groups.

[8] The polycarbonate resin composition according to any one of [1] to [7], wherein the repeating unit (A) is a repeating unit represented by the following formula (7) or (8).

^{[9] The polycarbonate resin according to any one of [1] to [8], wherein W 2} in the formula (2) is selected from a single bond, a methylene group, an ethylidene group, and an isopropylidene group. Composition.

[10] The ratio of the sum of the repeating unit (C) and the repeating unit (D) contained in the repeating unit (B) is 80 mol% or more with respect to all the repeating units (B). The polycarbonate resin composition according to any one of [1] to [9].

[11] The polycarbonate resin according to any one of [1] to [10], wherein the amount of terminal hydroxyl groups measured by a colorimetric method using titanium tetrachloride / acetic acid is 130 to 1,000 ppm. Composition.

[12] The polycarbonate resin composition according to any one of [1] to [11], wherein the ratio of the repeating unit (A) to the repeating unit (B) is 1:99 to 90:10. thing.

[13] The polycarbonate resin composition according to any one of [1] to [12], wherein the polycarbonate resin has a viscosity average molecular weight (Mv) in the range of 16,000 to 32,000.

[14] A molded product obtained by using the polycarbonate resin composition according to any one of [1] to [13].

[15] An injection-molded article obtained by using the polycarbonate resin composition according to any one of [1] to [13].

[16] An extruded product obtained by using the polycarbonate resin composition according to any one of [1] to [13].

[17] A cover for a millimeter wave radar obtained by using the polycarbonate resin composition according to any one of [1] to [13].

Since the polycarbonate resin composition of the present invention has excellent heat resistance and mechanical strength, a low relative permittivity, and a low dielectric loss tangent, a polycarbonate resin composition having a low transmission loss and easily transmitting high frequency radio waves can be obtained. Can be provided. Such a polycarbonate resin composition can be used for housings of mobile phones and the like using radio waves in a high frequency band, millimeter-wave radars for various in-vehicle sensors, millimeter-wave radars for railways and aircraft, transportation, medical care / nursing, security, and information. It can be widely used for millimeter-wave radar and the like in the field of content transmission.

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below.

In addition, in this specification, "~" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value, unless otherwise specified.

[Polycarbonate resin]
The polycarbonate resin composition of the present invention is a polycarbonate resin composition containing a repeating unit (A) represented by the following formula (1) and a polycarbonate resin containing the repeating unit (B) represented by the following formula (2). Therefore, the sum of the ratios of the repeating unit (C) represented by the following formula (3) and the repeating unit (D) represented by the following formula (4) included in the repeating unit (B) is the total repeating unit (all repeating units ( It is characterized in that it is 40 mol% or more with respect to B).
A polycarbonate resin composition containing a polycarbonate resin containing a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), wherein the repeating unit (B) The sum of the ratios of the repeating unit (C) represented by the following formula (3) and the repeating unit (D) represented by the following formula (4) contained in the above is 40 mol% or more, so that the heat resistance and the machine are improved. It is possible to achieve a low specific dielectric constant and a low dielectric tangent while having excellent strength.

[In the formula (1), W ¹ is an organic group containing a cyclic structure and may contain a hetero atom. R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, may contain a hetero atom, or may be bonded to ^{W 1 to form a ring.}
In the formula (2), R ^{5 to} R ⁸ are independent groups having a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group having 6 to 12 carbon atoms including an aryl group, and W ² is a group. , A single bond, an oxygen atom, a sulfur atom, and at least one selected from a divalent organic group.
In formula (3), R ⁹ and R ¹⁰ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or groups having 6 to 12 carbon atoms including an aryl group, and R ¹¹ and R are R 11 and R, respectively. ^{Reference numeral 12} is an alkyl group having 1 to 10 carbon atoms independently, or a group having 6 to 12 carbon atoms including an aryl group.
In the formula (4), R ^{13 to} R ¹⁶ are independent alkyl groups having 1 to 10 carbon atoms or groups having 6 to 12 carbon atoms including an aryl group. ]

The polycarbonate resin composition of the present invention may contain a polycarbonate resin mixture of a polycarbonate resin containing a repeating unit (A) and a polycarbonate resin containing a repeating unit (B), and the repeating unit (A) and the repeating unit may be contained. It may contain a copolymerized polycarbonate resin containing (B), a polycarbonate resin containing a repeating unit (A) and / or a polycarbonate resin containing a repeating unit (B), and a repeating unit (A) and a repeating unit. It may contain the copolymerized polycarbonate resin containing (B).

<Repeating unit (A) represented by equation (1)>
In the polycarbonate resin composition of the present invention, in the above formula (1), W ¹ is an organic group containing a cyclic structure and may contain a heteroatom. R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, may contain a hetero atom, or may be bonded to ^{W 1 to form a ring.} Here, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. It is preferably an oxygen atom.

In the above formula (1), W ¹ is not particularly limited as long as it is an organic group containing a cyclic structure, but preferably contains a hetero atom.

In the above formula (1), ^{more preferable specific examples of W 1} include the following formula (5) or (6).

[In formula (6), R ¹⁷ and R ¹⁸ each independently have a hydrogen atom, a group containing a hetero atom, a group containing a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom containing an aryl group. Represents a group of 6-12. ]

When W ¹ is represented by the above formula (6), R ¹ or R ² in the above formula (1) is at the position of * 1 and R ³ or R ⁴ is * as shown in the following formula (6B). It is preferable to combine at the position of 2 to form a ring.

R ¹⁷ and R ¹⁸ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom.

A particularly suitable specific example of the repeating unit (A) is a repeating unit represented by the following general formula (7) or (8). By setting the repeating unit (A) as the repeating unit represented by the following formula (7) or (8), the thermal stability of the polycarbonate resin composition of the present invention can be improved and the relative permittivity can be effectively lowered. Can be done.

<Repeating unit (B) represented by equation (2)>
In the polycarbonate resin composition of the present invention, in the above formula (2), R ^{5 to} R ⁸ each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 6 carbon atoms. It is a group of 12, and W ² represents at least one selected from a single bond, an oxygen atom, a sulfur atom, and a divalent organic group.

Of R ⁵ to R ^8, Specific examples of the alkyl group having 1 to 10 carbon atoms, a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- hexyl, n- Heptyl group, n-octyl group, n-nonyl group, n-decyl group;
Methylethyl group, Methylpropyl group, Methylbutyl group, Methylpentyl group, Methylhexyl group, Methylheptyl group, Methyloctyl group, Methylnonyl group;
Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group;
Trimethylpropyl group, trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group;
Ethylbutyl group, ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group;
Examples thereof include a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a tetramethylcyclohexyl group, an ethylcyclohexyl group, a diethylcyclohexyl group, a methylethylcyclohexyl group and the like.

Specific examples of the groups of R ^{5 to} R ⁸ containing an aryl group and having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a naphthyl group and the like.

R ⁵ to R ⁸ is, among these, preferably are each independently hydrogen atom, or a methyl ^group, all hydrogen atoms of the R 5 to R ^8, or any ^R 5 to R ⁸ is a methyl group Is more preferable.

In the formula (2), W ² represents at least one selected from a single bond, an oxygen atom, a sulfur atom, and a divalent organic group.
The ^{divalent organic group of W 2} is not particularly limited as long as it is conventionally known and can be appropriately selected and used. As a specific example, the organic represented by the following formulas (9a) to (9h) can be used. The group is mentioned.

