JP6839617B2 - Aromatic polycarbonate resin composition - Google Patents

Description

The present invention relates to an aromatic polycarbonate resin composition, and more particularly to an aromatic polycarbonate resin composition having an excellent balance of flame retardancy, fluidity, heat resistance and impact resistance.

Aromatic polycarbonate resins are resins with excellent heat resistance, mechanical properties, and electrical properties, and are widely used, for example, in automobile materials, electrical and electronic equipment materials, housing materials, and materials for manufacturing parts in other industrial fields. There is. In particular, the flame-retardant polycarbonate resin composition is suitably used as a member of information / mobile devices such as computers, notebook personal computers, tablet terminals, smartphones and mobile phones, and OA devices such as printers and copiers. ing.

However, when a flame retardant is added to the polycarbonate resin, the impact resistance is lowered. ABS resin is blended in order to improve impact resistance (for example, Patent Document 1), but when ABS resin is contained, the resin composition has a problem that flame retardancy and fluidity are deteriorated. ..

Special Fair 7-98892

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin composition having an excellent balance of flame retardancy, fluidity, heat resistance and impact resistance.

As a result of diligent studies to achieve the above problems, the present inventor has made the aromatic polycarbonate resin flame retardant and fluid by containing a phosphorus-based flame retardant (B) and a specific polycarbonate resin. We have found that a polycarbonate resin composition having an excellent balance of properties, heat resistance and impact resistance can be obtained, and have completed the present invention.
The present invention relates to the following aromatic polycarbonate resin compositions.

[1] A resin composition containing 1 to 50 parts by mass of a phosphorus-based flame retardant (B) with respect to 100 parts by mass of the aromatic polycarbonate resin (A), which constitutes the aromatic polycarbonate resin (A). An aromatic polycarbonate resin composition containing 1 to 15 mol% of a carbonate structural unit derived from the dihydroxy compound (i) represented by the following formula (1) in 100 mol% of the carbonate structure.
[In the formula (1), W ¹ represents any one of a single bond, an oxygen atom, a sulfur atom, and a divalent organic group represented by the formula (2). In formula (2), X ¹ represents an oxygen atom or NR ⁷ , X ^{2 represents a divalent hydrocarbon group having 3} to 18 carbon atoms, X 3 represents an alkylene group having 1 to 7 carbon atoms, and m represents an alkylene group having 1 to 7 carbon atoms. Represents an integer from 1 to 500. Further, in the formulas (1) and (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 24, respectively. Representing a monovalent hydrocarbon group ^{, at least one of R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is an alkyl group having 7 to 24 carbon atoms. ]

[2] The aromatic polycarbonate resin (A) is represented by the following formula (4) and the aromatic polycarbonate resin (a1) containing a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1). The aromatic polycarbonate resin composition according to the above [1], which comprises an aromatic polycarbonate resin (a2) composed of a carbonate structural unit derived from the dihydroxy compound (ii).
[In the formula (4), W ² represents any one of a single bond, an oxygen atom, a sulfur atom, and a divalent organic group represented by the formula (5). In formula (5), X ⁴ represents a divalent hydrocarbon group having 3 to 18 carbon atoms, X ⁵ represents an oxygen atom or NR ¹⁴ , X ⁶ represents an alkylene group having 1 to 7 carbon atoms, and n represents an alkylene group having 1 to 7 carbon atoms. Represents an integer from 1 to 500. Further, in the formulas (4) and (5), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 6, respectively. Represents a monovalent hydrocarbon group. ]

[3] The aromatic polycarbonate resin (a1) is derived from a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) and the dihydroxy compound (ii) represented by the above formula (4). The aromatic polycarbonate resin composition according to the above [2], which comprises a carbonate structural unit.
[4] In 100 mol% of the total carbonate structure constituting the aromatic polycarbonate resin (a1), 2.5 to 36.5 mol% of the carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) is contained. The aromatic polycarbonate resin composition according to the above [3].
[5] The above-mentioned characteristic that the aromatic polycarbonate resin (A) contains the aromatic polycarbonate resin (a1) and the aromatic polycarbonate resin (a2) in a mass ratio of 55/45 to 4/96. The aromatic polycarbonate resin composition according to any one of [2] to [4].

[6] The aromatic polycarbonate resin composition according to any one of the above [1] to [5], wherein the dihydroxy compound (i) is represented by the following formula (7).
[In formula (7), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a halogen atom, and a monovalent hydrocarbon group having 1 to 24 carbon atoms, and R ¹⁵ has 7 carbon atoms. Represents ~ 24 alkyl groups. ]
[7] The aromatic polycarbonate resin composition according to the above [6], wherein the dihydroxy compound (i) is a compound of the following formula (9).

[8] The above-mentioned [2] to [7], wherein the aromatic polycarbonate resin (a2) is composed of a carbonate structural unit derived from 2,2-bis (4-hydroxyphenyl) propane. Aromatic polycarbonate resin composition.
[9] The polycarbonate resin according to any one of the above [1] to [8], wherein the phosphorus-based flame retardant (B) is at least one selected from a condensed phosphoric acid ester compound or a phosphazene compound. Composition.

The aromatic polycarbonate resin composition of the present invention has an excellent balance of flame retardancy, fluidity, heat resistance and impact resistance. Therefore, it can be suitably used for housings of electric / electronic devices and automobile parts, particularly housings of various mobile terminals, electronic devices, and image display devices.

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not construed as being 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. Further, "part" means a mass part based on a mass standard unless otherwise specified.

[Aromatic Polycarbonate Resin (A)]
The aromatic polycarbonate resin (A) used in the aromatic polycarbonate resin composition of the present invention contains a carbonate structural unit derived from the dihydroxy compound (i) represented by the following formula (1). By including the carbonate structural unit derived from the dihydroxy compound (i) represented by the following formula (1) in this way, the fluidity is improved without impairing the impact resistance of the aromatic polycarbonate resin composition of the present invention. It becomes possible to make it. The fluidity is improved by including the polycarbonate unit derived from the dihydroxy compound (i) of the formula (1). Therefore, for example, when the fluidity is the same as that of the polycarbonate resin derived from bisphenol A, the molecular weight is increased. Therefore, it is possible to improve the impact resistance. Further, by containing the polycarbonate derived from the dihydroxy compound (i) of the formula (1), transparency and total light transmittance can be expected to be improved.

In the formula (1), W ¹ represents any one of a single bond, an oxygen atom, a sulfur atom, and a divalent organic group represented by the following formula (2).
In formula (2), X ¹ represents an oxygen atom or NR ⁷ . R ⁷ is as described later.

X ² represents a divalent hydrocarbon group having 3 to 18 carbon atoms.
Examples of the divalent hydrocarbon group having 3 to 18 carbon atoms include a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group and the like. It may 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.

A preferable example of such a ^{divalent organic group of the formula (2) having X 2} is an organic group of the following formula (3).

X ³ represents an alkylene group having 1 to 7 carbon atoms.
The alkylene group having 1 to 7 carbon atoms may be a straight chain or a branched chain, and may have a cyclic structure. Examples of such an alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group and a cyclobutylene group. , 1-Methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1 , 1-Dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, cyclopentylene group, 1-methyl- Cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2- Ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1 -Dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group Group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2- Trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl- Cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1, 3-Dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1- n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2, 3-trimethyl-cyclopropylene group, 2,2,3-tri Methyl-cyclopropylene group, 1-ethyl-2-methyl-cyclopropylene group, 2-ethyl-1-methyl-cyclopropylene group, 2-ethyl-2-methyl-cyclopropylene group and 2-ethyl-3-methyl- Cyclopropylene group, n-heptylene group and the like can be mentioned, but among them, an alkylene group having 1 to 3 carbon atoms is preferable.

Further, m represents an integer of 1 to 500, and among them, 5 to 300 is preferable, and 10 to 100 is more preferable.

R ¹ , R ² , R ³ and R ⁴ in formula (1) and R ⁵ , R ⁶ and R ⁷ in formula (2) are independently hydrogen atoms, halogen atoms and carbon atoms 1 to 24, respectively. Representing a monovalent hydrocarbon group ^{, at least one of R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is an alkyl group having 7 to 24 carbon atoms.
The monovalent hydrocarbon group having 1 to 24 carbon atoms includes an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, and an aryl group having 6 to 24 carbon atoms. , Arylalkyl groups having 7 to 24 carbon atoms and the like.

Examples of the alkyl group having 1 to 24 carbon atoms include linear and branched alkyl groups and alkyl groups having a partially cyclic structure. Among them, the fluidity of the aromatic polycarbonate resin composition of the present invention can be determined. It is preferably a linear or branched alkyl group because it can be enhanced more effectively.
Specific examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-. Nonyl group, n-decyl, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl, n-octadecyl group, n-nonadecil group. , N-Icosyl group, n-Henikosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group and the like.

Specific examples of the branched alkyl group include methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, and methyl. Tridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl, methyloctadecyl group, methylnonadecil group, methylicosyl group, methylicosyl group, methylhenicosyl group, methyldocosyl group, methyltricosyl group,
Dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl Group, dimethylhexadecyl group, dimethylheptadecyl, dimethyloctadecyl group, dimethylnonadesyl group, dimethylicosyl group, dimethylicosyl group, dimethylhenicosyl group, dimethyldocosyl group,
Trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group, Trimethyloctadecyl group, trimethylnonadesyl group, trimethylicosyl group, trimethylicosyl group, trimethylhenicosyl group,
Ethylpropyl group, ethylbutyl group, ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group Group, ethyl hexadecyl group, ethyl heptadecyl, ethyl octadecyl group, ethyl nonadecyl group, ethyl icosyl group, ethyl icosyl group, ethyl hen icosyl group, ethyl docosyl group,

Propylbutyl group, propylpentyl group, propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group. Group, propyl hexadecyl group, propyl heptadecyl group, propyl octadecyl group, propyl nonadesyl group, propyl icosyl group, propyl icosyl group, propyl hen icosyl group,
Butylpentyl group, butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group. Examples thereof include a group, a butyl heptadecyl, a butyl octadecyl group, a butyl nonadecyl group, a butyl icosyl group, and a butyl icosyl group. In the above example of the branched alkyl group, the branching position is arbitrary.
Specific examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

The alkenyl group having 2 to 24 carbon atoms is not particularly limited as long as it has a structure having one or more carbon-carbon double bonds in the structure of the linear alkyl group and the branched alkyl group. As specific examples, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group. , Heptadecenyl group, octadecenyl group, nonadesenyl group, icosenyl group, henicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, 4,8,12-trimethyltridecyl group.

Examples of the alkoxy group having 1 to 24 carbon atoms include a linear, branched, and partially cyclic alkoxy group, and among them, a linear alkoxy group is preferable. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, and a tridecyloxy group. Examples include groups, tetradecyloxy groups, phenoxy groups and the like.
Examples of the aryl group having 6 to 24 carbon atoms include a phenyl group, a naphthyl group, a methylphenyl group, a dimethylphenyl group and a trimethylphenyl group, and examples of the arylalkyl group having 7 to 24 carbon atoms include a benzyl group and the like. Can be mentioned.

