JP2011089050A - Siloxane-copolymerized polycarbonate, polycarbonate resin composition, and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a siloxane-copolymerized polycarbonate excellent in heat resistance, good in lubricity, and useful as a raw material for a molding requiring a good appearance. <P>SOLUTION: The polycarbonate is obtained by allowing at least one siloxane compound having phenol, at least one specific bisphenol compound (A) having a fluorene structure and at least one specific bisphenol compound (B) having a structure different therefrom to react with a carbonate ester-forming compound, wherein the content of the at least one siloxane compound having phenol is ≥0.1 wt.% and <10 wt.% based on the whole monomer component ((at least one siloxane compound having phenol)+(the compound represented by at least one bisphenol compound (A))+(the compound represented by the at least one bisphenol compound (B))); and the siloxane-copolymerized polycarbonate has a glass transition temperature (Tg) of 180 to 240°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a siloxane copolymer polycarbonate, a polycarbonate resin composition, and a molded part comprising the same. More specifically, a siloxane compound having phenol, a bisphenol compound having a fluorene structure, and a siloxane copolymer polycarbonate comprising other bisphenol compounds, a polycarbonate resin composition containing the same, and an excellent heat resistance and good appearance. It relates to molded products.

  Polycarbonate resins are widely used in the fields of electrical and electronics, automobiles, and building materials because of their excellent electrical properties, flame retardancy, transparency, dimensional stability, mechanical properties, and light weight. Since it is particularly excellent in transparency, it is widely used as an optical material and is used in various optical lenses, automotive headlamp lenses, illumination gloves, crazing applications, and the like. It is also used as a flat display substrate film and retardation film for home appliances and mobile devices.

  Optical parts obtained from ordinary polycarbonate resin made of bisphenol A are used as optical parts in the vicinity of the heat source, or processed in a process exposed to a high temperature of 180 ° C. or higher, such as an alignment film formation process or an electrode formation process When used as a member such as a flat display film, there is a problem that heat resistance is insufficient.

  As means for solving this problem, there is a method of improving heat resistance using a polycarbonate resin derived from a bisphenol compound having a bulky structure, and various polycarbonate resins have been proposed. For example, a polycarbonate resin having a fluorene structure has been proposed (see Patent Documents 1 and 2). However, although these polycarbonate resins having a fluorene structure are excellent in heat resistance, when used as a raw material for a heat-melt molding method superior in mass production, the resin is inferior in fluidity, and therefore receives heat history inside the molding machine, resulting in heat deterioration. There was a problem that it was easy (it was easy to burn).

On the other hand, a polycarbonate resin derived from a siloxane compound having phenol, a bisphenol compound having a fluorene structure, and other bisphenol compounds, wherein the bisphenol compound component having a siloxane structure is a total monomer component (bisphenol compound having a siloxane structure + fluorene) A siloxane copolymer polycarbonate of 10 to 50% by weight with respect to a bisphenol compound having a structure + another bisphenol compound) has been proposed (see Patent Document 3). This siloxane copolymer polycarbonate resin is a resin excellent in wear resistance and weather resistance. However, it has been found that when the polycarbonate resin disclosed in Patent Document 3 is molded into a sheet film, the molded product may become slightly cloudy, which may be inappropriate for optical materials that require transparency.
Further, in order to continuously produce a film-like or sheet-like molded body, a process such as transporting and winding a long film on a support is necessary, and the transport is stably performed. The sheet-like and film-like molded bodies are required to have a certain degree of slipperiness.

JP-A-8-134198 JP-A-11-174424 JP 2002-284871 A

The problem to be solved by the present invention is to improve the appearance of a molded member made of a siloxane copolymer polycarbonate resin having excellent heat resistance and slipperiness.
More specifically, the present invention provides a siloxane-copolymerized polycarbonate and a polycarbonate resin composition that are excellent as heat resistance, and are useful as raw materials for molded articles that require good slipperiness and good appearance. This is the issue.
Moreover, this invention makes it a subject to provide the siloxane copolymer polycarbonate and polycarbonate resin composition which are hard to be thermally deteriorated and are suitable as a raw material of the molded object by a heat-melt-molding method.
Moreover, this invention makes it a subject to provide the molded article which consists of a polycarbonate resin composition which is excellent in heat resistance, is excellent in sliding property, and has a favorable external appearance.

  As a result of intensive studies to solve the conventional problems, the present inventors have found that a siloxane compound produced using a siloxane compound having phenol, a bisphenol compound having a fluorene structure, and another bisphenol compound having a predetermined structure. Obtained knowledge that polymerized polycarbonate is a material that is difficult to be thermally deteriorated (easily burned) and can also act as a lubricant, and in particular, the ratio of phenolic siloxane compound to all monomer components is within a predetermined range, And the above-mentioned siloxane copolymer polycarbonate having a glass transition point within a predetermined range is found to be useful as a raw material for a molded product having excellent heat resistance, good slipperiness, and good appearance. It came to be completed.

（式中、Ｒ¹〜Ｒ⁴は各々独立して水素原子、炭素原子数１〜５のアルキル基、炭素原子数６〜１２のアリール基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基、又は炭素原子数７〜１７のアラルキル基を表し、これらの基に炭素原子を有する場合には置換基として、炭素原子数１〜５のアルキル基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基を有していてもよい。） Means for solving the above problems are as follows.
[1] A siloxane compound having one or more phenols, a compound represented by one or more general formulas (A), and a compound represented by one or more general formulas (B) are converted to a carbonate ester-forming compound. A polycarbonate obtained by reacting, wherein the siloxane compound having one or more phenols is a monomer component (a siloxane compound having one or more phenols + one or more compounds represented by the general formula (A) + one kind) The siloxane copolymer polycarbonate which is 0.1 weight% or more and less than 10 weight% with respect to the compound represented by the said general formula (B), and whose glass transition temperature (Tg) is 180-240 degreeC.