In the above formula (9a), R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, or an alkoxy group having 1 to 24 carbon atoms, and among them, carbon. It is preferably a monovalent hydrocarbon group having 1 to 24 atoms.
The monovalent hydrocarbon group having 1 to 24 carbon atoms may have an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, and a substituent having 6 to 24 carbon atoms. Examples thereof include 24 aryl groups and arylalkyl groups having 7 to 24 carbon atoms.

Examples of the alkyl group having 1 to 24 carbon atoms include a linear group, a branched alkyl group, and an alkyl group having a partially cyclic structure, and among them, a linear alkyl group is preferable. Examples of such an alkyl group having 1 to 24 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and n. -The octyl group and the like can be mentioned.

Examples of the alkenyl group having 2 to 24 carbon atoms include a linear alkenyl group, a branched alkenyl group, and an alkenyl group having a partially cyclic structure, and among them, a linear alkenyl group is preferable. Examples of such an alkenyl group having 2 to 24 carbon atoms include a vinyl group, an n-propenyl group, an n-butenyl group, an n-pentenyl group, an n-hexenyl group, an n-heptenyl group, and an n-. Examples thereof include an octenyl group.

Examples of the aryl group having 6 to 24 carbon atoms include an aryl group which may have a substituent such as an alkyl group such as a phenyl group, a naphthyl group, a methylphenyl group, a dimethylphenyl group and a trimethylphenyl group.
Examples of the arylalkyl group having 7 to 24 carbon atoms include a benzyl group.

Examples of the alkoxy group having 1 to 24 carbon atoms include linear, branched, and partially cyclic alkoxy groups, and among them, a linear alkoxy group is preferable. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like.

In the above formula (9b), X ¹ represents an oxygen atom or NRa. Here, Ra has the same definition ^{as R 19} and R ^{20 described above.}

In the above formula (9c), X ² represents a divalent hydrocarbon group having 3 to 18 carbon atoms, and for example, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and the like. Examples thereof include a decylene group, an undecylene group, a dodecynylene group and the like, and each of them may further have a substituent. Examples of the substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a phenyl group and the like. Further, it may have a partially crosslinked structure.

In the above formula (9h), 2 two ^{X 3} represents an alkylene group having 1 to 7 carbon atoms independently. Such an alkylene group may be a linear group or a branched chain, and may have a cyclic structure, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. Further, m represents an integer of 1 to 500, of which 5 to 300 is preferable, and 10 to 100 is more preferable.

Of these, W ² is more preferably a single bond, a methylene group, an ethylidene group, or an isopropylidene group.

<Repeating unit (C) represented by equation (3)>
In the polycarbonate resin composition of the present invention, in the above formula (3), R ⁹ and R ¹⁰ each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, or a group having an aryl group and having 6 to 12 carbon atoms.

Specific examples of the alkyl groups of R ⁹ and R ¹⁰ having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-. Heptyl group, n-octyl group, n-nonyl group, n-decyl group;
Methylethyl group, Methylpropyl group, Methylbutyl group, Methylpentyl group, Methylhexyl group, Methylheptyl group, Methyloctyl group, Methylnonyl group;
Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group;
Trimethylpropyl group, trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group;
Ethylbutyl group, ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group;
Examples thereof include a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a tetramethylcyclohexyl group, an ethylcyclohexyl group, a diethylcyclohexyl group, a methylethylcyclohexyl group and the like.

Specific examples of the groups of R ⁹ and R ¹⁰ having 6 to 12 carbon atoms including an aryl group include a phenyl group, a tolyl group, a naphthyl group and the like.

It is preferable that R ⁹ and R ¹⁰ are independently hydrogen atoms or methyl groups, respectively. Further, it is more preferable that at least one of them is a methyl group, and it is most preferable that both ^{R 9} and R ^{10 are methyl groups.}

Specific examples of the alkyl groups of R ¹¹ and R ¹² having 1 to 10 carbon atoms are the same as those of R ⁹ and R ¹⁰ .

Specific examples of the groups of R ¹¹ and R ¹² having 6 to 12 carbon atoms including an aryl group are the same as those of R ⁹ and R ¹⁰ .

R ¹¹ and R ¹² are preferably alkyl groups having 1 to 10 carbon atoms independently, and most preferably methyl groups.

<Repeating unit (D) represented by equation (4)>
In the polycarbonate resin composition of the present invention, in the above formula (4), R ^{13 to} R ¹⁶ are independently alkyl groups having 1 to 10 carbon atoms or groups having 6 to 12 carbon atoms including an aryl group. Is.

Specific examples of the alkyl groups of R ^{13 to} R ¹⁶ having 1 to 10 carbon atoms are the same as those of R ⁹ and R ¹⁰ in the above formula (3).

Specific examples of the groups of R ^{13 to} R ¹⁶ containing an aryl group and having 6 to 12 carbon atoms are the same as those of R ⁹ and R ¹⁰ in the above formula (3).

Preferably any one or more of R ¹³ to R ¹⁶ is a methyl ^group, and most preferably R 13 ^{to R 16} are all methyl groups.

<Preferable repeating unit (B)>
The most suitable as the repeating unit (B) of the polycarbonate resin composition of the present invention is the repeating unit represented by the following formula (10) and / or the following formula (11). That is, the repeating unit (B) preferably includes the repeating unit represented by the following formula (10) as the repeating unit (C), and the repeating unit represented by the following formula (11) as the repeating unit (D). It is preferable to include it. By setting the repeating unit (B) as a repeating unit represented by the following formula (10) and / or the following formula (11), the mechanical properties including the surface hardness of the polycarbonate resin composition of the present invention and the heat resistance can be further improved. It will be excellent.

<Repeating unit (A), (B)>
The polycarbonate resin composition of the present invention contains a repeating unit (A) represented by the formula (1) and a repeating unit (B) represented by the formula (2), and is included in the repeating unit (B). The sum of the ratios of the repeating unit (C) represented by the formula (3) and the repeating unit (D) represented by the formula (4) is 40 mol% or more with respect to the total repeating unit (B). be.

The ratio of the repeating unit (A) to the repeating unit (B) in the polycarbonate resin contained in the polycarbonate resin composition of the present invention is not particularly limited, but the ratio of the repeating unit (A) to the repeating unit (B) (mol). The ratio) is preferably 1:99 to 90:10, particularly preferably 10:90 to 80:20, particularly preferably 15:85 to 70:30. Further, from the viewpoint of improving the dielectric property, it is preferable that the polycarbonate resin composition of the present invention contains 10% by mass or more of the repeating unit (A), particularly 15% by mass or more, and from the viewpoint of improving heat resistance and dielectric property. It is preferable that the polycarbonate resin composition of the present invention contains the repeating unit (B) in an amount of 10% by mass or more, particularly 20% by mass or more, and particularly preferably 30% by mass or more.
The sum of the content of the repeating unit (A) and the content of the repeating unit (B) in the polycarbonate resin contained in the polycarbonate resin composition of the present invention is preferably 80% by mass or more from the viewpoint of improving the dielectric property. 85% by mass or more is more preferable, and 90% by mass or more is particularly preferable.

The ratios of the repeating units (A) and (B) in the polycarbonate resin contained in the polycarbonate resin composition can be calculated by measuring ^{1 H-NMR of the polycarbonate resin dissolved in deuterated chloroform.} In the present invention, a deuterated chloroform solution of a polycarbonate resin was prepared so that the concentration of the polycarbonate resin was 50 mg / mL, the relaxation time was 6 seconds, and the number of integrations was 128 times at 30 ° C.