R ¹ , R ² , R ³ and R ^{4 in} the formula (1), and R ⁵ , R ⁶ and R ⁷ in the formula (2) are independently hydrogen atom, halogen atom and carbon, respectively, as described above. Representing a monovalent hydrocarbon group of numbers 1 to 24 ^{, at least one of R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is an alkyl group having 7 to 24 carbon atoms. Is.
By having an alkyl group having 7 to 24 carbon atoms in this way, the entanglement of the polymer chains of the aromatic polycarbonate resin is appropriately inhibited, the friction of the polymer chains is reduced, and high fluidity is also exhibited. At the same time, the effect of improving the fluidity of the aromatic polycarbonate resin composition of the present invention can be obtained. Further, when compared with the same melt viscosity, it is possible to improve the impact resistance as compared with the aromatic polycarbonate resin having no alkyl group having 7 to 24 carbon atoms.
When the number of carbon atoms is less than 7, the above-mentioned effect of improving fluidity and impact resistance cannot be sufficiently obtained, while when the number of carbon atoms exceeds 24, the heat resistance is extremely lowered, and further. Is not preferable because the impact resistance is also lowered. ^{From this point of view, in the aromatic polycarbonate resin composition of the present invention, R 1} , R ² , R ³ , R ⁴ , R in the dihydroxy compound (i) forming the structural unit represented by the above formula (1). ⁵ , At ^{least one of R 6} and R ⁷ preferably has an alkyl group having 8 to 20 carbon atoms, more preferably having an alkyl group having 9 to 15 carbon atoms, and having 9 to 11 carbon atoms. It is particularly preferred to have an alkyl group.

Specific examples of such an alkyl group having 7 to 24 carbon atoms include a linear or branched alkyl group and an alkyl group having a partially cyclic structure. Among them, the aromatic group of the present invention. A linear or branched alkyl group is preferable because the fluidity of the polycarbonate resin composition can be enhanced more effectively.

Specific examples of the linear alkyl group include n-heptyl group, n-octyl group, n-nonyl group, n-decyl, n-undecylic group, n-dodecyl group, n-tridecylic group and n-tetradecyl group. , N-pentadecylic group, n-hexadecyl group, n-heptadecyl, n-octadecyl group, n-nonadecil group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tridecylic group, n-tetracosyl group, etc. Can be mentioned.

Specific examples of the branched alkyl group include methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group and methyl. Hexadecyl group, methylheptadecyl, methyloctadecyl group, methylnonadecil group, methylicosyl group, methylicosyl group, methylhenicosyl group, methyldocosyl group, methyltricosyl group,
Dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethyl Heptadecyl, dimethyloctadecyl group, dimethylnonadecil group, dimethylicosyl group, dimethylicosyl group, dimethylhenicosyl group, dimethyldocosyl group,
Trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group, Trimethyloctadecyl group, trimethylnonadesyl group, trimethylicosyl group, trimethylicosyl group, trimethylhenicosyl group,
Ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl, Ethyloctadecyl group, ethylnonadecil group, ethylicosyl group, ethylicosyl group, ethylhenicosyl group, ethyldocosyl group,
Propylpentyl group, propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexa Decyl group, propylheptadecyl group, propyloctadecyl group, propylnonadecil group, propylicosyl group, propylicosyl group, propylhenicosyl group,
Butylpentyl group, butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group. Examples thereof include a group, a butyl heptadecyl, a butyl octadecyl group, a butyl nonadecyl group, a butyl icosyl group, and a butyl icosyl group.
In the above example of the branched alkyl group, the branching position is arbitrary.

Alkyl groups having 7 to 24 carbon atoms include n-heptyl group, n-octyl group, ethylhexyl group, n-nonyl group, n-decyl, n-undecylic group, n-dodecyl group and n-tridecyl group. , N-tetradecyl group, n-pentadecyl group are preferable, n-octyl group, ethylhexyl group, n-nonyl group, n-decyl, n-undecylic group, n-dodecyl group are more preferable, n-nonyl group, n- A decyl or n-undecyl group is particularly preferable. By having such an alkyl group, the fluidity and mechanical strength of the aromatic polycarbonate resin composition of the present invention can be more effectively enhanced.

Further, the dihydroxy compound (i) forming the structural unit represented by the above formula (1) may have only one type or a plurality of types, but it is preferably two types and only one type. This is more preferable because the aromatic polycarbonate resin composition of the present invention tends to have a good balance of fluidity, impact resistance, and heat resistance.

In the aromatic polycarbonate resin composition of the present invention, the aromatic polycarbonate resin (A) contains a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) in 100 mol% of the total carbonate structure. , 1 to 15 mol%. When the carbonate structural unit derived from the dihydroxy compound (i) is less than the above lower limit value, the effect of improving the fluidity of the aromatic polycarbonate resin composition of the present invention cannot be sufficiently obtained, and the appearance is also insufficient. Therefore, it is not preferable. On the other hand, when the carbonate structural unit derived from the dihydroxy compound (i) exceeds the above upper limit value, the impact resistance and heat resistance of the aromatic polycarbonate resin composition of the present invention are also lowered, which is also not preferable.

From this point of view, the carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) is preferably 1.5 mol% or more, more preferably 2.5 mol% or more. It is more preferably 3 mol% or more, particularly preferably 3.5 mol% or more, and most preferably 4 mol% or more. Further, it is preferably 13 mol% or less, more preferably 12 mol% or less, further 11 mol% or less, particularly 10 mol% or less, particularly 9 mol% or less, and most preferably 7.5 mol% or less.

The aromatic polycarbonate (A) contained in the aromatic polycarbonate resin composition of the present invention contains a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) within the above range. For example, it may be a copolymer or a mixture.

When the aromatic polycarbonate (A) is a copolymer, a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) and a carbonate derived from a dihydroxy compound other than the dihydroxy compound (i). Has a structural unit. The dihydroxy compound other than the dihydroxy compound (i) is not particularly limited, but is preferably the dihydroxy compound (ii) represented by the following formula (4).

In the formula (4), W ² represents any one of a single bond, an oxygen atom, a sulfur atom, and a divalent organic group represented by the following formula (5).

In formula (5), X ⁴ represents an oxygen atom or NR ¹⁴ , X ⁵ represents a divalent hydrocarbon group having 3 to 18 carbon atoms, X ⁶ represents an alkylene group having 1 to 7 carbon atoms, and n represents an alkylene group having 1 to 7 carbon atoms. Represents an integer from 1 to 500. Further, in the formulas (4) and (5), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 6, respectively. Represents a monovalent hydrocarbon group.

The divalent hydrocarbon group having 3 to 18 carbon atoms of ^{X 5 is the same as that exemplified as the divalent hydrocarbon group having 3 to 18 carbon atoms of X 2 in} the above formula (2), and is the same as that exemplified as the divalent hydrocarbon group having 3 to 18 carbon atoms of X ⁶ . alkylene group having 1 to 7 carbon atoms are the same as those exemplified as the alkylene group having 1 to 7 carbon atoms X ³ in the formula (2). Further, n represents an integer of 1 to 500, and among them, 5 to 300 is preferable, and 10 to 100 is more preferable.

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in formula (4) and R ¹² , R ¹³ and R ¹⁴ in formula (5) are independently hydrogen atoms, halogen atoms, and carbon atoms 1 to 6. Represents a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group.

Examples of the alkyl group having 1 to 6 carbon atoms include linear and branched alkyl groups and alkyl groups having a partially cyclic structure. Among them, the fluidity of the aromatic polycarbonate resin composition of the present invention can be determined. It is preferably a linear or branched alkyl group because it can be enhanced more effectively.
Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group and the like.
Specific examples of the branched alkyl group include a methylpropyl group, a methylbutyl group, a methylpentyl group, a dimethylbutyl group, an ethylpropyl group, an ethylbutyl group and the like. In the above example of the branched alkyl group, the branching position is arbitrary. Specific examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

The alkenyl group having 2 to 6 carbon atoms is not particularly limited as long as it has a structure having one or more carbon-carbon double bonds in the structure of the linear alkyl group and the branched alkyl group. Specific examples thereof include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.
Examples of the alkoxy group having 1 to 6 carbon atoms include a linear, branched, and partially cyclic alkoxy group, and among them, a linear alkoxy group is preferable. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexyloxy group.

In the aromatic polycarbonate resin composition of the present invention, the aromatic polycarbonate (A) has a carbonate structure derived from the aromatic polycarbonate resin (a1) and the dihydroxy compound (i) containing a carbonate structural unit derived from the dihydroxy compound (i). It is also preferable that it is a mixture with an aromatic polycarbonate resin containing no unit. As described above, the aromatic polycarbonate resin (a1) containing the carbonate structural unit derived from the dihydroxy compound (i) and the like, as opposed to the existing aromatic polycarbonate resin not containing the carbonate structural unit derived from the dihydroxy compound (i). By appropriately mixing desired additives, materials corresponding to various compounding designs can be industrially and efficiently produced, and the fluidity, impact resistance, and heat resistance of the aromatic polycarbonate resin composition of the present invention can be obtained. It becomes easy to adjust the balance.

Among the aromatic polycarbonate resins containing no carbonate structural unit derived from the dihydroxy compound (i) contained in the above-mentioned aromatic polycarbonate resin (A), the dihydroxy compound (ii) represented by the above formula (4) It is preferably an aromatic polycarbonate resin (a2) composed of a carbonate structural unit derived from.
Further, the aromatic polycarbonate resin (a1) containing the carbonate structural unit derived from the dihydroxy compound (i) described above contains a carbonate structural unit derived from the dihydroxy compound (i) and a carbonate structural unit derived from the dihydroxy compound (ii). It is also preferable to include it, and more preferably, it is a copolymer composed of a carbonate structural unit derived from the dihydroxy compound (i) and a carbonate structural unit derived from the dihydroxy compound (ii). By including the carbonate structural unit derived from the dihydroxy compound (i) and the carbonate structural unit derived from the dihydroxy compound (ii) in this way, the aromatic polycarbonate resin (a1) and the aromatic polycarbonate resin (a2) of the present invention can be used. The compatibility tends to be improved, and the fluidity, heat resistance, and impact resistance of the aromatic polycarbonate resin composition of the present invention tend to be improved.

The dihydroxy compound (i) represented by the above formula (1) in 100 mol% of the total carbonate structure constituting the aromatic polycarbonate resin (a1) in the aromatic polycarbonate resin (A) in the aromatic polycarbonate resin composition of the present invention. The ratio of the carbonate structural unit derived from the above can be appropriately selected within a range that does not impair the characteristics of the aromatic polycarbonate resin composition of the present invention, but is usually 1 mol% or more, preferably 2.5 mol% or more, more. It is preferably 4 mol% or more, more preferably 8 mol% or more, particularly preferably 16 mol% or more, and most preferably 20 mol% or more. Further, it is usually 49 mol% or less, preferably 36.5 mol% or less, more preferably 36 mol% or less, still more preferably 34 mol% or less, particularly preferably 33 mol% or less, and most preferably 32 mol% or less. Within such a range, the fluidity and impact resistance of the aromatic polycarbonate resin composition of the present invention become excellent.