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or the number of carbon atoms. Represents an alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, 2 to 2 carbon atoms 5 may have an alkenyl group and an alkoxy group having 1 to 5 carbon atoms.)

（Ｒ⁵〜Ｒ¹²は各々独立して、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１２のアリール基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基、炭素原子数７〜１７のアラルキル基を表し、これらの基に炭素原子を有する場合には置換基として、炭素原子数１〜５のアルキル基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基を有していてもよく；Ｘは、

(R ^{5 to} R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atom. Represents an alkoxy group having 5 carbon atoms and an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, the substituent may be an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Group, may have an alkoxy group of 1 to 5 carbon atoms;

であり；Ｒ¹³〜Ｒ¹⁶はそれぞれ、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基、又は炭素原子数６〜１２のアリール基を表すか、Ｒ¹³とＲ¹⁴又はＲ¹⁵とＲ¹⁶はそれぞれ、互いに結合して、炭素原子数３〜６の炭素環又は複素環を形成する基を表し、これらの基に炭素原子を有する場合には置換基として、炭素原子数１〜５のアルキル基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基を有していてもよく； aは０〜２０の整数を表す。）

R ^{13 to} R ¹⁶ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 to 6 carbon atoms. R ¹³ and R ¹⁴ or R ¹⁵ and R ¹⁶ are each bonded to each other to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms. In the case of having a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; The integer of 0-20 is represented. )

（式中、Ｒ¹⁷〜Ｒ²¹は各々独立して、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１２のアリール基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基、又は炭素原子数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素原子数１〜５のアルキル基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基を有していてもよく；Ｒ²²は炭素原子数１〜１０の脂肪族基を表すか、結合を表し；Ｙは、 [2] The compound having a siloxane structure having at least one phenol is a compound selected from the group consisting of General Formula (C), General Formula (D), General Formula (E), and General Formula (F). [1] Siloxane copolymer polycarbonate.

Wherein R ^{17 to} R ²¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. An alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms as a substituent. May have an alkenyl group of ˜5, an alkoxy group of 1 to 5 carbon atoms; R ²² represents an aliphatic group of 1 to 10 carbon atoms or represents a bond;

から選ばれた１種以上の構造単位の組合せからなる直鎖状もしくは分岐状の単独重合体、又はブロックもしくはランダム共重合体を表し、重合度は１〜２００であり；Ｒ²³〜Ｒ²⁷は各々独立して水素原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１２のアリール基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基、又は炭素原子数７〜１７のアラルキル基を表し、これらの基に炭素原子を有する場合には置換基として、炭素原子数１〜５のアルキル基、炭素原子数２〜５のアルケニル基、炭素原子数１〜５のアルコキシ基を有していてもよく；Ｚは、

Represents a linear or branched homopolymer or a block or random copolymer comprising a combination of one or more structural units selected from: a polymerization degree of 1 to 200; and R ^{23 to} R ²⁷ are Each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom Represents an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, the substituent is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to Optionally having 5 alkoxy groups; Z is

であり；Ｒ²⁸及びＲ²⁹はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又は各々置換基を有してもよい、炭素原子数１〜２０のアルキル基、炭素原子数１〜５のアルコキシ基、もしくは炭素原子数６〜１２アリール基を表すか、Ｒ²⁸とＲ²⁹が結合して、炭素原子数５〜２０の炭素環又は元素数５〜１２の複素環を形成する基を表し；Ｒ³⁰及びＲ³¹はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又は各々置換基を有してもよい、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、炭素原子数２〜１２のアルケニル基、もしくは炭素原子数６〜１２アリール基を表し；ｂは０〜２０の整数を表す。）

Each of R ²⁸ and R ²⁹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R ²⁸ and R ²⁹ are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements. R ³⁰ and R ³¹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 9 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; b represents an integer of 0 to 20; )

[3] The siloxane copolymer polycarbonate according to [2], wherein the compound having a siloxane structure having at least one phenol is a compound represented by the general formula (E).
[4] The siloxane copolymer polycarbonate of [2], wherein the compound having a siloxane structure having one or more phenols is a compound represented by the general formula (F).
[5] The siloxane copolymer polycarbonate according to [2], wherein the compound having a siloxane structure having at least one phenol is a compound represented by the general formula (C).
[6] The siloxane copolymer polycarbonate according to [2], wherein the compound having a siloxane structure having at least one phenol is a compound represented by the general formula (D).
[7] The siloxane copolymer polycarbonate according to any one of [1] to [6], which has an intrinsic viscosity [η] of 0.2 to 1.0 [dl / g].
[8] R ^{23 to} R ^{27 in} General Formula (C), General Formula (D), General Formula (E), and General Formula (F) are selected from a methyl group, an n-butyl group, and a phenyl group. The siloxane copolymer polycarbonate according to any one of [1] to [7], which is at least one kind.
[9] The compound represented by the one or more general formulas (A) is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, And the siloxane copolymer polycarbonate of any one of [1] to [8], which is a compound selected from the group consisting of 9,9-bis (4-hydroxy-2-methylphenyl) fluorene.
[10] The one or more compounds represented by the general formula (B) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenyl The siloxane copolymer polycarbonate of any one of [1] to [9], which is a compound selected from the group consisting of ethane.
[11] A polycarbonate resin composition containing the siloxane copolymer polycarbonate of any one of [1] to [10].
[12] The polycarbonate resin composition according to [11], further comprising a polycarbonate resin having a unit derived from 2,2-bis (4-hydroxyphenyl) propane.
[13] A molded article comprising the polycarbonate resin composition according to [11] or [12].
[14] A sheet-like or film-like molded article comprising the polycarbonate resin composition according to [11] or [12].