Further, among the repeating units (B) in the polycarbonate resin contained in the polycarbonate resin composition of the present invention, the repeating unit (C) represented by the formula (3) and the repeating unit represented by the formula (4). The ratio of the sum of (D) is 40 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more, and particularly preferably 100 mol% with respect to the total repeating unit (B). %.

The ratio of the sum of the repeating unit (C) and the repeating unit (D) to the repeating unit (B) in the polycarbonate resin contained in the polycarbonate resin composition of the present invention is ^{1 of the polycarbonate resin dissolved in heavy chloroform.} It can be calculated by measuring H-NMR. In the present invention, a deuterated chloroform solution of a polycarbonate resin was prepared so that the concentration of the polycarbonate resin was 50 mg / mL, the relaxation time was 6 seconds, and the number of integrations was 128 times at 30 ° C.

The ratio of the repeating unit (A), (B) and the repeating unit (C), (D) in the repeating unit (B) in the polycarbonate resin contained in the polycarbonate resin composition is the polycarbonate resin production. It can also be calculated from the charged composition ratio of the dihydroxy compound at the time, and in the examples described later, it is obtained from this charged composition ratio.

The polycarbonate resin contained in the polycarbonate resin composition of the present invention may contain only one type of the repeating unit (A), or may contain two or more types. That is, it may contain two or more kinds of repeating units (A) represented by the above formula (1). Further, the repeating unit (B) may also contain only one type, or may include two or more types. That is, it may contain two or more kinds of repeating units (B) represented by the above formula (2). The same applies to the repeating unit (C) and the repeating unit (D).

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention may contain components other than the above-mentioned repeating units (A) and (B) as long as the characteristics of the present invention are not impaired. However, in order to ensure the effect of the present invention, the sum of the repeating units (A) and (B) is preferably contained in the polycarbonate resin composition of the present invention in an amount of 65% by mass or more, preferably 70% by mass or more. It is more preferably contained, and it is particularly preferable that it is contained in an amount of 75% by mass or more.

The components of the polycarbonate resin composition of the present invention other than the above-mentioned repeating units (A) and (B) include, for example, other repeating units (E) other than the repeating units (A) and (B), and various resins. Examples thereof include additives and resins other than polycarbonate resins.
The content of the polycarbonate resin in the polycarbonate resin composition of the present invention is preferably 80% by mass or more with respect to 100% by mass of the polycarbonate resin composition of the present invention in order to effectively bring out the features of the present invention. It is more preferably 85% by mass or more, and particularly preferably 90% by mass or more.

<Other repeating units>
The polycarbonate resin composition of the present invention may contain a repeating unit (E) other than the above-mentioned repeating units (A) and (B) as long as the characteristics of the present invention are not impaired. Examples of the other repeating unit (E) include a repeating unit represented by the following formula (12).

In the above formula (12), R ^{21 to} R ²⁶ are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and among them, alkyl groups having 1 to 6 carbon atoms are preferable. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group and the like. As such another repeating unit (E), a repeating unit in which R ^{21 to} R ²⁴ are methyl groups and R ²⁵ and R ²⁶ are hydrogen atoms is preferable.

Specific examples of the other repeating unit (E) include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) cyclohexane, and 2,2-bis. Derived from aromatic dihydroxy compounds such as (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 6,6'-dihydroxy-3,3,3', 3'-tetramethyl-1,1'-spirobiindan Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 6,6'-dihydroxy-3,3,3', 3. '-Tetramethyl-1,1'-spirobiindan is more preferred.

<Seed resin additive>
Examples of the resin additive that the polycarbonate resin composition of the present invention may contain include a heat stabilizer, an antioxidant, a mold release agent, a lightfastening agent (HALS), a flame retardant, an antistatic agent, and an antifogging agent. Examples thereof include lubricants, antiblocking agents, fluidity improving agents, plasticizers, dispersants, antibacterial agents, dyes, pigments and the like. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.

<Other resins>
Other resins that can be contained in the polycarbonate resin composition of the present invention include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), and the like. Acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin) and other styrene resins; polyethylene resin, polypropylene Examples thereof include polyolefin resins such as resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins; polymethacrylate resins and the like.
As the other resin, one type may be contained, or two or more types may be contained in any combination and ratio.

<Amount of terminal hydroxyl group measured by colorimetric method>
The amount of terminal hydroxyl groups measured by the colorimetric quantitative method using titanium tetrachloride / acetic acid of the polycarbonate resin composition of the present invention is not particularly limited, but is preferably 2,500 ppm or less, preferably 2,000 ppm or less. It is more preferably 1,500 ppm or less, and particularly preferably 1,000 ppm or less. By setting the amount of terminal hydroxyl groups measured by the colorimetric quantitative method to the above upper limit or less, the relative permittivity of the polycarbonate resin composition of the present invention can be effectively reduced. Further, the amount of terminal hydroxyl groups measured by the colorimetric quantitative method in the polycarbonate resin composition of the present invention is preferably 100 ppm or more, more preferably 110 ppm or more, further preferably 120 ppm or more, and even more preferably 130 ppm. The above is particularly preferable. By setting the amount of terminal hydroxyl groups measured by the colorimetric quantitative method to be equal to or higher than the above lower limit, the hue, thermal stability, and wet heat stability of the polycarbonate resin composition of the present invention can be further improved.

The amount of terminal hydroxyl groups measured by the colorimetric quantitative method of the polycarbonate resin composition of the present invention is adjusted to a preferable value by controlling the molar ratio of raw materials, the amount of catalyst, the temperature during the reaction and the degree of vacuum. It is possible.

The unit of the amount of the terminal hydroxyl group measured by the specific color quantification method of the polycarbonate resin composition of the present invention is the mass of the terminal hydroxyl group with respect to the mass of the polycarbonate resin composition of the present invention expressed in ppm. The measuring method is as described in Examples of the colorimetric method using titanium tetrachloride / acetic acid. According to the measuring method, the terminal hydroxyl group derived from the aromatic diol can be detected without detecting the terminal hydroxyl group derived from the aliphatic diol.
In a polycarbonate resin composition having a plurality of structures, a sample in which the corresponding raw material dihydroxy compound is mixed according to the copolymerization ratio is prepared at a concentration of at least 3 levels, and a calibration curve is drawn from the data of 3 points or more. Then, measure the amount of terminal hydroxyl groups. The detection wavelength is 546 nm.

<Viscosity average molecular weight>
The molecular weight of the polycarbonate resin contained in the polycarbonate resin composition of the present invention is not particularly limited, but is the viscosity average molecular weight (Mv) converted from the solution viscosity, preferably 16,000 to 32,000. By setting the viscosity average molecular weight within the above range, the characteristics of the present invention can be effectively brought out. That is, when the viscosity average molecular weight of the polycarbonate resin contained in the polycarbonate resin composition of the present invention is at least the above lower limit, the relative permittivity and the dielectric loss tangent of the polycarbonate resin composition of the present invention are low, which is preferable. Further, when the viscosity average molecular weight of the polycarbonate resin contained in the polycarbonate resin composition of the present invention is not more than the above upper limit, the fluidity of the polycarbonate resin composition of the present invention is good, which is preferable. From such a viewpoint, the viscosity average molecular weight (Mv) of the polycarbonate resin composition of the present invention is more preferably 17,000 or more, still more preferably 18,000 or more. Further, it is more preferably 31,000 or less, still more preferably 30,000 or less.

For the viscosity average molecular weight (Mv) of the polycarbonate resin, the intrinsic viscosity (extreme viscosity) [η] (unit: dL / g) at a temperature of 20 ° C. was determined using a Ubbelohde viscometer using methylene chloride as a solvent. It means the viscosity formula, that is, the value calculated from ^{η = 1.23 × 10 -4} Mv ^0.83. The intrinsic viscosity (extreme viscosity) [η] is a value calculated by the following formula by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dL).