When the aromatic polycarbonate resin (A) contains the aromatic polycarbonate resin (a1) and the aromatic polycarbonate resin (a2) in the aromatic polycarbonate resin composition of the present invention, the blending ratio thereof is the aromatic of the present invention. There is no particular limitation as long as the characteristics of the polycarbonate resin composition are not impaired, but the mass ratio of the aromatic polycarbonate resin (a1) and the aromatic polycarbonate resin (a2) is usually 99/1 to 1/99, preferably 99/1 to 1/99. 90/10 to 2/98, more preferably 70/30 to 3/97, still more preferably 55/45 to 4/96, particularly preferably 50/50 to 5/95, most preferably 30/70 to 5/ It is 95. Within such a range, the fluidity and impact resistance of the aromatic polycarbonate resin composition of the present invention will be excellent.

As a specific example of the dihydroxy compound (i), the compounds represented by the following formulas (6) to (7) are more preferable, and the compound represented by (7) is further preferable.
Wherein ^{(6), R 1, R} 2, R 3, R 4 has the same meaning as ^{R 1, R 2, R 3} , R 4 in the formula ^{(1), R 5, R} 6 has the formula ( 2) in the same meaning as ^R 5, ^{R 6 of, R 1, R 2, R} 3, R 4, R 5, of ^{R 6,} at least one is an alkyl group having 7 to 24 carbon atoms ..
Wherein ^{(7), R 1, R} 2, R 3, R 4 has the same meaning as ^{R 1, R 2, R 3} , R 4 in the formula ^{(1), R 15} is a carbon number 7 to 24 Represents the alkyl group of.

Specific examples of the alkyl groups having 7 to 24 carbon atoms ^{of R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ^{15 in} the formulas (6) to (7) are linear. Examples thereof include branched alkyl groups and alkyl groups having a partially cyclic structure. Among them, linear and branched alkyls are used because the fluidity of the aromatic polycarbonate resin composition of the present invention can be more effectively enhanced. It is preferably a group.

Specific examples of the linear alkyl group include n-heptyl group, n-octyl group, n-nonyl group, n-decyl, n-undecylic group, n-dodecyl group, n-tridecylic group and n-tetradecyl group. , N-pentadecylic group, n-hexadecyl group, n-heptadecyl, n-octadecyl group, n-nonadecil group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tridecylic group, n-tetracosyl group, etc. Can be mentioned.

Specific examples of the branched alkyl group include methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group and methyl. Hexadecyl group, methylheptadecyl, methyloctadecyl group, methylnonadecil group, methylicosyl group, methylicosyl group, methylhenicosyl group, methyldocosyl group, methyltricosyl group,
Dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethyl Heptadecyl, dimethyloctadecyl group, dimethylnonadecil group, dimethylicosyl group, dimethylicosyl group, dimethylhenicosyl group, dimethyldocosyl group,
Trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group, Trimethyloctadecyl group, trimethylnonadesyl group, trimethylicosyl group, trimethylicosyl group, trimethylhenicosyl group,
Ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl, Ethyloctadecyl group, ethylnonadecil group, ethylicosyl group, ethylicosyl group, ethylhenicosyl group, ethyldocosyl group,
Propylpentyl group, propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexa Decyl group, propylheptadecyl group, propyloctadecyl group, propylnonadecil group, propylicosyl group, propylicosyl group, propylhenicosyl group,
Butylpentyl group, butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group. Examples thereof include a group, a butyl heptadecyl, a butyl octadecyl group, a butyl nonadecyl group, a butyl icosyl group, and a butyl icosyl group. In the above example of the branched alkyl group, the branching position is arbitrary.

Alkyl groups having 7 to 24 carbon atoms include n-heptyl group, n-octyl group, ethylhexyl group, n-nonyl group, n-decyl, n-undecylic group, n-dodecyl group and n-tridecyl group. , N-tetradecyl group, n-pentadecyl group are preferable, n-octyl group, ethylhexyl group, n-nonyl group, n-decyl, n-undecylic group, n-dodecyl group are more preferable, n-nonyl group, n- A decyl or n-undecyl group is particularly preferable. By having such an alkyl group, the fluidity and mechanical strength of the aromatic polycarbonate resin composition of the present invention can be more effectively enhanced.

Specific examples of such formulas (6) and (7) include compounds (6) -1 to (6) -18 exemplified in Table 1 below and compounds (7) -1 exemplified in Table 2 below. ~ (7) -18 can be mentioned.

As the dihydroxy compound (i), compounds (6) -1 to (6) -15 and (7) -1 to (7) -11 are more preferable, and compounds (6) -3 to (6) -5 are more preferable. , And (7) -1 to (7) -6 are more preferable, and the compound represented by the following formulas (8) and (9) is particularly preferable, and the compound (9) is most preferable. By selecting such a dihydroxy compound (i), not only the fluidity and impact resistance of the aromatic polycarbonate resin assembly of the present invention are excellent, but also the thermal stability and heat resistance are excellent.

Examples of the dihydroxy compound (ii) represented by the formula (4) include, for example.
2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1-bis (4-hydroxyphenyl) ethane,
2-Bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1-bis (4-hydroxyphenyl) butane,
2-Bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
4,4-Bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
1,4-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (hydroxyaryl) arylalkyls such as;
Cardo-structure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;
Dihydroxydiarylsulfides such as 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide;
Dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;
Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; and the like.

The other dihydroxy compounds described above are not particularly limited, and heteroatoms and heterobonds such as N (nitrogen), S (sulfur), P (phosphorus), and Si (silicon) are introduced in order to impart various properties. It may be a obtained dihydroxy compound. As a dihydroxy compound into which such a hetero atom or a hetero bond is introduced,
3,3-bis (4-hydroxyphenyl) phthalide (phenolphthalein),
2-Methyl-3,3'-bis (4-hydroxyphenyl) phthalimidine,
2-Phenyl-3,3'-bis (4-hydroxyphenyl) phthalimidine,
Examples thereof include bisphenol compounds having a dimethylsiloxane skeleton.
As the dihydroxy compound (ii), one type may be used, or two or more types may be used in combination in any combination and ratio.

In the present invention, the dihydroxy compound (ii) represented by the above formula (4) is preferably 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A). By selecting such a dihydroxy compound (ii), the thermal stability and impact resistance of the aromatic polycarbonate resin composition of the present invention tend to be good.

In the polycarbonate resin composition of the present invention, the aromatic polycarbonate resin (A) is represented by i) the aromatic polycarbonate resin (a1), the polycarbonate structural unit represented by the following formula (10), and the following formula (11). It is particularly preferable that the copolymerized polycarbonate resin composed of the polycarbonate structural unit to be used is a blend of ii) the polycarbonate resin composed of the polycarbonate structural unit represented by the formula (11) as the aromatic polycarbonate resin (a2). ..

Wherein ^(10), R ^1, R ^2, R 3, ^{R 4} and ^{R 15} is the same as defined in the ^{R 1,} R ^{2, R 3} in the formula ^{(7), R 4, R} 15.

The preferred structural units of the above formula (10) as R ¹ , R ² , R ³ , R ⁴ and R ¹⁵ are as described above. The polycarbonate unit of the above formula (10) is preferably a polycarbonate structural unit derived from 1,1-bis (4-hydroxylphenyl) dodecane, and the polycarbonate unit of the above formula (11) is preferably derived from bisphenol A. It is a polycarbonate structural unit.

The ratio of the polycarbonate structural unit of the formula (10) in the copolymerized polycarbonate resin composed of the polycarbonate structural unit of the formula (10) and the polycarbonate structural unit of the formula (11) is usually 1 mol% or more in 100 mol% of the copolymerized polycarbonate resin. It is preferably 2.5 mol% or more, more preferably 4 mol% or more, further preferably 8 mol% or more, particularly preferably 16 mol% or more, and most preferably 20 mol% or more. Further, it is usually 49 mol% or less, preferably 36.5 mol% or less, more preferably 36 mol% or less, still more preferably 34 mol% or less, particularly preferably 33 mol% or less, and most preferably 32 mol% or less.

The mixing ratio of the copolymerized polycarbonate resin composed of the polycarbonate structural units of the formulas (10) and (11) and the polycarbonate resin of the formula (11) is the mass ratio of the former and the latter, and is usually 99/1 to 1/99. Yes, preferably 90/10 to 2/98, more preferably 70/30 to 3/97, still more preferably 55/45 to 4/96, particularly preferably 50/50 to 5/95, most preferably 30/ It is 70 to 5/95.

In the polycarbonate resin composition of the present invention, the proportion of the carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) in 100 mol% of the total carbonate structure constituting the aromatic polycarbonate resin (A). And the ratio of the carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (1) in 100 mol% of the total carbonate structure constituting the aromatic polycarbonate resin (a1) can be easily determined by NMR. it can. When the aromatic polycarbonate resin (a1) and (a2) are used in combination, the ratio of the carbonate structural units derived from the dihydroxy compound (i) can be determined by NMR in the same manner as described above. Further, it may be calculated by a weighted average in consideration of the molecular weight and the mixing ratio of the carbonate structural unit derived from the dihydroxy compound (i) in each of the used polycarbonate resins.
The measurement conditions are not particularly limited, but deuterated chloroform is usually preferably used as the deuterated solvent, but deuterated acetone, deuterated dimethyl sulfoxide, deuterated dichloromethane, etc. are used according to the characteristics of the aromatic polycarbonate resin. The heavy solvent can be appropriately selected. When the polycarbonate resin composition of the present invention is difficult to dissolve in a heavy solvent, the dihydroxy compound (i) obtained by hydrolyzing under strong alkaline conditions such as sodium hydroxide and filtering the insoluble material, and the dihydroxy compound. A method of analyzing a mixture sample with a dihydroxy compound other than the dihydroxy compound (i) containing (ii) by NMR is also conceivable.

Molecular Weight of Aromatic Polycarbonate Resin (A) The molecular weight of the aromatic polycarbonate resin (A) in the aromatic polycarbonate resin composition of the present invention is a viscosity average molecular weight (Mv) converted from the solution viscosity, and is usually 10,000 to 100, It is characterized by being 000. If the viscosity average molecular weight is less than the above lower limit, the mechanical properties of the aromatic polycarbonate resin composition of the present invention are deteriorated, which is not preferable. Further, when the viscosity average molecular weight exceeds the above upper limit value, the fluidity of the aromatic polycarbonate resin composition of the present invention tends to be extremely insufficient, which is not preferable. From this point of view, the viscosity average molecular weight (Mv) of the aromatic polycarbonate resin (A) in the aromatic polycarbonate resin composition of the present invention is preferably 15,000 or more, more preferably 18,000 or more, still more preferably 18,000 or more. It is 19,000 or more, and particularly preferably 20,000 or more. Further, it is preferably 80,000 or less, more preferably 40,000 or less, further preferably 30,000 or less, and particularly preferably 28,000 or less.