  The siloxane copolymer polycarbonate of the present invention is a siloxane copolymer polycarbonate produced using a siloxane compound having phenol, a bisphenol compound having a fluorene structure, and other bisphenol compounds. It is a material that acts as a lubricant and is difficult to be thermally deteriorated (easily burned). Therefore, the molded article of the present invention formed using the siloxane copolymer polycarbonate of the present invention has the effects of excellent heat resistance, good slipperiness, and good appearance.

1. Siloxane copolymer polycarbonate The present invention comprises a siloxane compound having one or more phenols, a compound represented by one or more general formulas (A), and a compound represented by one or more general formulas (B), A polycarbonate obtained by reacting with a carbonate ester-forming compound, wherein the siloxane compound having one or more phenols is represented by all monomer components (a siloxane compound having one or more phenols plus one or more general formulas (A)). Siloxane having a glass transition temperature (Tg) of 180 to 240 ° C. and not less than 0.1% by weight and less than 10% by weight with respect to the compound of formula (1) or a compound represented by one or more general formulas (B) The present invention relates to a copolymerized polycarbonate.

In the formula, R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 carbon atom. Represents an alkoxy group having 5 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, the substituent is an alkyl group having 1 to 5 carbon atoms or 2 to 5 carbon atoms. Or an alkoxy group having 1 to 5 carbon atoms.
In the above formula, R ¹ and R ² , and R ³ and R ⁴ , each preferred combination is an alkyl having one hydrogen atom and the other having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms). It is a group.

Examples of the compound represented by the general formula (A) that can be used in the present invention include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl). Fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, 3,6-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methoxy-4-) Hydroxyphenyl) fluorene, 9,9-bis (3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (3-methyl) Such as 4-hydroxyphenyl) fluorene and 3,6-diphenyl-9,9-bis (4-hydroxyphenyl) fluorene are included.
Among these, in particular, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methyl) Phenyl) fluorene is preferred.
In the present invention, only one type of the compound represented by the formula (A) may be used, or two or more types may be used in combination.

  In the present invention, as the bisphenol compound having a fluorene structure represented by the general formula (A), it is preferable to use a compound purified to 98% or more, and a compound purified to 99% or more is used. More preferred. In particular, the use of materials containing various isomers such as isomers including 2,4'-dihydroxy compounds is not preferred because the reactivity is lowered and the control of polymerization becomes difficult.

In the formula, R ^{5 to} R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or the number of carbon atoms. An alkoxy group having 1 to 5 carbon atoms and an aralkyl group having 7 to 17 carbon atoms are represented, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms or a carbon atom having 2 to 5 carbon atoms can be used as a substituent. Or an alkoxy group having 1 to 5 carbon atoms; X is

R ^{13 to} R ¹⁶ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 to 6 carbon atoms. R ¹³ and R ¹⁴ or R ¹⁵ and R ¹⁶ are each bonded to each other to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms. In the case of having a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; The integer of 0-20 is represented.

In the formula (B), R ^{5 to} R ⁸ are preferably all hydrogen atoms, or one is an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) and the others are And R ^{9 to} R ¹² are preferably all hydrogen atoms, or one is an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) and the others are hydrogen atoms. Is an atom.
R ¹³ and R ¹⁴ are preferably both hydrogen atoms, or one is a hydrogen atom and the other or both are the same or different, each having 1 to 10 carbon atoms, An alkenyl group having 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms; more preferably, both are hydrogen atoms, or both are the same or different. An alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
Further, a is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 or 3.

Examples of the bisphenol compound represented by formula (B) that can be used in the present invention include 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis ( 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1 -Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) ) Butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Droxy-3-methylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-allylphenyl) propane, 3,3,5-trimethyl-1,1- Bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4 ′-[1,3-phenylene (1-methylethylidene)] bisphenol, 4,4 ′-[ 1,4-phenylene (1-methylethylidene)] bisphenol and the like.
Among these, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1, 1-bis (4-hydroxyphenyl) -1-phenylethane and 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane are preferred.
In the present invention, only one type of compound represented by the formula (B) may be used, or two or more types may be used in combination.

  Examples of the siloxane compound having phenol that can be used in the present invention include compounds represented by general formula (C), general formula (D), general formula (E), and general formula (F).

In the formula, R ^{17 to} R ²¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or the number of carbon atoms. An alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms or 2 to 2 carbon atoms as a substituent. 5 may have an alkenyl group and an alkoxy group having 1 to 5 carbon atoms; R ²² represents an aliphatic group having 1 to 10 carbon atoms or a bond. Y is

Represents a linear or branched homopolymer or a block or random copolymer composed of a combination of one or more structural units selected from: a degree of polymerization of 1 to 200 (preferably 5 to 100, more preferably 10 to 80, more preferably 20 to 70, and still more preferably 20 to 60); R ^{23 to} R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. Represents an aryl group having 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and if these groups have a carbon atom, they are substituted As a group, you may have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group. Z is

Is preferred. R ²⁸ and R ²⁹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or each having 1 to 20 carbon atoms (preferably 1 to 10, more preferably, each having a substituent). 1-5) represents an alkyl group, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or R ²⁸ and R ²⁹ are bonded to each other to form 5 to 20 carbon atoms (preferably 5 to 10, more preferably 5 to 7) represents a group that forms a carbocyclic ring or a heterocyclic ring having 5 to 12 elements; R ³⁰ and R ³¹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, An iodine atom, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 6 to 6 carbon atoms, each optionally having a substituent 12 represents an aryl group; b is 0 to 20 (preferably Ku 1 to 10, more preferably an integer of more preferred) that is 1～5,2 or 3.