<Pencil hardness>
The pencil hardness of the polycarbonate resin composition of the present invention is measured by a method according to ISO 15184. The pencil hardness is not particularly limited, but a pencil having a high hardness property such as HB or higher is preferable. Further, it is more preferable that the pencil hardness is F or more.
The pencil hardness of the polycarbonate resin composition is measured with a load of 750 g on a test piece of a polycarbonate resin having a thickness of 3 mm, a length of 25 mm, and a width of 25 mm using a pencil hardness tester. The test piece can be obtained by performing injection molding using an injection molding machine.

<Glass transition temperature>
The glass transition temperature (Tg) of the polycarbonate resin composition of the present invention is not particularly limited, but is preferably 100 to 200 ° C. When Tg is 100 ° C. or higher, high heat resistance can be obtained. On the other hand, when Tg is 200 ° C. or lower, the fluidity is good and high molding processability can be obtained.
The polycarbonate resin composition Tg is measured by heating about 10 mg of a sample of the polycarbonate resin composition at a temperature rise rate of 20 ° C./min using a differential operation calorimeter, and measuring the calorific value in accordance with ISO 3146. , The temperature of the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepwise change part of the glass transition is maximized. The temperature was determined, and the extra glass transition temperature was defined as the glass transition temperature (Tg).

<Relative permittivity (ε _r ), dielectric loss tangent (tan δ)>
_{The polycarbonate resin composition of the present invention preferably has a relative permittivity (ε r} ) measured at a temperature of 23 ° C. and a frequency of 10 GHz, preferably 2.47 or less, more preferably 2.45 or less, and particularly preferably 2.43 or less. Further, the dielectric loss tangent (tan δ) is ^{preferably 4.00 × 10 -3} or less, more preferably 3.00 × 10 ^-3 or less, and particularly preferably ^{2.50 × 10 -3 or less.} When the relative permittivity and the dielectric loss tangent are not more than the above upper limit, the transparency of radio waves in the high frequency band becomes good.
The relative permittivity (ε _r ) and the dielectric loss tangent (tan δ) of the polycarbonate resin composition are a strip having a length of 70 mm and a width of 2 mm from a film having a thickness of 30 to 250 μm formed by using this polycarbonate resin composition. The film is cut out and adjusted for 48 hours under the conditions of room temperature of 23 ° C. and humidity of 50%, and then measured at a frequency of 10 GHz using a cavity resonator.

<Amount of residual phenol>
The amount of residual phenol in the polycarbonate resin composition of the present invention is not particularly limited, but is preferably 250 ppm or less, more preferably 230 ppm or less, still more preferably 200 ppm or less. By adjusting the amount of residual phenol to the above upper limit or less, the relative permittivity of the polycarbonate resin composition of the present invention can be lowered. The amount of residual phenol in the polycarbonate resin composition of the present invention is preferably 5 ppm or more. By adjusting the amount of residual phenol to the above lower limit or more, the amount of foreign matter in the polycarbonate resin composition of the present invention can be reduced.
The amount of residual phenol in the polycarbonate resin composition is preferably adjusted according to the pressure, temperature, and catalyst amount at the time of reaction.
The amount of residual phenol in the polycarbonate resin composition may be adjusted after the reaction is completed. For example, a commonly used single-screw or twin-screw extruder, various kneaders, and other kneading devices can be used to remove volatilization at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C. good.
As for the amount of residual phenol in the polycarbonate resin composition, 1.25 g of the polycarbonate resin composition was dissolved in 7 mL of methylene chloride, 30 mL of acetonitrile was added to the solution while stirring to reprecipitate the mixture, and the mixture was further increased to 50 mL with acetonitrile. The supernatant can be quantified by measuring the supernatant by liquid chromatography (column: reverse phase, detector: UV210 nm).

[Manufacturing method of polycarbonate resin]
The polycarbonate resin in the polycarbonate resin composition of the present invention can be produced by a conventionally known polymerization method, and the polymerization method is not particularly limited. Examples of the polymerization method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, a solid phase transesterification method of a prepolymer, and the like. Hereinafter, particularly suitable of these methods will be specifically described.

<Interfacial polymerization method>
In the interfacial polymerization method, the pH is usually kept at 9 or higher in the presence of an organic solvent and an alkaline aqueous solution inert to the reaction, the dihydroxy compound as a raw material is reacted with the carbonate-forming compound, and then in the presence of a polymerization catalyst. A polycarbonate resin is obtained by performing interfacial polymerization. If necessary, a molecular weight modifier (terminal terminator) may be present in the reaction system, or an antioxidant may be present to prevent oxidation of the raw material dihydroxy compound.

The organic solvent inert to the reaction is not particularly limited, and is, for example, chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, dichlorobenzene and the like; aromatic hydrocarbons such as benzene, toluene and xylene. Hydrogen; etc. As the organic solvent, one kind may be used, or two or more kinds may be used in any combination and ratio.

The alkaline compound contained in the alkaline aqueous solution is not particularly limited, and examples thereof include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogencarbonate, and alkaline earth metal compounds. Of these, sodium hydroxide and potassium hydroxide are preferable. As the alkaline compound, one kind may be used, or two or more kinds may be used in any combination and ratio.

Although the concentration of the alkaline compound in the alkaline aqueous solution is not limited, the alkaline compound concentration is usually used at 5 to 10% by mass in order to control the pH of the alkaline aqueous solution to 10 to 12. Further, for example, when injecting phosgene, the molar ratio of the raw material dihydroxy compound to the alkaline compound is usually 1: 1.9 in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Above, above all, it is preferably 1: 2.0 or more, and usually 1: 3.2 or less, and above all, 1: 2.5 or less is preferable.

As the carbonate-forming compound, a carbonyl halide is preferably used, and among them, phosgene is preferably used, and the method when phosgene is used is particularly called a phosgene method.

The polymerization catalyst is not particularly limited, but is, for example, an aliphatic tertiary amine such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine; N, N'-dimethylcyclohexylamine, N, N'-diethylcyclohexyl. Alicyclic tertiary amines such as amines; aromatic tertiary amines such as N, N'-dimethylaniline, N, N'-diethylaniline; trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride and the like. Tetra-ammonium salts and the like; pyridines; guanines; guanidine salts; etc. As the polymerization catalyst, one kind may be used, or two or more kinds may be used in any combination and ratio.

The molecular weight adjusting agent is not particularly limited, and examples thereof include aromatic phenols having a monovalent phenolic hydroxyl group; fatty alcohols such as methanol and butanol; mercaptans; phthalic acid imides, and the like, among which aromatic phenols are used. preferable. Specific examples of such aromatic phenols include phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, o. -T-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexyl Phenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol , Mn-nonylphenol, pn-nonylphenol, 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, tri Bromophenol, a monoalkylphenol having linear or branched alkyl groups with an average number of carbon atoms of 12 to 35 at the ortho-position, meta-position or para-position, 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl). ) Fluolene, 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl) fluorene, 4- (1-adamantyl) phenol and the like. Among these, pt-butylphenol, p-phenylphenol and p-cumylphenol are preferably used. As the molecular weight adjusting agent, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the molecular weight adjusting agent used is not particularly limited, but is, for example, usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol with respect to 100 mol of the raw material dihydroxy compound. It is less than a mole.