When controlling the viscosity average molecular weight of the aromatic polycarbonate resin (A) contained in the aromatic polycarbonate resin composition of the present invention within the above range, two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights are mixed. In this case, aromatic polycarbonate resins having a viscosity average molecular weight outside the above-mentioned suitable range are mixed using (a1) and (a2), and the aromatic polycarbonate resin (A) of the present invention is used. ), The viscosity average molecular weight (Mv) may be controlled.

Molecular Weight of Aromatic Polycarbonate Resin (a1) The molecular weight of the aromatic polycarbonate resin (a1) in the aromatic polycarbonate resin composition of the present invention is a viscosity average molecular weight (Mv) converted from the solution viscosity, and is usually 5,000 to 40, It is preferably 000. If the viscosity average molecular weight is less than the above lower limit, the mechanical properties of the aromatic polycarbonate resin composition of the present invention are deteriorated, which is not preferable. When the viscosity average molecular weight exceeds the above upper limit, the fluidity of the aromatic polycarbonate resin composition of the present invention tends to be extremely insufficient, and the dispersibility in the aromatic polycarbonate resin (a2) tends to decrease. Therefore, it is not preferable. From this point of view, the viscosity average molecular weight (Mv) of the aromatic polycarbonate resin (a1) in the aromatic polycarbonate resin composition of the present invention is more preferably 8,000 or more, still more preferably 10,000 or more, and above all. 12,000 or more, particularly 13,000 or more is preferable. Further, it is more preferably 30,000 or less, further preferably 28,000 or less, particularly preferably 24,000 or less, particularly preferably 22,000 or less, and most preferably 20,000 or less.

When controlling the viscosity average molecular weight of the aromatic polycarbonate resin (a1) in the aromatic polycarbonate resin composition of the present invention within the above range, two or more kinds of aromatic polycarbonate resins (a1) having different viscosity average molecular weights are used. They may be mixed and used. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above-mentioned suitable range is used for mixing, and the viscosity average molecular weight of the aromatic polycarbonate resin (a1) of the present invention (a1). Mv) may be controlled.

Molecular Weight of Aromatic Polycarbonate Resin (a2) The molecular weight of the aromatic polycarbonate resin (a2) in the aromatic polycarbonate resin composition of the present invention is the viscosity average molecular weight (Mv) converted from the solution viscosity, and is the above-mentioned aromatic polycarbonate resin (Mv). It is the same as the range of the preferable viscosity average molecular weight of A).
When controlling the viscosity average molecular weight of the aromatic polycarbonate resin (a2) in the aromatic polycarbonate resin composition of the present invention within the above range, two or more kinds of aromatic polycarbonate resins (a2) having different viscosity average molecular weights are used. They may be mixed and used. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above-mentioned suitable range is used for mixing, and the viscosity average molecular weight of the aromatic polycarbonate resin (a2) of the present invention (a2). Mv) may be controlled.

The viscosity average molecular weight (Mv) of the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1) and the aromatic polycarbonate resin (a2) contained in the aromatic polycarbonate resin composition of the present invention is methylene chloride as a solvent. In use, the intrinsic viscosity (extreme viscosity) [η] (unit: dl / g) at a temperature of 20 ° C. was determined using a polycarbonate viscous meter, and the viscosity formula of Schnell, that is, η = 1.23 × 10 ^-4 Mv ^{0. It} means the value calculated from .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).

Amount of terminal hydroxyl groups of aromatic polycarbonate resin (A), aromatic polycarbonate resin (a1), and aromatic polycarbonate resin (a2) Aromatic polycarbonate resin (A) and aromatics contained in the aromatic polycarbonate resin composition of the present invention. The amount of terminal hydroxyl groups of the polycarbonate resin (a1) and the aromatic polycarbonate resin (a2) is not particularly limited, but is usually 10 to 2,000 ppm. Further, it is preferably 20 ppm or more, more preferably 50 ppm or more, still more preferably 100 ppm or more, while preferably 1800 ppm or less, more preferably 1,600 ppm or less, still more preferably 1200 ppm or less. .. By setting the amount of terminal hydroxyl groups within the above range, the thermal stability of the aromatic polycarbonate resin composition of the present invention can be further improved.

The amount of terminal hydroxyl groups of the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) contained in the aromatic polycarbonate resin composition of the present invention can be determined by any known method. It can be easily adjusted to the above range.

The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2). The measuring method is colorimetric quantification by the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)). For an aromatic polycarbonate resin copolymer composed of a plurality of dihydroxy compounds, a sample in which the corresponding dihydroxy compounds are mixed according to the copolymerization ratio is prepared at a concentration of at least 3 levels, and a calibration curve is obtained from the data of 3 points or more. After subtracting, the amount of terminal hydroxyl groups of the aromatic polycarbonate resin is measured. The detection wavelength is 546 nm.

Method for Producing Aromatic Polycarbonate Resin (A), Aromatic Polycarbonate Resin (a1), and Aromatic Polycarbonate Resin (a2) Aromatic Polycarbonate Resin (A), Aromatic Polycarbonate Resin (a1), and Aromatic Polycarbonate of the present invention. The method for producing the resin (a2) is not particularly limited as long as it is a known method and can be appropriately selected and used. However, the aromatic dihydroxy compound necessary for forming the above-mentioned carbonate structural unit (i) and any of the above-mentioned aromatic dihydroxy compounds. It is obtained by polycondensing a dihydroxy compound containing the other dihydroxy compound selected in 1 and a carbonate-forming compound.

Examples of carbonate-forming compounds include carbonyl halides, carbonate esters and the like. As the carbonate-forming compound, one kind may be used, or two or more kinds may be used in any combination and ratio.
Specific examples of the carbonyl halide include phosgene; a bischloroformate of a dihydroxy compound, a haloformate of a monochloroformate of a dihydroxy compound, and the like.

Specifically, the carbonate ester may be a compound represented by the following formula (12), and may be an aryl carbonate, a dialkyl carbonate, a biscarbonate of a dihydroxy compound, a monocarbonate of a dihydroxy compound, or a cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.
In formula (12), Z ¹ and Z ² independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group, or an arylalkyl group, respectively. Hereinafter, when Z ¹ and Z ² 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 diaryl carbonate. Among them, from the viewpoint of reactivity with the dihydroxy compound ^{, both Z 1} and Z ² are preferably aryl groups, and more preferably diaryl carbonate represented by the following formula (13).

In formula (13), Z ³ and Z ⁴ independently represent 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 4 to 20 carbon atoms, respectively. Cycloalkyl group and 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 referred to as "DPC"), and bis (4-methyl). Phenyl) carbonate, bis (4-chlorophenyl) carbonate, bis (4-fluorophenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (2,4-difluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, bis Examples thereof include (substituted) diaryl carbonates such as (2-nitrophenyl) carbonate, bis (methylsalitylphenyl) carbonate, and ditril carbonate, and diphenyl carbonate is preferable. In addition, these carbonate esters can be used alone or in mixture of 2 or more types.

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 isophthalate and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

As a method for producing the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) of the present invention, it can be produced by a conventionally known polymerization method. The polymerization method is not particularly limited. Examples of the polymerization method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, particularly suitable of these methods will be specifically described.

Interfacial Polymerization Method First, a case where the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) of the present invention are produced by the interfacial polymerization method will be described. In the interfacial polymerization method, the pH is usually maintained at 9 or higher in the presence of an organic solvent and an alkaline aqueous solution inert to the reaction, and the raw material dihydroxy compound is reacted with a carbonate-forming compound (preferably phosgen). An aromatic polycarbonate copolymer is obtained by performing interfacial polymerization in the presence of a polymerization catalyst. If necessary, a molecular weight modifier (terminal terminator) may be present in the reaction system, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.
The raw material dihydroxy compounds and carbonate-forming compounds are as described above. Among the carbonate-forming compounds, it is preferable to use phosgene, and the method when phosgene is used is particularly called a phosgene method.

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 type may be used, or two or more types may be used in any combination and ratio.
Examples of the alkaline compound contained in the alkaline aqueous solution include, but are not limited to, alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium hydrogen carbonate, and alkaline earth metal compounds. Sodium hydroxide and potassium hydroxide are preferred. As the alkaline compound, one type may be used, or two or more types may be used in any combination and ratio.
The concentration of the alkaline compound in the alkaline aqueous solution is not limited, but is usually used in an amount of 5 to 10% by mass in order to control the pH of the reaction in the alkaline aqueous solution to 10 to 12. Further, for example, when phosgene is blown, the molar ratio of the raw material dihydroxy compound to the alkaline compound is usually 1: 1 in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. It is preferably 9 or more, particularly 1: 2.0 or more, and usually 1: 3.2 or less, especially 1: 2.5 or less.

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. Tertiary ammonium salts and the like; pyridines; guanines; guanidine salts; etc. As the polymerization catalyst, one type may be used, or two or more types may be used in any combination and ratio.

The molecular weight modifier is not particularly limited, and examples thereof include aromatic phenols having a monovalent phenolic hydroxyl group; fatty alcohols such as methanol and butanol; mercaptans; phthalates, 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, and 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, m-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, tribromo Phenol, a monoalkylphenol having a linear or branched alkyl group with an average carbon number of 12 to 35 at the ortho-position, meta-position or para-position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene 9- (4-Hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl) fluorene; 4- (1-adamantyl) phenol and the like can be mentioned. 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 modifier used is not particularly limited, but is, for example, usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol with respect to 100 mol of the raw material dihydroxy compound. It is less than a mole. By setting the amount of the molecular weight adjusting agent used in this range, the thermal stability of the aromatic polycarbonate resin can be improved.

In the reaction, the order of mixing the reaction substrate (reaction raw material), reaction medium (organic solvent), catalyst, additives, etc. is arbitrary as long as the desired aromatic polycarbonate resin can be obtained, and the appropriate order is arbitrary. You can set it. For example, when phosgene is used as the carbonate-forming compound, the molecular weight modifier is mixed at any time between the reaction (phosgenation) between the raw material dihydroxy compound and phosgene and the start of the polymerization reaction. it can.
The reaction temperature is not particularly limited, but is usually 0 to 40 ° C., and the reaction time is not particularly limited, but is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

Molten Transesterification Method Next, a case where the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) of the present invention are produced by the molten transesterification method will be described. In the melt ester exchange method, for example, a transesterification reaction between a carbonate ester and a raw material dihydroxy compound is performed.
The raw material dihydroxy compound and carbonate ester are as described above.
The ratio of the raw material dihydroxy compound to the carbonate ester (including the substituted dicarboxylic acid or dicarboxylic acid ester described above; the same applies hereinafter) is the desired aromatic polycarbonate resin (A), aromatic polycarbonate resin (a1) of the present invention. And, as long as the aromatic polycarbonate resin (a2) can be obtained, these carbonate esters are preferably used 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 to 1.30 times (molar ratio), more preferably 1.02 to 1.20 times (molar ratio) with respect to the dihydroxy compound. .. If the molar ratio is too small, the number of terminal OH groups in the obtained aromatic polycarbonate resin increases, and the thermal stability of the resin tends to deteriorate. On the other hand, if the molar ratio is too large, the reaction rate of transesterification is lowered, and the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) of the present invention having a desired molecular weight are used. May become difficult to produce, or the residual amount of carbonate ester in the resin may increase, which may cause an odor during molding or molding.