In the formula (C), the hydroxy group is preferably substituted at the para position with respect to —C (R ²¹ ) (R ²² —Y) —. In formula (C), R ^{17 to} R ²⁰ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms). One of R ¹⁷ and R ¹⁸ is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms); and one of R ¹⁹ and R ²⁰ is a hydrogen atom, and the other is More preferably, it is an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms). Incidentally, the substitution position of the alkyl ^{group, -C (R 21) (R} 22 -Y) - preferably a meta-position with respect to.

In formula (D), the hydroxy group is preferably substituted at the ortho position or para position relative to -R ²² -Y, more preferably substituted at the ortho position. In Formula (D), R ¹⁷ and R ¹⁸ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms), or an alkoxy group having 1 to 5 carbon atoms. Preferably, both are hydrogen atoms.

In formula (E), the hydroxy group is preferably substituted at the para position with respect to -Z-, and -R ²² -Y is substituted at the meta position with respect to -Z-. Is preferred. In the formula (E), R ^{17 to} R ²⁰ are each preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms), and all are hydrogen atoms. It is more preferable that

Wherein (F), hydroxy ^{group, -R 22 -Y-Si (R} 23) (R 24) -R 22 - respect is preferably substituted at the ortho or para position, the ortho position More preferably, it is substituted. In the formula (F), R ^{17 to} R ²⁰ are each an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms) or an alkoxy group having 1 to 5 carbon atoms. It is more preferable that all are hydrogen atoms.

In the formulas (C) to (F), the substituent of the shiroquine segment, that is, R ^{23 to} R ²⁷ is preferably selected from a methyl group, an n-butyl group, and a phenyl group. These may be the same or different from each other.

Examples of the siloxane compound represented by the formula (C) include a compound represented by the following formula (C ′).

R ²² and R ²⁷ in the formula (C ') are respectively synonymous with R ²² and R ²⁷ in the formula (C), x is a number from 10 to 80.
Wherein (C '), R ²² is C ₁ ~ ₁₀ (more preferably C ₅ ~ ₁₀₎ is preferably an alkylene group, and R ²⁷ is C ₁ ~ ₁₀ (more preferably C ₁ ~ ₅₎ It is preferably an alkyl group, and x is preferably a number of 20 to 60.

  Examples of the siloxane compound represented by the formula (C) include, but are not limited to, compounds having the following structural formula. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

The Y ^c preferably contains 1 to 200 (preferably 5 to 100, more preferably 10 to 80, still more preferably 20 to 70, still more preferably 20 to 60) dimethylsiloxane units. Among them, in particular, α-11-bis (4-hydroxyphenyl) undecane-ω-butyl-polydimethylsiloxane and α-3-bis (4-hydroxyphenyl) -2-methylpropane-ω-butyl-polydimethylsiloxane Is preferred.

Examples of the compound represented by the formula (D) include a compound represented by the following formula (D ′).

R ²² and R ²⁷ in the formula (D ') are respectively synonymous with R ²² and R ²⁷ in the formula (D), x is a number from 10 to 80.
Wherein (D '), R ²² is C ₁ ~ ₁₀ (more preferably C ₅ ~ ₁₀₎ is preferably an alkylene group, and R ²⁷ is C ₁ ~ ₁₀ (more preferably C ₁ ~ ₅₎ It is preferably an alkyl group, and x is preferably a number of 20 to 60.

  Examples of the siloxane compound represented by the formula (D) include, but are not limited to, the following structural formulas. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

Y ^d contains 1 to 200 (preferably 5 to 100, more preferably 10 to 80, more preferably 20 to 70, and still more preferably 20 to 60) dimethylsiloxane. Among them, in particular, α-3- (2-hydroxyphenyl) propyl-ω-butyl-polydimethylsiloxane, α-3- (4-hydroxyphenyl) propyl-ω-butyl-polydimethylsiloxane, α-3- (4 -Hydroxy-3-methoxy-phenyl) propyl-ω-butyl-polydimethylsiloxane is preferred.

Examples of the compound represented by the formula (E) include a compound represented by the following formula (E ′).

R ²² and R ²⁷ in the formula (E ') has the same meaning as R ²² and R ²⁷ in formula (E), x is a number from 10 to 80.
Wherein (E '), is preferably R ²² is an alkylene group of C ₁ ~ ₁₀ (more preferably C ₁ ~ _5), alkyl R ²⁷ is C ₁ ~ ₁₀ (more preferably C ₁ ~ ₅₎ It is preferably a group, and x is more preferably 20 to 60.

  Examples of the siloxane compound represented by the formula (E) include, but are not limited to, the following structural formulas. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

The Y ^e preferably contains 1 to 200 (preferably 5 to 100, more preferably 10 to 80, still more preferably 20 to 70, and still more preferably 20 to 60) dimethylsiloxane. Among these, 2,2-bis (4-hydroxy-3-polydimethylsiloxypropyl) propane is particularly preferable.