The antioxidant is not particularly limited, and examples thereof include a hindered phenolic antioxidant. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and 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 "-(mecitylene-2,4,6-triyl) tri-p- Cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene bis [3 -(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2-ylamino ) Phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and the like.

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. .. Examples of commercially available products of such phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by BASF, "ADEKA STAB AO-50" and "ADEKA STAB AO-60" manufactured by ADEKA.

As the antioxidant, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the antioxidant used is not particularly limited, but is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and further preferably 0.1 part by mass with respect to 100 parts by mass of the raw material dihydroxy compound. That is all. Within the above range, the effect as an antioxidant is sufficient. The amount of the antioxidant used is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, based on 100 parts by mass of the raw material dihydroxy compound. Within the above range, gas generation during injection molding can be suppressed.

The order in which the reaction substrate (reaction raw material), reaction solvent (organic solvent), catalyst, additives, etc. are mixed at the time of the reaction is arbitrary as long as the desired polycarbonate resin composition can be obtained, and an appropriate order is arbitrary. Just set it. For example, when phosgene is used as the carbonate-forming compound, the molecular weight adjusting agent can be mixed at any time from the reaction (phosgenation) between the raw material dihydroxy compound and phosgene to the start of the polymerization reaction. ..

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

<Melted transesterification method>
In the melt transesterification method, for example, a transesterification reaction between a carbonate ester and a raw material dihydroxy compound is performed.
The raw material dihydroxy compound is the same as that in the interfacial polymerization method.

The carbonate ester may be, for example, a compound represented by the following formula (13), and is a dihydroxy compound such as an aryl carbonate, a dialkyl carbonate, a biscarbonate of a dihydroxy compound, a monocarbonate of a dihydroxy compound, or a cyclic carbonate. Examples include the carbonate compound of.

In the above general formula (13), R ²⁷ and R ²⁸ each independently represent an alkyl group, an aryl group, or an arylalkyl group having 1 to 30 carbon atoms. Hereinafter, when R ²⁷ and R ²⁸ are an alkyl group or an arylalkyl group, they may be referred to as a dialkyl carbonate, and when they are an aryl group, they may be referred to as a diallyl carbonate. Among them, from the viewpoint of reactivity with the dihydroxy compound ^{, both R 27} and R ²⁸ are preferably aryl groups, and more preferably diaryl carbonate represented by the following general formula (14).

In the above general formula (14), R ²⁹ and R ³⁰ are independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and carbon. It is a cycloalkyl group having 4 to 20 atoms or an aryl group having 6 to 20 carbon atoms, and p and q each independently represent an integer of 0 to 5.

Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter, may be abbreviated as "DPC"), and 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, Examples thereof include diaryl carbonates (which may have a substituent) such as bis (2-nitrophenyl) carbonate, bis (methylsalitylphenyl) carbonate, and ditril carbonate, and diphenyl carbonate is preferable. These carbonate esters can be used alone or in admixture of two or more.

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

The ratio of the raw material dihydroxy compound to the carbonate ester is arbitrary as long as the desired polycarbonate resin composition can be obtained, but it is preferable to use these carbonate esters in excess with respect to the raw material dihydroxy compound when polymerizing with the dihydroxy compound. .. That is, the amount of the carbonate ester is preferably 1.01 times (molar ratio) or more, and more preferably 1.02 times or more with respect to the dihydroxy compound. By setting the molar ratio in the above range, the thermal stability of the obtained polycarbonate resin composition becomes good. The amount of the carbonate ester is preferably 1.30 times (molar ratio) or less, and more preferably 1.20 times or less with respect to the dihydroxy compound. By setting the molar ratio within the above range, the reactivity is improved, the productivity of the polycarbonate resin composition having a desired molecular weight is improved, and the amount of residual carbonate ester in the resin is reduced. It is suitable because it can suppress the generation of odor when it is molded or made into a molded product.

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

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

Here, the polycarbonate resin composition of the present invention is significantly affected by thermal history and oxidation in the presence of an alkaline catalyst, leading to deterioration of hue. Therefore, it is preferable to set the reaction temperature to 320 ° C. or lower, and to select a decompression condition with a lower limit of about 0.05 mmHg in order to prevent oxygen from leaking from the equipment due to excessive depressurization.

The reaction form can be either a batch method or a continuous method. In the case of a batch method, the order in which the reaction substrate, reaction solvent, catalyst, additives and the like are mixed is arbitrary as long as the desired polycarbonate resin composition can be obtained, and an appropriate order may be arbitrarily set.

In the melt transesterification method, a catalyst deactivating agent may be used if necessary. As the catalyst deactivating agent, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof, phosphorus-containing acidic compounds and derivatives thereof, and the like. As the catalyst deactivating agent, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the catalyst deactivating agent used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, and usually 50 equivalents, relative to the transesterification catalyst. Hereinafter, it is preferably 10 equivalents or less, more preferably 8 equivalents or less. The amount of the catalyst deactivating agent used is usually 1 ppm or more, 100 ppm or less, and preferably 50 ppm or less with respect to the polycarbonate resin composition.

[Manufacturing method of molded products]
In order to produce the molded product of the present invention from the polycarbonate resin composition of the present invention, a normal extrusion molding machine or an injection molding machine is used.

The molding temperature at the time of molding the polycarbonate resin composition of the present invention is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and most preferably 280 ° C. or higher. By setting the molding temperature within the above range, the fluidity is improved and the moldability is improved. The molding temperature when molding the polycarbonate resin composition of the present invention is preferably 350 ° C. or lower, particularly preferably 320 ° C. or lower. By setting the molding temperature in the above range, the color tone of the obtained molded product can be made good.

In injection molding or extrusion molding, pigments, dyes, mold release agents, heat stabilizers and the like can be appropriately added to the polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired.

<Injection molded product>
An ordinary injection molding machine is used to produce an injection molded product from the polycarbonate resin composition of the present invention.

When using an injection molding machine or the like, the mold temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and most preferably 100 ° C. or lower. By setting the mold temperature within the above range, the cooling time at the time of molding can be shortened, and the manufacturing cycle of the molded product is shortened, so that the productivity is improved. Further, when using an injection molding machine or the like, the mold temperature is preferably 30 ° C. or higher, particularly preferably 50 ° C. or higher. By setting the mold temperature within the above range, a uniform molded product can be obtained, which is preferable.

<Extruded product>
An ordinary extrusion molding machine is used to produce an extrusion molded product from the polycarbonate resin composition of the present invention. Generally, the extruder is equipped with a T-die, a round die, or the like, and extrusion-molded products having various shapes can be obtained. Examples of the extruded product include sheets, films, plates, tubes, pipes and the like. Among these, a sheet or a film is preferable.

In the extruded product of the polycarbonate resin composition of the present invention, a hard coat layer may be laminated on both sides or one side of the extruded product in order to improve adhesiveness, coatability and printability, and weather resistance and / or scratch resistance may be obtained. The property improving film may be heat-laminated on both sides or one side of the extruded product. Further, the surface may be subjected to a wrinkling process, a translucent process, an opaque process, or the like.

The polycarbonate resin composition of the present invention is excellent in heat resistance and mechanical strength, and also has a low relative permittivity and a low dielectric loss tangent. From this, it is expected to be used in a wide range of fields, and for example, it can be suitably used as a module for an in-vehicle, railway / aviation millimeter-wave radar. Further, it can be suitably used as a housing for information communication devices such as mobile phones and smartphones.

[Cover for millimeter wave radar]
The molded product of the present invention using the polycarbonate resin composition of the present invention having excellent heat resistance, mechanical strength, and molding processability, as well as a low relative permittivity and a low dielectric loss tangent, is particularly suitable as a cover for a millimeter-wave radar. Is.