When producing the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) of the present invention 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. Alternatively, 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 under the above conditions while removing by-products.
The reaction form can be either a batch method or a continuous method. When the batch method is used, the order of mixing the reaction substrate, reaction medium, catalyst, additives, etc. is the desired aromatic polycarbonate resin (A), aromatic polycarbonate resin (a1), and aromatic polycarbonate resin (a1) of the present invention. It is arbitrary as long as a2) can be obtained, and an appropriate order may be set arbitrarily. However, in consideration of the stability of the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) of the present invention, the melt polycondensation reaction can be carried out continuously. preferable.

In the molten transesterification method, a catalytic deactivator may be used if necessary. As the catalyst deactivator, 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 deactivator, one type may be used, or two or more types may be used in any combination and ratio.
The amount of the catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, and more than 1 equivalent, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. It is usually 20 equivalents or less, preferably 10 equivalents or less. Furthermore, it is usually 1 ppm or more, and usually 100 ppm or less, preferably 50 ppm or less, with respect to the aromatic polycarbonate resin (A), the aromatic polycarbonate resin (a1), and the aromatic polycarbonate resin (a2) of the present invention. Is.

[Phosphorus flame retardant (B)]
The polycarbonate resin composition of the present invention contains a phosphorus-based flame retardant (B). By containing an aromatic polycarbonate resin (A) containing a specific amount of a carbonate structural unit derived from the dihydroxy compound (i) represented by the formula (1) and a phosphorus-based flame retardant (B), flame retardancy and resistance are achieved. Impact resistance, fluidity and heat resistance can be improved in a well-balanced manner.

The phosphorus-based flame retardant (B) is a compound containing phosphorus in the molecule, and may be a small molecule, an oligomer, or a polymer, but from the viewpoint of thermal stability, the following general The condensed phosphate compound represented by the formula (14) and the phosphazene compound represented by the general formulas (15) and (16) are particularly preferable.

Condensed Phosphate Ester Compound The condensed phosphoric acid ester compound represented by the above general formula (14) may be a mixture of compounds having different numbers of k, and in the case of a mixture of condensed phosphoric acid esters having different k. Is the average value of their mixture. k is usually an integer from 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

Further, X ¹ represents a divalent arylene group, for example, resorsinol, hydroquinone, bisphenol A, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. It is the basis. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3'-dihydroxybiphenyl are particularly preferred.

Further, p, q, r and s in the general formula (14) represent 0 or 1, respectively, and are preferably 1 among them.

Further, R ¹ , R ² , R ³ and R ⁴ each indicate an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such an aryl group include a phenyl group, a cresyl group, a xsilyl group, an isopropylphenyl group, a butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a p-cumylphenyl group and the like. A group, a cresyl group, and a xylyl group are more preferable.

As a specific example of the condensed phosphoric acid ester compound represented by the general formula (14),
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyldiphenyl phosphate (CDP), 2-ethylhexyldiphenyl phosphate (EHDP), tert-butylphenyldiphenyl phosphate, bis- ( Aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
And so on.

The acid value of the condensed phosphoric acid ester compound represented by the general formula (14) is preferably 0.2 mgKOH / g or less, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less. Particularly preferably, it is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by mass or less, and further preferably 0.9 parts by mass or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the thermal stability and hydrolysis resistance of the polycarbonate resin composition of the present invention are deteriorated.

Examples of the phosphate ester compound include 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3-dihydroxyphenyl) in addition to the above. Contains -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphate ester moiety Of course, polyester resin, polycarbonate resin or epoxy resin is also included.

-Phosphazene compounds Examples of the phosphazene compounds represented by the above general formulas (15) and (16) include phenoxyphosphazene and (poly) triloxyphosphazene (eg, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-. Cyril oxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xsilyloxyphosphazene, etc. And / or chain C _1-6 alkyl C _6-20 aryloxyphosphazene and (poly) phenoxytriloxyphosphazene (eg, phenoxyo-tolyloxyphosphazene, phenoxym-tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, Phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (Poly) phenoxyxysilyloxyphosphazene, ( Poly) Cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxyphosphazene such as phenoxytriloxyxysilyloxyphosphazene can be exemplified.
Of these, preferably cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20. Aryloxyphosphazene (eg, cyclic and / or chain triloxyphosphazene, cyclic and / or chain phenoxytrilphenoxyphosphazene, etc.).

The cyclic phosphazene compound represented by the general formula (15), R ⁵ and R ⁶ may be the same or different, an aryl group or an alkylaryl group. Examples of such aryl group or alkylaryl group, a phenyl group, a naphthyl group, methylphenyl group, and a benzyl group. Among them R ⁵ and R ⁶ are particularly preferably a cyclic phenoxyphosphazene a phenyl group.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene and octachloro from a cyclic and linear chlorophosphazene mixture obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples thereof include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene, which are obtained by taking out cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting them with a phenoxy group. ..

Further, in the formula (15), t represents an integer of 3 to 25, and among them, a compound in which t is an integer of 3 to 8 is preferable, and a mixture of compounds having different t may be used. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less in total is preferable.

In formula (16), R ⁷ and R ⁸ may be the same or different and represent an aryl group or an alkylaryl group. Examples of such aryl group or alkylaryl group, a phenyl group, a naphthyl group, methylphenyl group, and a benzyl group, a chain-like phenoxyphosphazene R ⁷ and R ⁸ is a phenyl group is particularly preferred.
In such a chain phenoxyphosphazene compound, for example, hexachlorocyclotriphosphazene obtained by the above method is reclaim-polymerized at a temperature of 220 to 250 ° C., and the obtained linear dichloro having a degree of polymerization of 3 to 10,000 Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group.

Further, ^{R 9 _{may, -N = P (OR 7)}} 3 _{^{group, -N = P (OR 8)}} 3 group, -N = P (O) OR 7 group, a -N = P (O) OR ⁸ group represents at least one ^{selected, R 10} is, -P ^(OR _{7) 4} group, -P ^(OR _{8) 4} ^{group, -P (O) (OR 7} ) 2 group, -P (O) (OR ⁸ ) At least one selected from _{two units is shown.}

Further, in the formula (16), u represents an integer of 3 to 10,000, preferably 3 to 1,000, more preferably 3 to 100, and further preferably 3 to 25.

Further, the phosphazene compound may be a crosslinked phosphazene compound in which a part thereof is crosslinked. Having such a crosslinked structure tends to improve heat resistance.
Examples of such a crosslinked phosphazene compound include a crosslinked group represented by the following general formula (17), for example, a compound having a crosslinked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), 2,2- (4). , 4'-Diphenylene) A compound having a crosslinked structure of an isopropylidene group, a compound having a crosslinked structure of a 4,4′-oxydiphenylene group, a compound having a crosslinked structure of a 4,4′-thiodiphenylene group, etc. Examples thereof include compounds having a crosslinked structure of a 4,4'-diphenylene group.

[In equation (17), X ² is -C (CH ₃ ) _2- , -SO _2- , -S-, or -O-, and v is 0 or 1. ]

Further, as the crosslinking phosphazene compound, a cyclic phenoxyphosphazene compound is cross-linked by a cross-linking group represented by the general formula (17) the crosslinked phenoxyphosphazene compound is R ⁵ and R ⁶ in the general formula (15) a phenyl group ^{Alternatively, the cross-linked phenoxyphosphazene compound in which the chain phenoxyphosphazene compound in which R 7} and R ⁸ are phenyl groups in the general formula (16) is crosslinked by the cross-linking group represented by the general formula (17) is flame-retardant. From the above viewpoint, the cyclic phenoxyphosphazene compound is more preferably a crosslinked phenoxyphosphazene compound in which the cyclic phenoxyphosphazene compound is crosslinked by the crosslinking group represented by the above general formula (17).

The content of the phenylene group in the crosslinked phenoxyphosphazene compound is the total phenyl group in the cyclic phosphazene compound represented by the general formula (15) and / or the chain phenyl group represented by the general formula (16). Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. Further, the crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in its molecule.

In the present invention, the phosphazene compound is a crosslinked phenoxy in which the cyclic phenoxyphosphazene compound represented by the general formula (15) and the cyclic phenoxyphosphazene compound represented by the general formula (16) are crosslinked by a crosslinking group. At least one selected from the group consisting of phosphazene compounds is preferable from the viewpoint of flame retardancy and mechanical properties.

The content of the phosphorus-based flame retardant (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). If the content of the phosphorus-based flame retardant (B) is less than 1 part by mass, the flame retardancy tends to be insufficient, and if it exceeds 50 parts by mass, the heat resistance and the mechanical properties are likely to be lowered. The content of the phosphorus-based flame retardant (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

The aromatic polycarbonate resin composition of the present invention has an excellent balance of flame retardancy, fluidity, heat resistance and impact resistance. Here, the balance between fluidity and impact resistance is usually in a trade-off relationship. The aromatic polycarbonate resin composition of the present invention has superior impact strength when it has the same fluidity as the conventionally known aromatic polycarbonate resin composition, while maintaining the same impact resistance. Then, it is a feature that higher fluidity can be imparted. Specifically, a carbonate structural unit derived from the dihydroxy compound (i) in the total carbonate structure constituting the aromatic polycarbonate resin (A) according to the desired fluidity and impact resistance required for the aromatic polycarbonate resin composition. By controlling the ratio of the above, it is possible to achieve a balance between fluidity and impact resistance superior to those of conventionally known aromatic polycarbonate resin compositions.

Here, regarding the fluidity of the aromatic polycarbonate resin composition of the present invention, the higher the fluidity is, the higher the molding processability is, so that it is preferable, and there is no particular upper limit. The value of MVR measured under the condition of 1.2 kg, the lower limit thereof is usually 3 or more, preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and particularly preferably 7. The above is most preferably 8 or more. On the other hand, the upper limit of MVR is not particularly limited, but is usually 50 or less, preferably 40 or less, more preferably 30 or less, still more preferably 25 or less, particularly preferably 20 or less, and most preferably 15 or less. If the MVR is below the lower limit, it may not be possible to obtain a molded product having a desired thickness and size due to insufficient fluidity when molding the aromatic polycarbonate resin composition of the present invention. On the other hand, if the upper limit is exceeded, burrs may easily come out from the molded product.