Examples of the compound represented by the formula (F) include a compound represented by the following formula (F ′).

R ²² in the formula (F ') has the same meaning as R ²² in formula (F), x is a number from 10 to 80.
Wherein (F '), R ²² is preferably (more preferably _{C 1 ~ 5) C 1 ~} 10 alkylene group, x is preferably a number of 20 to 60.

  Examples of the siloxane compound represented by the formula (F) include, but are not limited to, the following structural formulas. In the compound of the following structural formula, the siloxane segment may be linear or branched, and two or more segments may be the same as or different from each other.

The Y ^f preferably contains 1 to 100 (preferably 5 to 100, more preferably 10 to 80, still more preferably 20 to 70, and still more preferably 20 to 60) dimethylsiloxane. Among these, α, ω-bis [3- (2-hydroxyphenyl) propyl] polydimethylsiloxane is particularly preferable.

The siloxane compound having one or more phenols used in the production of the siloxane copolymer polycarbonate of the present invention is represented by all monomer components (siloxane compound having one or more phenols + 1 general formula (A)). Compound + 1 or more compounds represented by general formula (B); hereinafter referred to as “total monomer component” means the total weight of these three monomers) and is 0.1% by weight or more and less than 10% by weight It is preferable that it is 0.3% by weight or more and less than 8% by weight, and more preferably 0.5% by weight or more and less than 6% by weight.
On the other hand, the compound represented by the one or more general formulas (A) is preferably more than 60% by weight and less than 98% by weight, and more than 65% by weight and less than 90% by weight with respect to all monomer components. More preferably. On the other hand, the compound represented by the one or more general formulas (B) is lower in weight ratio than the compound represented by the one or more general formulas (A), and has the one or more phenols. It is preferably higher than the weight ratio of the siloxane compound, specifically, more than 1% by weight and less than 39% by weight, preferably 9% by weight or more and 34% by weight or less.
In the present invention, two or more kinds of the siloxane compound having phenol, the compound represented by the general formula (A), and the compound represented by the general formula (B) may be used. This siloxane copolymer polycarbonate does not contain units derived from bisphenols other than the above three types of monomers.

On the other hand, examples of the carbonic acid ester forming compound usable in the present invention include phosgene and diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. And bisallyl carbonate.
In the production of the polycarbonate of the present invention, only one type of carbonate ester-forming compound may be used, or two or more types may be used in combination.

  The siloxane copolymer polycarbonate of the present invention can be produced by various methods used in producing a polycarbonate from bisphenol A and a carbonic acid ester-forming compound, for example, a direct reaction between bisphenols and phosgene (phosgene method), and bisphenols and bisphenols. It can be produced by adopting any method such as a transesterification reaction with an aryl carbonate (transesterification method).

  In the phosgene method and the transesterification method, the phosgene method is preferable in consideration of the reactivity of the siloxane compound having phenol, the compound represented by the general formula (A), and the compound represented by the general formula (B). .

  In the phosgene method, the bisphenols and phosgene are usually reacted in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride and chloroform. Furthermore, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used to accelerate the condensation polymerization reaction, and phenol, pt-butylphenol, p-cumylphenol are used for adjusting the degree of polymerization. It is preferable to add a monofunctional compound such as a long-chain alkyl-substituted phenol as a molecular weight regulator. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction is usually in the range of 0 to 150 ° C, preferably 5 to 40 ° C. While the reaction time depends on the reaction temperature, it is generally 0.5 min-10 hr, preferably 1 min-2 hr. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

  On the other hand, in the transesterification method, the bisphenols and bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, but is usually about 1 to 24 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding a molecular weight regulator, antioxidant, and a branching agent as needed.

  The siloxane copolymer polycarbonate of the present invention can be molded by a known molding method such as melt extrusion molding, injection molding, compression molding or wet molding in order to form a sheet film. In particular, since it is difficult to be thermally deteriorated, it is suitable as a raw material for a heat melt molding method such as a melt extrusion molding method.

  In order to use the raw material for the melt extrusion molding, the intrinsic viscosity is preferably in the range of 0.2 to 1.0 dl / g, and the intrinsic viscosity is more preferably in the range of 0.3 to 0.6 dl / g. The intrinsic viscosity is particularly preferably in the range of 0.33 to 0.42 dl / g. If the intrinsic viscosity of the polycarbonate resin is lower than 0.2 dl / g, the mechanical strength is low when it is formed into a sheet film, and if it is higher than 1.0 dl / g, the moldability is inferior.

  The siloxane copolymer polycarbonate of the present invention has a glass transition temperature (Tg) of 180 to 240 ° C, preferably 180 to 230 ° C, and more preferably 180 to 220 ° C. Since the siloxane copolymer polycarbonate of the present invention has a glass transition temperature in the above-mentioned range, it is hardly subject to thermal deterioration, and maintains a good appearance even when a molded product is produced by a simple method such as a hot melt forming method. it can.

2. Polycarbonate resin composition The present invention also relates to a polycarbonate resin composition containing the siloxane copolymer polycarbonate of the present invention.
The siloxane copolymer polycarbonate of the present invention can be used alone as a raw material for various molded articles. Moreover, the composition which added the 1 or more types of additive to the siloxane copolymer polycarbonate of this invention can also be utilized as raw materials, such as a molded article. Examples of additives include additives added for the purpose of ensuring the stability and releasability required during molding, specifically, hindered phenolic and phosphite antioxidants; Silicon-based, fatty acid ester-based, fatty acid-based, fatty acid glyceride-based, natural wax and other lubricants and mold release agents; benzotriazole-based, benzophenone-based, dibenzoylmethane-based, salicylate-based light stabilizers; polyalkylene glycol And antistatic agents such as fatty acid glycerides; These will be added in an amount of about 1% by weight or less based on the siloxane copolymer polycarbonate as the main component.