The method for processing the polycarbonate resin composition of the present invention into a cover for a millimeter-wave radar is not particularly limited, but it is preferable to obtain it by injection molding because it is excellent in dimensional accuracy and mass productivity. The injection molding method is not particularly limited, and any molding method generally used for thermoplastic resins can be arbitrarily adopted. Examples include ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding such as gas assist, molding using a heat insulating mold, and molding using a rapid heating and cooling mold. Foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method and the like can be mentioned. Further, a molding method using a hot runner method can also be used.

The millimeter-wave radar module provided with the millimeter-wave radar cover of the present invention thus obtained is an automatic brake control device, an inter-vehicle distance control device, a pedestrian accident reduction steering device, an erroneous transmission suppression control device, and acceleration when a pedal is pressed incorrectly. In-vehicle millimeter-wave radar used for restraint devices, approaching vehicle warning devices, lane keeping support devices, collision prevention warning devices, parking support devices, vehicle peripheral obstacle warning devices, etc .; home monitoring / crossing obstacle detection devices, Railroad / aviation millimeter-wave radar used for in-train content transmission equipment, road train / railroad collision prevention equipment, runway foreign matter detection equipment, etc .; Millimeter-wave radar for traffic infrastructure such as intersection monitoring equipment and elevator monitoring equipment; various security It can be suitably used for millimeter-wave radars for devices; millimeter-wave radars for medical / nursing care such as watching systems for children and the elderly; millimeter-wave radars for transmitting various information contents; and the like.

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

The physical characteristics of the polycarbonate resin compositions obtained in the following Examples and Comparative Examples were evaluated by the following methods.

(1) Amount of terminal hydroxyl groups by the colorimetric determination method The amount of terminal hydroxyl groups by the colorimetric determination method was measured by the colorimetric determination method using titanium tetrachloride / acetic acid. Specifically, it was measured by the method described below. This makes it possible to measure the amount of terminal hydroxyl groups measured by the colorimetric method using titanium tetrachloride / acetic acid in this example and the comparative example.
(A) Preparation of 5v / v% acetic acid solution A 5v / v% acetic acid solution was prepared by adding 50 ml of acetic acid to a 1000 ml volumetric flask, measuring with methylene chloride and mixing.
(B) Preparation of titanium tetrachloride solution Put 90 ml of methylene chloride in a 300 ml flask with a measuring cylinder, add 10 mL of 5v / v% acetic acid solution with a measuring cylinder, add a stirrer, and stir with a magnetic stirrer to make 5 ml. A titanium tetrachloride solution was prepared by slowly adding 2.5 mL of the titanium tetrachloride solution and 2.0 mL of methanol with a measuring pipette.
(C) Preparation of calibration curve sample A methylene chloride solution was prepared so that the amount of terminal hydroxyl groups of the raw material dihydroxy compound was 10 wt ppm, and 0, 3 and 5 mL were added to 25 mL volumetric flasks, respectively. Subsequently, 5 mL each of 5 v / v% acetic acid and 10 mL each of the titanium tetrachloride solution were added. Each was mixed up with methylene chloride and mixed well.
(D) Preparation of calibration curve The absorbance of the prepared calibration sample was measured at a detection wavelength of 546 nm. The resulting absorbance was plotted against the concentration of the calibration curve sample. The reciprocal of this slope was used as a factor.
(E) Preparation of measurement sample and measurement of absorbance 0.2 g of the polycarbonate resin composition and 5 mL of methylene chloride were added to a 25 mL volumetric flask and dissolved. Next, 5 mL of a 5 v / v% acetic acid solution and 10 mL of a titanium tetrachloride solution were added, and the mixture was mixed well with methylene chloride. The absorbance of the solution thus prepared was measured at a detection wavelength of 546 nm.
(F) Calculation of the amount of terminal hydroxyl groups The amount of terminal hydroxyl groups in the polycarbonate resin composition was calculated by dividing the product of the measured absorbance and the factor by the concentration of the measurement sample.
In the polycarbonate resin composition in which the raw material dihydroxy compound has a plurality of structures, a sample in which the corresponding raw material dihydroxy compound is mixed according to the copolymerization ratio is prepared at a concentration of at least 3 levels, and from the data of 3 points or more. After drawing a calibration curve, measure the amount of terminal hydroxyl group. The detection wavelength is 546 nm.

(2) Amount of residual phenol 1.25 g of the polycarbonate resin composition is dissolved in 7 mL of methylene chloride, 30 mL of acetonitrile is added thereto while stirring to reprecipitate the composition, and the mixture is further dispensed with acetonitrile to 50 mL, and the supernatant is prepared as follows. It was quantified by measuring with liquid chromatography under the conditions.
Equipment: LC-20AD manufactured by Shimadzu Corporation
Column: SUPELCO Ascentis Express C185 5 cm x 3.0 mm, 2.7 μm
Analysis temperature: 40 ° C
Eluent composition:
Liquid A 0.1% by mass phosphoric acid aqueous solution: acetonitrile = 5: 1
Liquid B acetonitrile gradient program:
When the analysis time is 0 minutes, liquid A: liquid B = 84:16 (volume ratio, the same applies hereinafter).
During the analysis time of 0 to 18 minutes, the eluent composition was gradually changed to solution A: solution B = 0: 100.
Analysis time 18 to 25 minutes is maintained at solution A: solution B = 0: 100 Flow rate: 1.0 mL / min Detection wavelength: 210 nm

(3) Viscosity average molecular weight (Mv)
The polycarbonate resin is dissolved in methylene chloride (concentration 6.0 g / L), and the intrinsic viscosity (extreme viscosity) [η] (unit: dL / g) at 20 ° C. is determined using an Ubbelohde viscosity tube (manufactured by Moriyu Rika Kogyo Co., Ltd.). The viscosity average molecular weight (Mv) was calculated from the viscosity formula (following formula) of Schnell.
η = 1.23 × 10 ^-4 Mv ⁰ . ⁸³

(4) Glass transition temperature (Tg)
Using a differential operation calorimeter (DSC6220 manufactured by SII), about 10 mg of a sample of the polycarbonate resin composition is heated at a temperature rise rate of 20 ° C./min to measure the calorific value, and the base on the low temperature side conforms to ISO 3146. The outer glass transition start temperature, which is the temperature of the intersection of the straight line extending to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepwise change part of the glass transition is maximized, is obtained. The extra glass transition temperature was defined as the glass transition temperature (Tg).

(5) Film formability _{At the time of film forming for measuring the following relative permittivity (ε r} ) and dielectric loss tangent (tan δ), the possibility (◯) or not (×) of film forming was evaluated.

(6) Relative permittivity (ε _r ) / dielectric loss tangent (tan δ)
The polycarbonate resin composition vacuum-dried at 80 ° C. for 5 hours was formed into a film by a hot press molding machine to prepare a film having a thickness of 30 to 250 μm. The molding conditions of the hot press molding machine were appropriately adjusted in the range of a temperature of 150 to 250 ° C. and a pressure of 10 to 15 MPa. A strip-shaped film with a length of 70 mm and a width of 2 mm is cut out from this film, and after adjusting the humidity for 48 hours under the conditions of room temperature of 23 ° C. and humidity of 50%, a cavity resonator (CP-531 manufactured by Kanto Applied Electronics Co., Ltd.) _{The relative permittivity (ε r} ) and the dielectric loss tangent (tan δ) were measured at a frequency of 10 GHz using a series network analyzer (E8631A PNA manufactured by KeySight Technology Co., Ltd.).

