JP2005126640A - Polycarbonate resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin excellent in wear resistance and solubility to organic solvents. <P>SOLUTION: The polycarbonate resin has repeating units represented by general formula (1) (in formula, R<SP>1</SP>and R<SP>2</SP>each represents a group selected from methyl, ethyl, cyclohexyl and phenyl). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polycarbonate resin, more specifically, it is excellent in abrasion resistance due to the introduction of a cyclopentyl skeleton, and has a substituent at the ortho position of the carbonate, or is a polycarbonate resin copolymerized with other components, The present invention relates to a polycarbonate resin having crystallinity reduced from that of a polycarbonate resin made of cyclopentyl bisphenol and having excellent solubility in an organic solvent.

Polycarbonate resin is used as a material in various fields, such as optical materials such as optical films, optical disks, and lenses, and housings for electrical equipment, etc., but with the expansion of application fields, development of polycarbonate resins with even better performance Is desired.
In particular, polycarbonate is often used in the form of dispersing substances (compounds, dyes, pigments, inorganic particles, organic particles) having various functions (electrical, optical, and mechanical functions). It is coming.
In such applications, the conventionally known bisphenol A type polycarbonates have been pointed out as problems such as being easily worn by friction and low solubility in organic solvents. Polycarbonates (for example, see Patent Document 1), siloxane-containing polycarbonates (for example, see Patent Document 2), cyclopentylidene bisphenol-type polycarbonates (for example, see Patent Document 3), and the like have been proposed, but satisfy the above problems at the same time. It has not reached.
In addition, due to the recent increase in environmental problems, halogen solvents such as liquefied methylene, which have been used as coating solvents for organic electrophotographic photoreceptors, have been changed to non-halogen solvents such as toluene and tetrahydrofuran (THF). Switching is advancing. In that case, if a conventional polycarbonate resin, particularly a polycarbonate resin containing bisphenol A, is used, the solubility in a non-halogen solvent is low, or even if dissolved, the coating solution gradually crystallizes, causing a problem in storage stability. In addition, there is a problem in that appearance defects such as whitening occur on the photoreceptor during film formation.

Japanese Patent No. 1807474 Japanese Patent Laid-Open No. 10-232503 JP-A 63-261267

The present invention has been made under the above circumstances, and solves the above-mentioned problems observed when a polycarbonate resin made from bisphenol A or bisphenol Z is used as a binder resin, and achieves the following matters: It is the purpose.
(1) To provide a polycarbonate resin capable of producing a good and stable coating solution even when a non-halogen solvent is used.
(2) A polycarbonate resin that has a new chemical structure that is suitable for use in various functional materials in a dispersed manner, and that is suitable for use in optical films, sheets, coatings, etc. I will provide a.
(3) To provide a polycarbonate resin that maintains excellent mechanical strength (wear resistance and scratch resistance) over a long period of time.

As a result of extensive research, the present inventors have obtained a polycarbonate resin having excellent wear resistance by introducing a cyclopentyl skeleton and having a substituent at the ortho position of the carbonate or copolymerized with other components. Thus, it has been found that the crystallinity is reduced as compared with the polycarbonate resin composed of cyclopentyl bisphenol, and therefore, it has excellent solubility in an organic solvent and is suitable for the above purpose. The present invention has been completed based on such findings.
That is, the gist of the present invention is as follows.
[1] The following general formula (1)

（式中、Ｒ¹ およびＲ² は、メチル基、エチル基、シクロヘキシル基およびフェニル基から選ばれる基を示す。）

(In the formula, R ¹ and R ² represent a group selected from a methyl group, an ethyl group, a cyclohexyl group, and a phenyl group.)

A polycarbonate resin having a repeating unit represented by:
[2] The polycarbonate resin further has a reduced viscosity [η _sp / C] at 20 ° C. of a 0.5 g / deciliter solution having a concentration of methylene chloride as a solvent of 0.35 deciliter / g or more and less than 3.6 deciliter / g. The polycarbonate resin of [1] above.
[3] Polycarbonate resin is further represented by the following general formula (2)

（式中、Ｒ³ 〜Ｒ⁶ は炭素数１〜６のアルキル基を示す。ａ〜ｃは０〜５の整数、ｄ〜ｇは０以上の整数であり、ｄ＋ｅ＋ｆ＋ｇは３〜１００の整数である。）

(Wherein R ^{3 to} R ⁶ represent an alkyl group having 1 to ⁶ carbon atoms, a to c are integers of 0 to 5, d to g are integers of 0 or more, and d + e + f + g is an integer of 3 to 100. is there.)

The polycarbonate resin according to [1] or [2] above, containing 0.1 to 20% by mass of the repeating unit represented by
[4] (A) The following general formula (3)

（式中、Ｒ⁷ 〜Ｒ¹⁰は、水素原子、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、炭素数３〜１２のシクロアルキル基およびハロゲン原子から選ばれる基を示す。）

(In the formula, R ^{7 to} R ¹⁰ represent a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a halogen atom. .)