  In addition, the siloxane copolymer polycarbonate of the present invention can be used by mixing with other polycarbonates. Examples of other polycarbonates include polycarbonate resins having units derived from 2,2-bis (4-hydroxyphenyl) propane. However, the transition temperature of the other polycarbonate resin is preferably about 140 to 155 ° C. so as not to impair effects such as heat resistance and resistance to thermal degradation of the siloxane copolymer polycarbonate of the present invention. Some polycarbonates having units derived from bisphenol A having a glass transition temperature in the above range are commercially available, for example, “Iupilon E-2000R”, “Iupilon S-3000R” (Mitsubishi). Engineering Plastics Co., Ltd.), Iupilon S-1000R, Iupilon S-2000R, Iupilon H-3000R, Iupilon H-4000 (all manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are examples, and these commercial products are used. It is also preferable to do this.

  In the aspect of the mixture of the siloxane copolymer polycarbonate of the present invention and the polycarbonate resin having a unit derived from 2,2-bis (4-hydroxyphenyl) propane, the mixing ratio is not particularly limited, depending on the application. It can be determined as appropriate. In order not to impair the effect of the siloxane copolymer polycarbonate of the present invention, the siloxane copolymer polycarbonate of the present invention is preferably mixed in an amount exceeding 50% by weight, more preferably 80% by weight or more. One aspect of the polycarbonate resin composition of the present invention includes a mixture of the siloxane copolymer polycarbonate of the present invention and a polycarbonate resin having units derived from 2,2-bis (4-hydroxyphenyl) propane, provided that It is a composition containing no other polycarbonates.

  In addition, there is no restriction | limiting in particular as a method of mixing 2 or more types of polycarbonate, The method of mixing in a solid state, The method of mixing in a molten state, One resin is made into a solid state, The other resin is mixed in a molten state Any method may be used.

3. Molded Article The present invention also relates to a molded article made of the siloxane copolymer polycarbonate of the present invention or composed of a composition containing the siloxane copolymer polycarbonate of the present invention. There is no restriction | limiting in particular about a shaping | molding method, It can shape | mold by various shaping | molding methods, such as melt extrusion molding, injection molding, compression molding, and wet molding. In particular, the melt extrusion molding method is preferable because it is a simple molding method.

There is no restriction | limiting in particular about the shape of the molded article of this invention. The thing shape | molded by the sheet form and the film form is mentioned.
The molded article of the present invention can be widely used as a member in the electric / electronic field, the automobile field, and the building material field. Particularly, since it exhibits high heat resistance, it is suitable for optical parts used in the vicinity of a heat source, flat display films produced through a process exposed to heat, and the like.
The molded product of the present invention is excellent in heat resistance, and can achieve a load deflection temperature (DTUL) of 1.80 MPa of 160 ° C. or higher.
Further, the molded article of the present invention has good slipperiness, and specifically can achieve a coefficient of static friction of 0.4 or less.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention does not receive a restriction | limiting at all to a following example.
1. Synthesis of Siloxane Copolymer Polycarbonate of the Present Invention [Synthesis Example 1]
To 700 ml of a 7.0 w / w% aqueous sodium hydroxide solution, 68.3 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as “BCFL”). 181 mol), 2,2-bis (4-hydroxyphenyl) propane (manufactured by Mitsui Chemicals, hereinafter abbreviated as “BPA”) 21.8 g (0.096 mol), triethylbenzylammonium chloride 0.08 g, and hydrosulfite 0.2 g was dissolved.
To this, 500 ml of methylene chloride was added, and 39 g of phosgene was continuously blown in 30 minutes while maintaining the temperature at 15 ° C. while stirring.
After completion of phosgene blowing, 1.73 g of pt-butylphenol (hereinafter abbreviated as “PTBP”) and 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-1”) were added. The mixture was vigorously stirred to emulsify the reaction solution. After emulsification, 1 ml of triethylamine was added, and the mixture was stirred at 20 to 25 ° C. for about 1 hour for polymerization.

After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the previous solution (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 60 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate. The resulting precipitate was filtered and dried at 120 ° C. for 24 hours to obtain a polymer powder.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.40 dl / g. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, represented by the following structural formula having a carbonate bond Polycarbonate resin (hereinafter abbreviated as PC-1).

[Synthesis Example 2]
Synthesis was performed in the same manner as in Example 1 except that 0.91 g of Si-1 was changed to 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-2”).

  The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-2) was 0.42 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 3]
Synthesis was performed in the same manner as in Example 1 except that 0.91 g of Si-1 was changed to 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-3”).

  The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-3) was 0.39 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 4]
The synthesis was performed in the same manner as in Example 1 except that 0.91 g of Si-1 was changed to 0.91 g of a siloxane monomer having the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “Si-4”).