(7) Pencil hardness A plate of a polycarbonate resin composition having a thickness of 3 mm, a length of 25 mm, and a width of 25 mm was molded into a test piece using a small injection molding machine (Shinshin Selvik C, Mobile Co., Ltd.). The pencil hardness of the test piece was measured with a load of 750 g using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with ISO 15184.

[Example 1]
A glass reactor with an internal capacity of 150 ml equipped with a reactor stirrer, a reactor heating device, and a reactor pressure regulator with a 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8 , 10-Tetraoxaspiro [5.5] Undecane (hereinafter, may be abbreviated as "SPG") (manufactured by Mitsubishi Gas Chemicals, Inc.) 39.36 g (about 0.129 mol) and 2,2-bis (4). -Hydroxy-3-methylphenyl) Propane (hereinafter sometimes abbreviated as "BPC") (manufactured by Honshu Chemical Co., Ltd.) 77.35 g (about 0.302 mol) and diphenyl carbonate (hereinafter abbreviated as "DPC") 94.65 g (about 0.442 mol) and a 4.0 mass% aqueous solution of cesium carbonate as a catalyst were added so that cesium carbonate was 25 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.

Next, the inside of the glass reactor was depressurized to about 50 Pa (0.38 Torr), and then the operation of restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. After the nitrogen substitution, the temperature outside the reactor was set to 220 ° C., the temperature inside the reactor was gradually raised, and the mixture was dissolved. Then, the stirrer was rotated at 100 rpm. Then, while distilling off the phenol by-produced by the oligomerization reaction of the dihydroxy compound and DPC performed inside the reactor, the pressure inside the reactor was increased from 101.3 kPa (760 Torr) to 13. The pressure was reduced to 3 kPa (100 Torr).

Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reactor at 13.3 kPa and further distilling off phenol. After that, the reactor external temperature was raised to 250 ° C., and the reactor internal pressure was reduced in absolute pressure from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes to remove the distilled phenol to the outside of the system. .. Further, the outside temperature of the reactor was raised to 285 ° C., the absolute pressure inside the reactor was reduced to 30 Pa (about 0.2 Torr), and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the stirrer of the reactor became a predetermined stirring power.

Next, the inside of the reactor was restored to an absolute pressure of 101.3 kPa with nitrogen, and the pressure was increased to 0.2 MPa with a gauge pressure. After obtaining, pelletized using a rotary cutter.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Example 2]
SPG (manufactured by Mitsubishi Gas Chemical Company, Inc.) 39.36 g (about 0.129 mol), BPC (manufactured by Honshu Chemical Co., Ltd.) 77.35 g (about 0.302 mol), DPC 96.03 g (about 0.448 mol), and catalyst. The method described in Example 1 was carried out except that a 4.0% by mass aqueous solution of cesium carbonate was added so that the amount of cesium carbonate was 25 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Example 3]
SPG (manufactured by Mitsubishi Gas Chemical Company, Inc.) 39.36 g (about 0.129 mol), BPC (manufactured by Honshu Chemical Co., Ltd.) 77.35 g (about 0.302 mol), DPC 90.49 g (about 0.422 mol), and catalyst. The method described in Example 1 was carried out except that a 4.0% by mass aqueous solution of cesium carbonate was added so that the amount of cesium carbonate was 25 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Example 4]
A glass reactor with an internal capacity of 150 ml equipped with a reactor stirrer, a reactor heating device, and a reactor pressure regulator, SPG (manufactured by Mitsubishi Gas Chemicals, Inc.) 39.36 g (about 0.129 mol) and BPC (Honshu Kagaku). 77.35 g (about 0.302 mol), 93.45 g (about 0.436 mol) of DPC, and a 4.0 mass% aqueous solution of cesium carbonate as a catalyst so that the amount of cesium carbonate is 100 μmol per 1 mol of the total dihydroxy compound. To prepare a raw material mixture.

Next, the inside of the glass reactor was depressurized to about 50 Pa (0.38 Torr), and then the operation of restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. After the nitrogen substitution, the temperature outside the reactor was set to 220 ° C., the temperature inside the reactor was gradually raised, and the mixture was dissolved. Then, the stirrer was rotated at 100 rpm. Then, while distilling off the phenol by-produced by the oligomerization reaction of the dihydroxy compound and DPC performed inside the reactor, the pressure inside the reactor was increased from 101.3 kPa (760 Torr) to 13. The pressure was reduced to 3 kPa (100 Torr).

Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reactor at 13.3 kPa and further distilling off phenol. After that, the reactor external temperature was raised to 250 ° C., and the reactor internal pressure was reduced in absolute pressure from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes to remove the distilled phenol to the outside of the system. .. Further, the outside temperature of the reactor was raised to 280 ° C., the absolute pressure inside the reactor was reduced to 80 Pa (about 0.6 Torr), and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the stirrer of the reactor became a predetermined stirring power.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Example 5]
SPG (manufactured by Mitsubishi Gas Chemical Company, Inc.) 63.35 g (about 0.208 mol), BPC (manufactured by Honshu Chemical Co., Ltd.) 53.36 g (about 0.208 mol), DPC 92.30 g (about 0.431 mol), and catalyst. The method described in Example 1 was carried out except that a 4.0% by mass aqueous solution of cesium carbonate was added so that the amount of cesium carbonate was 25 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Example 6]
SPG (manufactured by Mitsubishi Gas Chemical Company) 85.76 g (about 0.282 mol), BPC (manufactured by Honshu Chemical Co., Ltd.) 30.95 g (about 0.121 mol), DPC 89.24 g (about 0.417 mol), and catalyst The method described in Example 1 was carried out except that a 4.0% by mass aqueous solution of cesium carbonate was added so that the amount of cesium carbonate was 30 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Example 7]
SPG (manufactured by Mitsubishi Gas Chemical Company, Inc.) 39.36 g (about 0.129 mol) and 4,4-methylenebis (2,6-dimethylphenol) (hereinafter, may be abbreviated as "TmBPF") (Deepak Novochem Technologies Limited) 77.35 g (about 0.302 mol), 95.57 g (about 0.446 mol) of DPC, and a 4.0 mass% aqueous solution of cesium carbonate as a catalyst so that cesium carbonate is 35 μmol per 1 mol of the total dihydroxy compound. The method described in Example 1 was carried out, except that the raw material mixture was prepared by adding to.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Example 8]
SPG (manufactured by Mitsubishi Gas Chemical Company) 106.72 g (about 0.351 mol), BPC (manufactured by Honshu Chemical Co., Ltd.) 9.99 g (about 0.039 mol), DPC 85.13 g (about 0.397 mol), and catalyst The method described in Example 1 was carried out except that a 4.0% by mass aqueous solution of cesium carbonate was added so that the amount of cesium carbonate was 25 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 1.

[Comparative Example 1]
SPG (manufactured by Mitsubishi Gas Chemicals Co., Ltd.) 34.92 g (about 0.115 mol), BPC (manufactured by Honshu Chemical Co., Ltd.) 29.41 g (about 0.115 mol), and 2,2-bis (4-hydroxyphenyl) propane (about 0.115 mol). Hereinafter, it may be abbreviated as "BPA") (manufactured by Mitsubishi Chemical Corporation) 52.38 g (about 0.229 mol), DPC 101.75 g (about 0.475 mol), and cesium carbonate 4.0% by mass as a catalyst. The method described in Example 1 was carried out except that an aqueous solution was added so that cesium carbonate was 25 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 2.