A repeating unit represented by formula (B) (b-1):

[Wherein, R ¹¹ and R ¹² represent a group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a halogen atom. m and n are integers of 0-4. X is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ¹³ R ¹⁴ — (wherein R ¹³ and R ¹⁴ are a hydrogen atom, CF ₃ , substituted Or a group selected from an unsubstituted alkyl group having 1 to 12 carbon atoms and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.), A substituted or unsubstituted cycloalkylidene group having 5 to 11 carbon atoms A substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, a substituted or unsubstituted 9,9-fluorenylidene group, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, the following general formula

（式中、Ｒ¹⁵〜Ｒ¹⁷は、ＣＦ₃ 、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基、炭素数３〜１２のシクロアルキル基、炭素数１〜６のアルコキシ基および炭素数６〜１２のアリールオキシ基から選ばれる基を示す。）

Wherein R ^{15 to} R ¹⁷ are CF ₃ , a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 1 to 6 carbon atoms. A group selected from an alkoxy group and an aryloxy group having 6 to 12 carbon atoms.)

A divalent group derived from natural terpenes represented by the formula:

（式中、Ｒ¹⁸〜Ｒ²¹は、Ｒ¹⁵〜Ｒ¹⁷と同様の基を示す。）

(In the formula, R ^{18 to} R ²¹ represent the same groups as R ^{15 to} R ^17. )

The group chosen from C8-C16 alkylidene arylene alkylidene group represented by these is shown. ]
And (b-2) the following general formula (5)

（式中、Ｒ²²およびＲ²³は、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、炭素数３〜１２のシクロアルキル基およびハロゲン原子から選ばれる基を示す。ｓおよびｔは０〜３の整数である。）

(Wherein R ²² and R ²³ represent a group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a halogen atom. S and t is an integer of 0-3.)

And a reduced viscosity [η _sp / C] at 20 ° C. of a 0.5 g / deciliter solution having methylene chloride as a solvent and having at least one repeating unit selected from A polycarbonate resin characterized by being not less than 3.6 g / l and less than 3.6 deciliter / g.
[5] The polycarbonate resin further comprises (C) the following general formula (2)

（式中、Ｒ³ 〜Ｒ⁶ は炭素数１〜６のアルキル基を示す。ａ〜ｃは０〜５の整数、ｄ〜ｇは０以上の整数であり、ｄ＋ｅ＋ｆ＋ｇは３〜１００の整数である。）

(Wherein R ^{3 to} R ⁶ represent an alkyl group having 1 to ⁶ carbon atoms, a to c are integers of 0 to 5, d to g are integers of 0 or more, and d + e + f + g is an integer of 3 to 100. is there.)

The polycarbonate resin of the above-mentioned [4], containing 0.1 to 20% by mass of the repeating unit represented by

  According to the present invention, a polycarbonate resin excellent in abrasion resistance and solubility in an organic solvent can be obtained.

  The polycarbonate resin (I) of the present invention has the following general formula (1):

（式中、Ｒ¹ およびＲ² は、メチル基、エチル基、シクロヘキシル基およびフェニル基から選ばれる基を示す。）

(In the formula, R ¹ and R ² represent a group selected from a methyl group, an ethyl group, a cyclohexyl group, and a phenyl group.)

A polycarbonate resin having a repeating unit represented by the formula: In the general formula (1), R ¹ and R ² are preferably methyl groups.
The polycarbonate resin (I) has a reduced viscosity [η _sp / C] at 20 ° C. of a 0.5 g / deciliter solution containing methylene chloride as a solvent at 0.35 deciliter / g or more and less than 3.6 deciliter / g. Is more preferable, 0.43-3.0 deciliter / g, more preferably 0.48-1.9 deciliter / g. When the reduced viscosity [η _sp / C] is 0.35 deciliter / g or more, this polycarbonate resin is used as a binder for a functional material, for example, when it is used for a photosensitive layer of an electrophotographic photoreceptor, printing durability. Is enough. In addition, when the reduced viscosity [η _sp / C] is less than 3.6 deciliter / g, for example, the coating viscosity does not become too high during the production of the photoreceptor, so that an operation for reducing the solid content concentration is unnecessary. Thus, there is an advantage that the productivity of the electrophotographic photosensitive member is not lowered and the solvent can be dried in a short time.
In addition to the above repeating unit, the polycarbonate resin (I) is further represented by the following general formula (2)

（式中、Ｒ³ 〜Ｒ⁶ は炭素数１〜６、好ましくは炭素数１〜４のアルキル基を示す。ａ〜ｃは０〜５、好ましくは２〜３の整数、ｄ〜ｇは０以上の整数、好ましくは１〜５０の整数であり、ｄ＋ｅ＋ｆ＋ｇは３〜１００、好ましくは１０〜６０の整数である。）

(Wherein, R ³ to R ⁶ is 1 to 6 carbon atoms, preferably .a~c represents an alkyl group having 1 to 4 carbon atoms 0-5, preferably 2-3 integer, D-G 0 The above integer, preferably an integer of 1-50, and d + e + f + g is an integer of 3-100, preferably 10-60.)