  The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-4) was 0.36 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 5]
68.3 g (0.181 mol) of BCFL and 21.8 g (0.096 mol) of BPA, 68.3 g (0.181 mol) of BCFL and 2,2-bis (4-hydroxy-3-methylphenyl) propane (Honshu Chemical) Kogyo Co., Ltd., hereinafter abbreviated as “BPC”) 22.3 g (0.087 mol), except that Si-1 0.91 g was changed to Si-1 0.46 g. Synthesis was performed. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-5) was 0.36 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 6]
BCFL 68.3 g (0.181 mol) and BPA 21.8 g (0.096 mol) were changed to BCFL 68.3 g (0.181 mol) and BPC 18.2 g (0.071 mol), and Si-1 0.91 g Was synthesized in the same manner as in Example 1 except that Si-1 was changed to 4.55 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-6) was 0.34 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 7]
BCFL 68.3 g (0.181 mol) and BPA 21.8 g (0.096 mol) were changed to BCFL 68.3 g (0.181 mol) and BPC 21.8 g (0.085 mol), and Si-1 0.91 g Was synthesized in the same manner as in Example 1 except that Si-1 was changed to 0.46 g and Si-4 0.45 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-7) was 0.35 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 8]
BCFL 68.3g (0.181mol) and BPA 21.8g (0.096mol), BCFL 59.2g (0.157mol) and 1,1-bis (4-hydroxyphenyl) ethane (Honshu Chemical Co., Ltd. make) The following synthesis was performed in the same manner as in Example 1 except that the amount was changed to 30.9 g (0.144 mol). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-8) was 0.41 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 9]
68.3 g (0.181 mol) of BCFL and 21.8 g (0.096 mol) of BPA, 81.9 g (0.217 mol) of BCFL and 1,1-bis (4-hydroxyphenyl) -1-phenylethane (Honshu Chemical) The synthesis was carried out in the same manner as in Example 1 except that it was changed to 8.2 g (0.028 mol) manufactured by Kogyo Co., Ltd. (hereinafter abbreviated as “BPAP”). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-9) was 0.36 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 10]
68.3 g (0.181 mol) of BCFL and 21.8 g (0.096 mol) of BPA, 68.3 g (0.181 mol) of BCFL and 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenyl Synthesis was carried out in the same manner as in Example 1 except that the amount was changed to 21.8 g (0.069 mol) of ethane (Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as “CBPAP”). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-10) was 0.33 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

2. Synthesis of Comparative Example Polycarbonate [Synthesis Example 11]
BCFL 68.3 g (0.181 mol) and BPA 21.8 g (0.096 mol) were changed to BCFL 68.3 g (0.181 mol) and BCPA 22.8 g (0.100 mol), and Si-1 0.91 g Synthesis was performed in the same manner as in Example 1 except that was not added. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-11) was 0.41 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 12]
BCFL 68.3 g (0.181 mol) and BPA 21.8 g (0.096 mol) were changed to BCFL 68.3 g (0.181 mol) and BPC 22.7 g (0.089 mol), and Si-1 0.91 g was changed to Si- 1 Synthesis was performed in the same manner as in Example 1 except that the amount was changed to 0.09 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-12) was 0.37 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 13]
BCFL 68.3 g (0.181 mol) and BPA 21.8 g (0.096 mol) were changed to BCFL 68.3 g (0.181 mol) and BPC 9.1 g (0.036 mol), and Si-1 0.91 g Was synthesized in the same manner as in Example 1 except that Si-1 was changed to 13.65 g. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-13) was 0.33 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 14]
Except that 68.3 g (0.181 mol) of BCFL and 21.8 g (0.096 mol) of BPA were changed to 54.6 g (0.144 mol) of BCFL and 35.5 g (0.139 mol) of BPC, Example 1 Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-14) was 0.41 dl / g.

[Synthesis Example 15]
Except that 68.3 g (0.181 mol) of BCFL and 21.8 g (0.096 mol) of BPA were changed to 89.2 g (0.236 mol) and 0.9 g (0.004 mol) of BCPA, Example 1 and Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-15) was 0.43 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

3. Properties of the synthesized polycarbonate The properties of the polycarbonates produced in Synthesis Examples 1 to 15 are summarized in Table 1 below.
The intrinsic viscosity is a value measured by preparing a 0.5% dichloromethane solution of each polymer at a temperature of 20 ° C. and using a Huggins constant of 0.45.
The glass transition temperature (Tg) is a value (Tg calculated by the tangent method) measured under a nitrogen stream with Shimadzu Corporation DCS-50.

4). Manufacture and evaluation of molded products [Examples 1 to 10]
After conducting scale-up trial production at the same raw material charging ratio as in Synthesis Examples 1 to 10 and securing 30 kg or more of polymer powder capable of measuring physical properties, respectively, tris (2,4-ditertiarybutylphenyl) phosphine was added to PC-1 to 10. The powder mixed with 0.01% by weight of phyto was introduced into an extruder with a vent (20 mm single screw extruder, manufactured by Ishinaka Iron Works Co., Ltd., cylinder temperature 320 ° C.) and pelletized.
(1) Heat resistance evaluation (measurement of DTUL)
Test pieces (dimensions 80 mm × 10 mm × 4 mm) were respectively molded with an injection molding machine (J50E-D manufactured by Nippon Steel Works, Ltd .: cylinder temperature 320 ° C.) using each of the produced pellets. About each test piece, DTUL was implemented and measured based on JISK7191 (1.80 Mpa). The results are shown in Table 2 below.
(2) Evaluation of slipperiness (coefficient of static friction) and sheet appearance In addition, each obtained pellet was introduced into an extruder (25 mm single-screw extruder with vent, MK-25 manufactured by Musashinokikai Co., Ltd., cylinder temperature 320 ° C.), After passing through a T die, the sheet was cooled by two horizontal rolls (roll temperature: 180 ° C.) to produce extruded sheets (thickness of 100 μm). With respect to the surface of each obtained sheet, the static friction coefficient was measured at 6 ball using a tribogear portable friction meter “TYPE: 94i-II” manufactured by Shinto Kagaku Co., Ltd. In addition, the visual appearance evaluation of the sheet was performed.