On the other hand, the impact resistance is not particularly limited as long as the effect of the present invention is not impaired, but can be represented by the Charpy impact strength measured under the condition of a thickness of 3 mm and a notch, in accordance with ISO179-1 & 2. Charpy notched impact strength is usually 1 kJ / ^{m 2} or more, preferably 2 kJ / ^{m 2} or more, more preferably 3 kJ / ^{m 2} or more, more preferably 3.5KJ / ^{m 2} or more, particularly preferably 4 kJ / ^{m 2} As mentioned above, it is most preferably 5 KJ / m ² or more. If the Charpy impact strength is less than the lower limit, the molded product may be extremely liable to crack. The upper limit of Charpy impact strength is not particularly limited.

The heat resistance of the aromatic polycarbonate resin composition of the present invention is not particularly limited as long as it does not impair the characteristics of the aromatic polycarbonate resin composition of the present invention, but is based on ISO75-1 & 2 and has a deflection of 1.80 MPa. The deflection temperature under load (DTUL) measured under the condition (A method) is preferably 75 ° C. or higher, more preferably 78 ° C. or higher, further preferably 80 ° C. or higher, and 85 ° C. or higher. This is particularly preferable, and 90 ° C. or higher is most preferable. By setting the value of DTUL in the above range, it has high dimensional stability even when used for a member close to a light source or a heat source, or in a high temperature environment such as in an automobile, and has been used for a long period of time. In this case, a molded product having a small decrease in strength can be obtained.
Although there is no particular upper limit on the DTUL value, it is usually 200 ° C. or lower, preferably 180 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 150 ° C. or lower, and particularly preferably 140 ° C. or lower. If the value of DTUL exceeds 200 ° C., the fluidity tends to be extremely lowered, which is not preferable.

The aromatic polycarbonate resin composition of the present invention may contain other components (resin additives) in addition to those described above, as long as the effects of the present invention and desired physical properties are not significantly impaired. Examples of resin additives include heat stabilizers, antioxidants, mold release agents, dye pigments, UV absorbers, fillers, brightness improvers, antistatic agents, antifogging agents, lubricants, and antiblocking agents. , Dispersants, antibacterial agents and the like. Among them, in order to use it as a general injection molding material, it is preferable to contain at least one selected from the group consisting of a heat stabilizer, an antioxidant, a mold release agent and an ultraviolet absorber.
In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.

Heat Stabilizer The heat stabilizer used in the aromatic polycarbonate resin composition of the present invention is not particularly limited as long as it is conventionally known to be blended with the aromatic polycarbonate resin, but for example, a phosphorus-based heat stabilizer and a sulfur-based heat. Stabilizers can be mentioned, but among them, phosphorus-based stabilizers are preferable because they tend to have excellent thermal stability of the aromatic polycarbonate resin composition of the present invention.

Specific examples of phosphorus-based heat stabilizers include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphite, phosphinic acid, and polyphosphoric acid; acidic pyrophosphorus such as acidic sodium pyrophosphate, potassium pyrophosphate, and acidic calcium pyrophosphate. Acid metal salts; Phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. may be mentioned. From the viewpoint of thermal stability, an organic phosphite compound and an organic phosphorite are particularly preferable, and an organic phosphite compound is the most preferable.

Examples of the organic phosphite compound include triphenylphosphite, tris (4-methylphenyl) phosphite, tris (4-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and tris (2-methyl-4). -Ethylphenyl) phosphite, tris (2-methyl-4-t-butylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,6-di-t-butyl) Phenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, bis (monononylphenyl) pentaerythritol-di-phosphite, Bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2, 4,6-tri-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butyl-5-methylphenyl) pentaerythritol-di-phosphite, (2,6-di) -T-butyl-4 Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-dimethylphenyl) octylphosphite, 2,2-methylenebis (4-t-butyl-6-methylphenyl) octyl Phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 2,2-methylenebis (4,6-dimethylphenyl) hexylphosphite, 2,2-methylenebis (4,6) Examples thereof include −di-t-butylphenyl) hexylphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) stearylphosphite, and examples of the organic phosphonite compound include tetrakis (2,4-di). Examples thereof include -t-butylphenyl) 4,4'-biphenylenediphosphonite and tetrakis (2,4-di-t-butyl-5 methylphenyl) 4,4'-biphenylenediphosphonite.

Specific examples of such an organic phosphite compound include "ADEKA STAB 1178", "ADEKA STAB (registered trademark) 2112", "ADEKA STAB PEP-8", "ADEKA STAB PEP-36", and "ADEKA" manufactured by ADEKA. ADEKA STAB HP-10 ”,“ JP-351 ”,“ JP-360 ”,“ JP-3CP ”manufactured by Johoku Chemical Industry Co., Ltd.,“ Irgafoss (registered trademark) 168 ”manufactured by BASF, etc. , BASF's "Irgafos P-EPQ" and the like.

The phosphorus-based stabilizer may contain one type or two or more types in any combination and ratio.

The content of the phosphorus-based stabilizer is not particularly limited, but is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and more preferably 0 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is 03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, and more preferably 0.5 parts by mass or less. If the content of the phosphorus-based stabilizer is less than the lower limit of the above range, the heat stabilizing effect may be insufficient, and if the content of the phosphorus-based stabilizer exceeds the upper limit of the above range, heat may be insufficient. There is a possibility that the stability will be reduced and gas will be easily emitted during injection molding.

Antioxidant The aromatic polycarbonate resin composition of the present invention preferably contains an antioxidant. The antioxidant used in the aromatic polycarbonate resin composition of the present invention is not particularly limited as long as it is conventionally known to be blended with the aromatic polycarbonate resin, and examples thereof include hindered phenolic antioxidants. 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''-(mesitylen-2,4,6-triyl) tri -P-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (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- Examples thereof include 2-ylamino) phenol and 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate.
Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. Specific examples of such phenolic antioxidants include BASF's "Irganox 1010" and "Irganox 1076", ADEKA's "ADEKA STAB AO-50" and "ADEKA STAB AO-60". Can be mentioned.

In addition, one type of antioxidant may be contained, and two or more types may be contained in arbitrary combinations and ratios.

The content of the antioxidant is not particularly limited, but is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and more preferably 0.1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is not less than 1 part by mass, and usually 1 part by mass or less, preferably 0.5 part by mass or less. If the content of the antioxidant is less than the lower limit of the above range, the effect as an antioxidant may be insufficient, and if the content of the phenolic stabilizer exceeds the upper limit of the above range, it may be insufficient. , There is a possibility that gas is likely to be emitted during injection molding.

Release Agent The aromatic polycarbonate resin composition of the present invention preferably contains a release agent. The mold release agent used in the aromatic polycarbonate resin composition of the present invention is not particularly limited as long as it is conventionally known to be blended with the aromatic polycarbonate resin, and for example, aliphatic carboxylic acid, aliphatic carboxylic acid and alcohol. , Aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, and the like.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, and adipine. Examples include acid and azelaic acid.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term aliphatic is used as a term including an alicyclic compound.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Can be mentioned.
The above ester may contain an aliphatic carboxylic acid and / or an alcohol as an impurity. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, as the aliphatic carboxylic acid and the alcohol which are combined to form one ester, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acid and alcohol include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, fisher-tropus wax, α-olefin oligomer having 3 to 12 carbon atoms, and the like. Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Moreover, these hydrocarbons may be partially oxidized.
Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.

The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, or a mixture of various constituents and molecular weights can be used as long as the main component is within the above range.
Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

The above-mentioned mold release agent may contain one type or two or more types in any combination and ratio.

The content of the release agent is not particularly limited, but is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is less than or equal to parts by mass, preferably less than or equal to 1 part by mass. If the content of the release agent is less than the lower limit of the above range, the effect of mold release may not be sufficient, and if the content of the release agent exceeds the upper limit of the above range, the thermal stability There is a possibility of deterioration and mold contamination during injection molding.

Ultraviolet absorber The aromatic polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organic compounds such as benzotriazole compound, benzophenone compound, salicylate compound, cyanoacrylate compound, triazine compound, ogizanylide compound, malonic acid ester compound and hindered amine compound. Examples include UV absorbers. Among these, an organic ultraviolet absorber is preferable, a benzotriazole compound, a cyanoacrylate compound, a triazine compound, and a malonic acid ester compound are more preferable, and a benzotriazole compound and a triazine compound are particularly preferable. By selecting the organic ultraviolet absorber, the transparency and mechanical characteristics of the aromatic polycarbonate resin composition of the present invention can be improved.

Specific examples of the benzotriazole compound include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- [2'-hydroxy-3', 5'-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5' -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3') , 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3) -Tetramethylbutyl) -6- (2N-benzotriazole-2-yl) phenol] and the like, among which 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2' -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole-2-yl) phenol] is preferable, and 2- (2'-hydroxy-5'-tert- is particularly preferable. Octylphenyl) benzotriazole is preferred.
Examples of commercially available products of such benzotriazole compounds include "Seasorb 701", "Seasorb 705", "Seasorb 703", "Seasorb 702", "Seasorb 704", "Seasorb 709" manufactured by Cytec Chemical Industries, Ltd. "Biosorb 520", "Biosorb 582", "Biosorb 580", "Biosorb 583", "Chemisorb 71", "Chemisorb 72", "Chemisorb 79", Cytec Industries "Cytec Industries UV5411", ADEKA's "LA-32", "LA-38", "LA-36", "LA-34", "LA-31", BASF's "Chinubin P", "Chinubin 234", "Chinubin 326" , "Cytec 327", "Cytec 328" and the like.

Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n-octoxy. Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 , 4'-dimethoxybenzophenone and the like.
Examples of commercially available products of such benzophenone compounds include "Seasorb 100", "Seasorb 101", "Seasorb 101S", "Seasorb 102", "Seasorb 103" manufactured by Cytec Chemical Industries, Ltd., and "Biosorb 100" manufactured by Kyodo Pharmaceutical Co., Ltd. , "Biosorb 110", "Biosorb 130", "Cytecobe 10", "Cytecove 11", "Cytecove 11S", "Cytecove 12", "Cytecove 13", "Cytecove 111", BASF's "Ubinal" 3049 ”,“ Ubinal 3050 ”,“ Cytec Industries UV9 ”,“ Cytec UV284 ”,“ Cytec UV531 ”,“ Cyathove UV24 ”, ADEKA“ ADEKA STAB 1413 ”,“ ADEKA STAB LA-51 ”, etc. ..

Specific examples of the salicylate compound include phenyl salicylate, 4-tert-butylphenyl salicylate and the like, and commercially available products of such salicylate compound include, for example, "Seasorb 201" and "Seasorb 202" manufactured by Cipro Chemical Co., Ltd. , "Chemisorb 21" manufactured by ChemiPro Kasei Co., Ltd., "Chemisorb 22" and the like.
Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and the like. Examples of commercially available products include "Sea Sorb 501" manufactured by Cipro Kasei Co., Ltd., "Biosorb 910" manufactured by Kyodo Yakuhin Co., Ltd., "Ubisorator 300" manufactured by Daiichi Kasei Co., Ltd. 3039 ”and the like.