[Comparative Example 2]
SPG (manufactured by Mitsubishi Gas Chemical Company) 42.44 g (about 0.139 mol), BPA (manufactured by Mitsubishi Chemical Company) 74.27 g (about 0.325 mol), DPC 96.03 g (about 0.448 mol), and catalyst. The method described in Example 1 was carried out except that a 4.0% by mass aqueous solution of cesium carbonate was added so that the amount of cesium carbonate was 20 μmol per 1 mol of the total dihydroxy compound to prepare a raw material mixture.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 2.

[Comparative Example 3]
SPG (manufactured by Mitsubishi Gas Chemical Company, Inc.) 119.77 g (about 0.393 mol), DPC 84.29 g (about 0.393 mol), 4.0% by mass aqueous solution of cesium carbonate as a catalyst, and 1 mol of all dihydroxy compounds with cesium carbonate. It was carried out by the method described in Example 1 except that the raw material mixture was prepared by adding the mixture so as to be 500 μmol per hit.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 2.

[Comparative Example 4]
BPA (manufactured by Mitsubishi Chemical Co., Ltd.) 116.71 g (about 0.511 mol), DPC 117.18 g (about 0.547 mol), and a 0.04 mass% aqueous solution of cesium carbonate as a catalyst, cesium carbonate per 1 mol of the total dihydroxy compound. It was carried out by the method described in Example 1 except that the raw material mixture was prepared by adding the mixture so as to be 0.5 μmol.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 2.

[Comparative Example 5]
BPC (manufactured by Honshu Kagaku Co., Ltd.) 100.00 g (about 0.390 mol), DPC 86.08 g (about 0.402 mol), and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst, with cesium carbonate per 1 mol of the total dihydroxy compound. It was carried out by the method described in Example 1 except that the raw material mixture was prepared by adding the mixture so as to be 4.5 μmol.
Each evaluation was carried out on the polycarbonate resin thus obtained by the above procedure. The results are shown in Table 2.

In Tables 1 and 2, the sum of the ratio of the repeating unit (C) and the ratio of the repeating unit (D) in the repeating unit (B) is "((C) + (D)) / (B) [mol%". ] ”.

[Discussion]
From the above results, the following can be understood.
Examples 1 to 8 including the repeating unit (A) and the repeating unit (C) or the repeating unit (D) as the repeating unit (B) are comparative examples not including the repeating unit (A) and the repeating unit (B). Compared with No. 4, the relative permittivity (ε _r ) and the dielectric tangent (tan δ) are lower, so that the dielectric properties are excellent. Comparative Example 5 having only the repeating unit (C) has a dielectric loss tangent (tan δ) at the same level as in Examples 1 to 8, _{but has a higher relative permittivity (ε r} ) and dielectric characteristics as compared with Examples 1 to 8. Is inferior. In Comparative Examples 1 to 3, when a film having a thickness of 30 to 250 μm was produced using a heat press forming machine and the film was cut into strips having a length of 70 mm and a width of 2 mm, the film was brittle and difficult to cut. The relative permittivity (ε _r ) and the dielectric loss tangent (tan δ) could not be measured. That is, Comparative Examples 1 and 2 in which "((C) + (D)) / (B) [mol%]" do not satisfy the provisions of the present invention, and Comparative Example 3 in which only the repeating unit (A) is used are in Example 1. Compared with -8, the mechanical strength and moldability are inferior.
Further, Examples 1 to 8 are superior in pencil hardness to Comparative Examples 1, 2 and 4.

From the above, the polycarbonate resin of Examples 1 to 8 which is the polycarbonate resin composition of the present invention is superior in mechanical strength and molding processability as compared with the polycarbonate resin of Comparative Examples 1 to 5, and has a low relative permittivity (ε). _Since it has both r) and a low dielectric loss tangent (tan δ), it can be seen that the dielectric properties are excellent.

Claims (17)

A polycarbonate resin composition containing a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), wherein the repeating unit (B) A polycarbonate resin composition in which the sum of the ratio of the repeating unit (C) represented by the following formula (3) and the ratio of the repeating unit (D) represented by the following formula (4) is 40 mol% or more.

[In the formula (1), W ¹ is an organic group containing a cyclic structure and may contain a hetero atom. R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, may contain a hetero atom, or may be bonded to ^{W 1 to form a ring.}
In the formula (2), R ^{5 to} R ⁸ are independent groups having a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group having 6 to 12 carbon atoms including an aryl group, and W ² is a group. , A single bond, an oxygen atom, a sulfur atom, and at least one selected from a divalent organic group.
In formula (3), R ⁹ and R ¹⁰ are independently hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or groups having 6 to 12 carbon atoms including an aryl group, and R ¹¹ and R are R 11 and R, respectively. ^{Reference numeral 12} is an alkyl group having 1 to 10 carbon atoms independently, or a group having 6 to 12 carbon atoms including an aryl group.
In the formula (4), R ^{13 to} R ¹⁶ are independent alkyl groups having 1 to 10 carbon atoms or groups having 6 to 12 carbon atoms including an aryl group. ] The polycarbonate resin composition according to claim 1, wherein the amount of terminal hydroxyl groups measured by a colorimetric quantitative method using a titanium tetrachloride / acetic acid method is 100 to 2,500 ppm. The polycarbonate resin composition according to claim 1 or 2, wherein the amount of residual phenol is 250 ppm or less. The polycarbonate resin composition according to any one of claims 1 to 3, ^{wherein W 1} in the formula (1) is selected from the following formula (5) or (6).

[In formula (6), R ¹⁷ and R ¹⁸ each independently have a hydrogen atom, a group containing a hetero atom, a group containing a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom containing an aryl group. Represents a group of 6-12. ] The polycarbonate resin composition according to any one of claims 1 to 4, ^{wherein R 9} and R ¹⁰ in the formula (3) are independently hydrogen atoms or methyl groups, respectively. The polycarbonate resin composition according to any one of claims 1 to 5, ^{wherein R 13 to} R ¹⁶ in the formula (4) are methyl groups. The polycarbonate resin composition according to any one of claims 1 to 6, ^{wherein R 9} and R ¹⁰ in the formula (3) are methyl groups. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the repeating unit (A) is a repeating unit represented by the following formula (7) or (8).

^{The polycarbonate resin composition according to any one of claims 1 to 8, wherein W 2} in the formula (2) is selected from a single bond, a methylene group, an ethylidene group, and an isopropylidene group. Claim 1 is characterized in that the ratio of the sum of the repeating unit (C) and the repeating unit (D) contained in the repeating unit (B) is 80 mol% or more with respect to all the repeating units (B). The polycarbonate resin composition according to any one of 9 to 9. The polycarbonate resin composition according to any one of claims 1 to 10, wherein the amount of terminal hydroxyl groups measured by a colorimetric method using titanium tetrachloride / acetic acid is 130 to 1,000 ppm. The polycarbonate resin composition according to any one of claims 1 to 11, wherein the ratio of the repeating unit (A) to the repeating unit (B) is 1:99 to 90:10. The polycarbonate resin composition according to any one of claims 1 to 12, wherein the polycarbonate resin has a viscosity average molecular weight (Mv) in the range of 16,000 to 32,000. A molded product obtained by using the polycarbonate resin composition according to any one of claims 1 to 13. An injection-molded article obtained by using the polycarbonate resin composition according to any one of claims 1 to 13. An extruded product obtained by using the polycarbonate resin composition according to any one of claims 1 to 13. A cover for a millimeter wave radar obtained by using the polycarbonate resin composition according to any one of claims 1 to 13.