[Example 11]
A scale-up trial was carried out at the same raw material charge ratio as in Synthesis Example 10 to ensure 20 kg or more of polymer powder. 20 kg of the powder and 10 kg of “Iupilon S-3000R” (Mitsubishi Engineering Plastics Co., Ltd.) were mixed and pelletized in the same manner as in Examples 1-10.
Using the obtained pellets, injection molding was performed in the same manner as in Examples 1 to 10, and DTUL measurement was performed.
Further, the obtained pellets were subjected to extrusion sheet molding in the same manner as in Examples 1 to 10, and the surface of the obtained sheet was subjected to measurement of the static friction coefficient and visual evaluation of the sheet appearance.

[Comparative example]
After performing scale-up trial production at the same raw material charging ratio as in Synthesis Examples 11 to 15 and securing 30 kg or more of polymer powder that can be formed into a sheet, the test piece for DTUL measurement of PC-11 to 15 is also used in the same manner as in the examples. Injection molding was performed and DTUL measurement was performed.
Further, extrusion sheet molding was performed in the same manner as in the examples. With respect to the surface of the obtained sheet, measurement of the coefficient of static friction and visual evaluation of the sheet appearance were performed.

Claims (14)

A siloxane compound having one or more phenols, a compound represented by one or more general formulas (A), and a compound represented by one or more general formulas (B) are reacted with a carbonate ester-forming compound. The obtained polycarbonate, wherein the siloxane compound having one or more phenols is a monomer component (a siloxane compound having one or more phenols + one or more compounds represented by the general formula (A) + one or more general compounds) The siloxane copolymer polycarbonate which is 0.1 weight% or more and less than 10 weight% with respect to the compound represented by Formula (B), and whose glass transition temperature (Tg) is 180-240 degreeC.

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or the number of carbon atoms. Represents an alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, 2 to 2 carbon atoms 5 may have an alkenyl group and an alkoxy group having 1 to 5 carbon atoms.)

(R ^{5 to} R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atom. Represents an alkoxy group having 5 carbon atoms and an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, the substituent may be an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Group, may have an alkoxy group of 1 to 5 carbon atoms;

R ^{13 to} R ¹⁶ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 to 6 carbon atoms. R ¹³ and R ¹⁴ or R ¹⁵ and R ¹⁶ are each bonded to each other to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms. In the case of having a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; The integer of 0-20 is represented. ) The compound having a siloxane structure having one or more phenols is a compound selected from the group consisting of General Formula (C), General Formula (D), General Formula (E), and General Formula (F). The siloxane copolymer polycarbonate described in 1.

Wherein R ^{17 to} R ²¹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom. An alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms as a substituent. May have an alkenyl group of ˜5, an alkoxy group of 1 to 5 carbon atoms; R ²² represents an aliphatic group of 1 to 10 carbon atoms or represents a bond;

Represents a linear or branched homopolymer or a block or random copolymer comprising a combination of one or more structural units selected from: a polymerization degree of 1 to 200; and R ^{23 to} R ²⁷ are Each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom Represents an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, the substituent is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to Optionally having 5 alkoxy groups; Z is

Each of R ²⁸ and R ²⁹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R ²⁸ and R ²⁹ are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 elements. R ³⁰ and R ³¹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 9 carbon atoms, each of which may have a substituent, carbon Represents an alkoxy group having 1 to 5 atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; b represents an integer of 0 to 20; ) The siloxane copolymer polycarbonate according to claim 2, wherein the compound having a siloxane structure having at least one phenol is a compound represented by the general formula (E). The siloxane copolymer polycarbonate according to claim 2, wherein the compound having a siloxane structure having at least one phenol is a compound represented by the general formula (F). The siloxane copolymer polycarbonate according to claim 2, wherein the compound having a siloxane structure having at least one phenol is a compound represented by the general formula (C). The siloxane copolymer polycarbonate according to claim 2, wherein the compound having a siloxane structure having at least one phenol is a compound represented by the general formula (D). The intrinsic viscosity [η] is 0.2 to 1.0 [dl / g]. The siloxane copolymer polycarbonate according to any one of claims 1 to 6. R ^{23 to} R ^{27 in the} general formula (C), the general formula (D), the general formula (E), and the general formula (F) are at least one selected from a methyl group, an n-butyl group, and a phenyl group. The siloxane copolymer polycarbonate according to any one of claims 1 to 7. The one or more compounds represented by the general formula (A) are 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9, The siloxane copolymer polycarbonate according to any one of claims 1 to 8, which is a compound selected from the group of 9-bis (4-hydroxy-2-methylphenyl) fluorene. The one or more compounds represented by the general formula (B) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Consisting of bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane The siloxane copolymer polycarbonate according to any one of claims 1 to 9, which is a compound selected from the group. The polycarbonate resin composition containing the siloxane copolymer polycarbonate of any one of Claims 1-10. The polycarbonate resin composition according to claim 11, further comprising a polycarbonate resin having units derived from 2,2-bis (4-hydroxyphenyl) propane. A molded article comprising the polycarbonate resin composition according to claim 11 or 12. A sheet-like or film-like molded article comprising the polycarbonate resin composition according to claim 11 or 12.