Examples of the triazine compound include, for example, a compound having a 1,3,5-triazine skeleton, and specific examples of such a triazine compound include "LA-46" and "LA-46" manufactured by ADEKA Corporation. Examples thereof include "F70", "Tinubin 1577ED" manufactured by BASF, "Tinubin 1600", "Tinubin 400", "Tinubin 405", "Tinubin 460", "Tinubin 477-DW", and "Tinubin 479".
Specific examples of the oxalinide compound include 2-ethoxy-2'-ethyl oxalinic acid bisarinide, and commercially available products of such oxalinide compounds include, for example, "Sanduboa VSU" manufactured by Clariant AG. , Etc. can be mentioned.
As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Examples of commercially available products of such malonic acid ester compounds include "PR-25" and "B-CAP" manufactured by Clariant AG.

The content of the ultraviolet absorber is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and further preferably 0.1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Parts or more, particularly preferably 0.15 parts by mass or more. Further, it is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, further preferably 1 part by mass or less, and particularly preferably 0.5 part by mass or less. If the content of the UV absorber is less than the lower limit of the above range, the effect of improving the weather resistance will be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the effect will only peak. However, it is not preferable because mold ultraviolet rays and the like are generated during injection molding, which may cause mold contamination, gas generation from the die during extrusion molding, and eyelid generation. The ultraviolet absorber may contain one type or two or more types in any combination and ratio.

Method for Producing Aromatic Polycarbonate Resin Composition The method for producing an aromatic polycarbonate resin composition of the present invention is not limited, and a known method for producing an aromatic polycarbonate resin composition can be widely adopted.
Specific examples include an aromatic polycarbonate resin (A) and a phosphorus-based flame retardant (B), other components blended as necessary, or an aromatic polycarbonate resin (a1) and an aromatic polycarbonate resin (a1). After premixing a2), the phosphorus-based flame retardant (B), and other components to be blended as needed using various mixers such as a tumbler and a Henschel mixer, a Banbury mixer, a roll, a brabender, and a single Examples thereof include a method of melt-kneading with a mixer such as a shaft kneading extruder, a twin-screw kneading extruder, and a kneader.

Further, for example, the aromatic polycarbonate resin composition of the present invention is obtained by premixing each component without premixing, or premixing only a part of the components, supplying the mixture to an extruder using a feeder, and melt-kneading the composition. It can also be manufactured.
Further, when the aromatic polycarbonate resin (A) of the present invention is produced, an additive may be directly added to the molten resin after the completion of polymerization and kneaded. When adding in this way, a method is preferable in which the molten resin is directly introduced into the extruder after the polymerization is completed, the additive is blended, and the mixture is melt-kneaded and pelletized.
Further, for example, a resin composition obtained by mixing some components in advance, supplying them to an extruder, and melt-kneading the resin composition is used as a masterbatch, and the masterbatch is mixed with the remaining components again and melt-kneaded. The aromatic polycarbonate resin composition of the present invention can also be produced.
Further, for example, when a component that is difficult to disperse is mixed, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance and kneaded with the solution or dispersion to disperse the component. It can also enhance the sex.

Aromatic Polycarbonate Resin Molded Body The aromatic polycarbonate resin composition of the present invention can be suitably used as an aromatic polycarbonate resin molded body by heat processing such as injection molding and extrusion molding. The shape, pattern, color, size, etc. of such an aromatic polycarbonate resin molded product are not limited and can be appropriately selected depending on the intended use of the molded product. For example, a plate shape, a plate shape, a rod shape, or a sheet can be selected. Various shapes such as shape, film shape, cylinder shape, ring shape, circular shape, elliptical shape, polygonal shape, deformed product, hollow product, frame shape, box shape, panel shape, etc., and special shape Can be mentioned. Further, for example, the surface may have irregularities or a three-dimensional shape having a three-dimensional curved surface.

The injection molding method is not particularly limited, and any molding method generally used for thermoplastic resins can be 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, molding using a rapid heating mold, and foaming. Examples include molding (including supercritical fluid), insert molding, and IMC (in-mold coating molding) molding method. Further, a molding method using a hot runner method can also be used.

Examples of molded bodies include various automobile parts, electrical and electronic equipment, information terminal equipment, OA equipment, mechanical parts, home appliances, vehicle parts, building parts, various containers, leisure goods / miscellaneous goods, lighting equipment, and other parts. Can be mentioned. Among these, the molded product of the present invention has an excellent balance of flame retardancy, fluidity, heat resistance and impact resistance, and is therefore particularly used for parts of electrical and electronic equipment, information terminal equipment, OA equipment, home appliances and the like. It is particularly suitable for use in the housings of electrical and electronic equipment, information terminal equipment, OA equipment, automobile interior parts, and home electric appliances.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or lower limit value. It may be in the range specified by the value of the following examples or the combination of the values of the examples. Further, in the following description, "part" means "part by mass" based on the mass standard unless otherwise specified.
Among the raw materials used in the following Examples and Comparative Examples, the polycarbonate resins (a1-1) and (a1-2) used as the aromatic polycarbonate resin (a1) were produced by the methods described below.

[Synthesis example: Synthesis of 1,1-bis (4-hydroxyphenyl) dodecane]
1,1-Bis (4-hydroxyphenyl) dodecane is a dihydroxy compound represented by the above formula (9), and is also referred to as "BPC-12" below.
Phenol (100 parts by mass) was heated to 40 ° C. to melt it, and then concentrated hydrochloric acid (1.33 parts by mass) was added. A mixed solution of dodecanal (39.0 parts by mass) and toluene (21.2 parts by mass) was added dropwise thereto over 4 hours. After the dropping, the mixture was aged at 40 ° C. for 1 hour, and then the reaction was stopped with an aqueous sodium hydrogen carbonate solution. After distilling off phenol from the reaction mixture under reduced pressure, it was extracted with toluene and washed with water three times. After distilling off the solvent, it was crystallized from toluene and heptane to obtain 27.8 parts by mass of BPC-12 as a white powder. The purity was 99.0% and the melting point was 86 ° C.

In the above synthesis example, the analysis conditions of the obtained BPC-12 are as follows.
<Purity>
0.01 parts by mass of the sample was dissolved in 1 part by mass of acetonitrile. The obtained solution was analyzed by an HPLC analyzer (manufactured by Shimadzu Corporation, LC-2010) under the following conditions.
Column: inertsilODS3V (manufactured by GL Sciences)
Elution solvent: acetonitrile / 0.1% by mass ammonium acetate solution Detector: UV (254 nm)
The purity was determined from the area% at 254 nm.
<Melting point>
An SMP3 melting point measuring device manufactured by Start Scientific Co., Ltd. was used.
The temperature was raised under the condition of 2 ° C./min, and the temperature at the time when all the solids were melted was defined as the melting point.

[Manufacturing of Polycarbonate Resin (a1-1)]
The first reactor equipped with a stirrer, heat medium jacket, vacuum pump, and reflux condenser includes Mitsubishi Chemical's bisphenol A (hereinafter, also referred to as "BPA"), BPC-12, and Mitsubishi Chemical's diphenyl carbonate (hereinafter, "BPA"). , also referred to as "DPC") and Kishida chemical Co., Ltd. cesium carbonate as a catalyst, in mol ratio, 70:. 30: 105.5: 1 × 10 was charged in a raw material charging ratio of ^-0.6, fully purged with nitrogen did.

Next, the inside of the first reactor was depressurized to 1.33 kPa (10 Torr), and then the operation of restoring the pressure to atmospheric pressure with nitrogen was repeated 5 times to replace the inside of the first reactor with nitrogen. After the nitrogen substitution, the internal temperature of the first reactor was gradually raised through a heat medium having a temperature of 230 ° C. in a heat medium jacket to dissolve the mixture. Then, the stirrer was rotated at 300 rpm to control the temperature inside the heat medium jacket, and the internal temperature of the first reactor was maintained at 220 ° C. Then, while distilling off the phenol produced as a by-product by the oligomerization reaction of the dihydroxy compound and DPC performed inside the first reactor, the pressure inside the first reactor was increased to 101.3 kPa (760 Torr) in absolute pressure over 40 minutes. ) To 13.3 kPa (100 Torr).
Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the first reactor at 13.3 kPa and further distilling off phenol. The inside of the system is restored to 101.3 kPa with absolute pressure with nitrogen, boosted to 0.2 MPa with gauge pressure, and the oligomer in the first reactor is stirred by a transfer pipe that has been preheated to 200 ° C or higher. , A second reactor with an internal temperature of 240 ° C. equipped with a heat medium jacket, a vacuum pump and a reflux condenser. Next, the oligomer pumped into the second reactor is stirred, the internal temperature is raised with a heat medium jacket, and the pressure inside the second reactor is reduced from 101.3 kPa to 13.3 kPa at absolute pressure over 40 minutes. did. Then, the temperature was continuously raised, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) in absolute pressure over another 40 minutes to remove the distilled phenol from the system. Further, the temperature was continuously raised, and after the absolute pressure in the second reactor reached 70 Pa (about 0.5 Torr), 70 Pa was maintained and the polycondensation reaction was carried out.
When the internal temperature inside the second reactor is raised to 250 ° C. and the stirrer of the second reactor reaches a predetermined stirring power, the polycondensation reaction is terminated and the inside of the reactor is recompressed with nitrogen. After that, pressure was applied to remove it from the bottom of the tank, and the mixture was cooled in a water-cooled tank to obtain an aromatic polycarbonate resin.
Then, 5 ppm of butyl paratoluenesulfonate was added to the obtained aromatic polycarbonate resin, melt-kneaded with a twin-screw extruder having a diameter of 30 mm, and the strands were cut with a pelletizer to have a pellet-shaped viscosity average molecular weight of 15. An aromatic polycarbonate resin (a1-1) having 600 and a terminal hydroxyl group content of 660 ppm was obtained.

[Manufacturing of Polycarbonate Resin (a1-2)]
BPA, cesium carbonate as a BPC-12, DPC and catalyst, in mol ratio, 94.7: 5.3: 105.5: 1 × 10 was charged in a raw material charging ratio of ^-0.6, the second reactor An aromatic polycarbonate resin (a1-2) produced under the same conditions as in (a1-1) except that the target value of the stirring power of the stirrer was changed, and the pellet-shaped viscosity average molecular weight was 15,000 and the terminal hydroxyl weight was 770 ppm. Got

As described above, the viscosity average molecular weight of the aromatic polycarbonate resin is the intrinsic viscosity (extreme viscosity) [η] (unit: dl /) of the methylene chloride solution at 20 ° C. using an Ubbelohde viscous meter (manufactured by Moriyu Rika Kogyo Co., Ltd.). g) is obtained, and the viscosity formula of Schnell, that is,
It is calculated from η = 1.23 × 10 ^-4 Mv ^0.83.
The amount of terminal hydroxyl groups of the aromatic polycarbonate resin is determined by colorimetric quantification by the titanium tetrachloride / acetic acid method as described above.

Further, the proportion of the carbonate structural unit derived from the dihydroxy compound (i) of the aromatic polycarbonate resin is such that the aromatic polycarbonate resins (a1-1) to (a1-2) are dissolved in deuterated chloroform at a concentration of 3% by mass. Proton NMR measurement was carried out by JNM-AL400 type NMR (400 MHz) manufactured by JEOL Ltd., and it was calculated from the integrated value of protons derived from each carbonate structure.
As a result, the aromatic polycarbonate resins (a1-1) to (a1-2) were 30 mol% and 5.3 mol%, respectively.

(Examples 1 to 6, Comparative Examples 1 to 5)
The raw material components used in Examples and Comparative Examples are shown in Table 3 below together with the aromatic polycarbonate resins (a1-1) to (a1-2).

Each component shown in Table 3 is blended and mixed at the ratios (parts by mass) shown in Tables 5 to 6 below, and then supplied to the Japan Steel Works (TEX30HSS) equipped with one vent, and the screw rotation speed. Kneading was performed under the conditions of 200 rpm, a discharge rate of 20 kg / h, and a barrel temperature of 260 ° C., and the molten resin extruded into a strand shape was rapidly cooled in a water tank and then pelletized using a pelletizer to obtain pellets of an aromatic polycarbonate resin composition. Obtained.

[Ratio of carbonate structural units derived from dihydroxy compound (i)]
The ratio of the carbonate structural unit derived from the dihydroxy compound (i) in 100 mol% of the total carbonate structure constituting the aromatic polycarbonate resin (A) is that the aromatic polycarbonate resin is dissolved in deuterated chloroform at a concentration of 3% by mass in Japan. Proton NMR measurement was carried out by JNM-AL400 type NMR (400 MHz) manufactured by JEOL Ltd., and it was calculated from the integrated value of protons derived from each carbonate structure.
When the aromatic polycarbonate resin (A) is a mixture of the aromatic polycarbonate resin (a1) and the aromatic polycarbonate resin (a2), the ratio of the carbonate structural units derived from the dihydroxy compound (i) is the molecular weight of the structural units. And, it was calculated by the weighted average in consideration of the mixing ratio, and it is described in the column of "(i) mol% of resin (A)" in the following table.

Moreover, the viscosity average molecular weight (Mv) of the aromatic polycarbonate resin (A) measured by the above-mentioned method is described.

[Evaluation of aromatic polycarbonate resin composition]
[Liquidity: Q value]
Using the pellets of the resin composition obtained above, the flow value (Q value, unit: ^10-2 cc / sec) was set by JIS (1999 version) using a CFT-500D type flow tester manufactured by Shimadzu Corporation. ) According to K7210 Annex C, the measurement was performed at 240 ° C. and 160 kgf / cm ² using a 1 mmφ × 10 mm orifice with a preheating time of 7 minutes.
A large flow value (Q value) indicates high fluidity and excellent moldability, and a small flow value (Q value) indicates low fluidity and poor moldability.

[Impact resistance: Charpy impact value (notched)]
After the pellets of the resin composition obtained above are dried at 80 ° C. for 5 hours, the cylinder temperature is 260 ° C., the mold temperature is 60 ° C., and the screw rotation speed is 100 rpm using an injection molding machine (J55-60H) manufactured by Japan Steel Works, Ltd. , An ISO multipurpose test piece (thickness of 3 mm) was prepared by injection molding under the condition of a molding cycle of 40 seconds. The obtained test piece was subjected to a Charpy impact test (notched) based on ISO179-1 & 2 under room temperature (23 ° C.) conditions, and an impact resistance value (unit: KJ / m ² ) was determined.

[Heat-resistant]
After the pellets of the resin composition obtained above are dried at 80 ° C. for 5 hours, the cylinder temperature is 260 ° C., the mold temperature is 60 ° C., and the screw rotation speed is 100 rpm using an injection molding machine (J55-60H) manufactured by Japan Steel Works, Ltd. , An ISO multipurpose test piece (4 mm thick) was prepared by injection molding under the condition of a molding cycle of 40 seconds. Based on ISO75-1 & 2, the obtained test piece was measured for DTUL (deflection temperature under load, unit: ° C.) under the condition of a load of 1.80 MPa (method A), and the heat resistance was evaluated.

[Flame retardancy: UL94 test]
The pellets obtained above are dried at 80 ° C. for 5 hours, and then injected with an injection molding machine (J55-60H) manufactured by Japan Steel Works, Ltd. under the conditions of a cylinder set temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds. The test piece for UL test was molded at a length of 125 mm × a width of 13 mm and a thickness of 1.5 mm.
The obtained test piece is humidity-controlled for 48 hours in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50%, and is subjected to a UL94 test (combustion of plastic material for equipment parts) specified by the US Underwriters Laboratories (UL). Test) was performed. UL94V is a method for evaluating flammability from the residual flame time and drip property after indirect flame of a burner flame for 10 seconds on a test piece of a predetermined size held vertically, and is V-0, V-1. And in order to have the flammability of V-2, it is necessary to meet the criteria shown in Table 4 below.

Here, the residual flame time is the length of time that the test piece continues to burn with flame after the ignition source is moved away. Further, cotton ignition by drip is determined by whether or not the cotton for labeling located about 300 mm below the lower end of the test piece is ignited by a drip object from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) as not satisfying V-2.

[Comprehensive evaluation]
The above four items of fluidity, impact resistance, heat resistance and flame retardancy were comprehensively evaluated according to the following criteria, and were judged to be ○ or ×.
<Criteria>
-Liquidity (Q value): 30 × 10 ^-2 cc / sec or more.
-Impact resistance (Charpy impact value): 5.2 KJ / m ² or more.
Heat distortion (DTUL): 85 ° C or higher.
-Flame retardant: V-0.
◯: All of the above four criteria are satisfied.
X: The above four criteria are satisfied with three or less items.
The above evaluation results are shown in Tables 5 to 6 below.

Examples 1 to 3 and Comparative Examples 1 to 5 are examples in which condensed phosphoric acid ester was selected as the phosphorus-based flame retardant.
Examples 1 to 3 of the aromatic polycarbonate resin composition of the present invention containing the aromatic polycarbonate resin (A) containing a specific amount of the carbonate structural unit derived from the dihydroxy compound (i) are derived from the dihydroxy compound (i). It can be seen that the fluidity and impact resistance are excellent as compared with Comparative Example 1, which is a conventional polycarbonate resin composition containing no carbonate structural unit. Further, when Comparative Example 2 to which the ABS resin is added and Examples 1 to 3 are compared, it can be seen that in Comparative Example 2, although the impact resistance is improved, the flame retardancy is lowered. Further, Comparative Example 3, which is an aromatic polycarbonate resin composition containing a carbonate structural unit derived from the dihydroxy compound (i) outside the specification of the present invention, has higher fluidity and impact resistance than those of Examples 1 to 3. It can be seen that it is decreasing.

Examples 4 to 6 and Comparative Examples 4 to 5 are examples in which a phenoxyphosphazene compound is selected as a phosphorus-based flame retardant.
Examples 4 to 6 of the aromatic polycarbonate resin composition of the present invention containing the aromatic polycarbonate resin (A) containing a specific amount of the carbonate structural unit derived from the dihydroxy compound (i) are derived from the dihydroxy compound (i). It can be seen that the fluidity and impact resistance are excellent as compared with Comparative Example 4, which is a conventional polycarbonate resin composition containing no carbonate structural unit. Further, when Comparative Example 6 in which the fluidity is improved by using the polycarbonate oligomer and Examples 5 to 6 are compared, it can be seen that Examples 5 to 6 are superior in fluidity and impact resistance.

From the above, it was shown that the aromatic polycarbonate resin composition of the present invention is superior in flame retardancy, fluidity, heat resistance and impact resistance as compared with the conventional aromatic polycarbonate resin composition. It is also clear that the effect is exhibited by containing a specific amount of the aromatic polycarbonate resin (A) containing a specific amount of the carbonate structural unit derived from the dihydroxy compound (i) and a phosphorus-based flame retardant.

Since the aromatic polycarbonate resin composition of the present invention has an excellent balance of flame retardancy, fluidity, heat resistance and impact resistance, housings for electric / electronic devices and automobile parts, particularly various mobile terminals and electronic devices, It can be suitably used for housings of image display devices and has very high industrial utility.

Claims (7)

A resin composition containing 1 to 50 parts by mass of a phosphorus-based flame retardant (B) with respect to 100 parts by mass of the aromatic polycarbonate resin (A), and 100 mol of a total carbonate structure constituting the aromatic polycarbonate resin (A). An aromatic polycarbonate resin composition containing 1 to 7.5 mol% of a carbonate structural unit derived from the dihydroxy compound (i) represented by the following formula ( 9).
The aromatic polycarbonate resin (A) is an aromatic polycarbonate resin (a1) containing a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (9) and a dihydroxy compound represented by the following formula (4). The aromatic polycarbonate resin composition according to claim 1, further comprising an aromatic polycarbonate resin (a2) composed of a carbonate structural unit derived from (ii).
[In the formula (4), W ² represents any one of a single bond, an oxygen atom, a sulfur atom, and a divalent organic group represented by the formula (5). In formula (5), X ⁴ represents a divalent hydrocarbon group having 3 to 18 carbon atoms, X ⁵ represents an oxygen atom or NR ¹⁴ , X ⁶ represents an alkylene group having 1 to 7 carbon atoms, and n represents an alkylene group having 1 to 7 carbon atoms. Represents an integer from 1 to 500. Further, in the formulas (4) and (5), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 6, respectively. Represents any of the monovalent hydrocarbon groups. In formula (5), * indicates the binding site with the benzene ring. ] The aromatic polycarbonate resin (a1) has a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (9 ) and a carbonate structure derived from the dihydroxy compound (ii) represented by the above formula (4). The aromatic polycarbonate resin composition according to claim 2, wherein the aromatic polycarbonate resin composition comprises a unit. It is characterized by containing 2.5 to 36.5 mol% of a carbonate structural unit derived from the dihydroxy compound (i) represented by the above formula (9 ) in 100 mol% of the total carbonate structure constituting the aromatic polycarbonate resin (a1). The aromatic polycarbonate resin composition according to claim 3. Claims 2 to 2, wherein the aromatic polycarbonate resin (A) contains the aromatic polycarbonate resin (a1) and the aromatic polycarbonate resin (a2) in a mass ratio of 55/45 to 4/96. The aromatic polycarbonate resin composition according to any one of 4. The aromatic polycarbonate according to any one of claims 2 to 5 , wherein the aromatic polycarbonate resin (a2) is composed of a carbonate structural unit derived from 2,2-bis (4-hydroxyphenyl) propane. Resin composition. The aromatic polycarbonate resin composition according to any one of claims 1 to 6 , wherein the phosphorus-based flame retardant (B) is at least one selected from a condensed phosphoric acid ester compound or a phosphazene compound. ..