0.1-20 mass% may be included in all repeating units. By including 0.1 to 20% by mass of the repeating unit represented by the general formula (2), it is possible to reduce the coefficient of friction and to obtain the advantage that the wear resistance is improved. The content of the repeating unit represented by the general formula (2) is preferably 0.5 to 10% by mass.
In the said General formula (2), as a C1-C6 alkyl group of R < ³ > -R < ⁶ >, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl Group, tert-butyl group, various pentyl groups, various hexyl groups and the like. When d + e + f + g is 3, d, e and f are preferably 0.

  The polycarbonate resin (II) of the present invention comprises (A) the following general formula (3)

A repeating unit represented by formula (B) (b-1):

And (b-2) the following general formula (5)

And at least one repeating unit selected from the repeating units represented by:
(A) In the above general formula (3) of the repeating unit, R ^{7 to} R ¹⁰ are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and 6 to 12 carbon atoms, preferably carbon. A group selected from an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, preferably 5 to 9 carbon atoms, and a halogen atom.
Examples of the alkyl group having 1 to 12 carbon atoms of R ^{7 to} R ¹⁰ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and various pentyl groups. Groups, various hexyl groups, various heptyl groups, various octyl groups, 2-methoxyethyl groups and the like. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, and a xylyl group. Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

(B) (b-1) In the general formula (4) of the repeating unit, R ¹¹ and R ¹² are alkyl groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, preferably 6 to 12 carbon atoms, preferably Represents a group selected from an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, preferably a cycloalkyl group having 5 to 9 carbon atoms, and a halogen atom. m and n are integers of 0-4. When m and n are 2 or more, the plurality of R ¹¹ and R ¹² may be the same or different. Specific examples of R ¹¹ and R ¹² include the same as those exemplified for R ^{7 to} R ¹⁰ in the general formula (3).
In the general formula (4), X is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ¹³ R ¹⁴ — (where R ¹³ and R ¹⁴ are , A hydrogen atom, CF ₃ , a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms A substituted or unsubstituted C5-C11, preferably a C5-C9 cycloalkylidene group, a substituted or unsubstituted C2-C12, preferably C2-C2; 6 α, ω-alkylene group, substituted or unsubstituted 9,9-fluorenylidene group, substituted or unsubstituted arylene group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, the following general formula

（式中、Ｒ¹⁵〜Ｒ¹⁷は、水素原子、ＣＦ₃ 、ハロゲン原子、炭素数１〜１０、好ましくは炭素数１〜６のアルキル基、炭素数６〜１２、好ましくは炭素数６〜１０のアリール基、炭素数３〜１２、好ましくは炭素数５〜９のシクロアルキル基、炭素数１〜６のアルコキシ基および炭素数６〜１２、好ましくは炭素数６〜１０のアリールオキシ基から選ばれる基を示す。）

(Wherein R ^{15 to} R ¹⁷ are a hydrogen atom, CF ₃ , a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. Selected from aryl groups having 3 to 12 carbon atoms, preferably cycloalkyl groups having 5 to 9 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and aryloxy groups having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. Represents a group to be selected.)

A divalent group derived from natural terpenes represented by the formula:

（式中、Ｒ¹⁸〜Ｒ²¹は、Ｒ¹⁵〜Ｒ¹⁷と同様の基を示す。）

(In the formula, R ^{18 to} R ²¹ represent the same groups as R ^{15 to} R ^17. )

And a group selected from alkylidenearylenealkylidene groups having 8 to 16 carbon atoms, preferably 12 to 16 carbon atoms.
The substituted or unsubstituted alkyl group having 1 to 12 carbon atoms and the substituted or unsubstituted aryl group having 6 to 12 carbon atoms in R ¹³ and R ¹⁴ in —CR ¹³ R ¹⁴ — of the above X includes the above general formula. The same thing as R < ⁷ > -R < ¹⁰ > in (3) is mentioned.
Examples of the substituted or unsubstituted cycloalkylidene group having 5 to 11 carbon atoms in X include a cyclopentylidene group, a cyclohexylidene group, and a cycloheptylidene group. Examples of the substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms include α, ω-ethylene group, α, ω-propylene group, α, ω-butylene group and the like. Examples of the substituted or unsubstituted arylene group having 6 to 12 carbon atoms include a phenylene group, an alkyl-substituted phenylene group, a naphthylene group, and an alkyl-substituted naphthylene group.

In the divalent group derived from the natural terpenes of X, a halogen atom of R ^{15 to} R ¹⁷ , an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms in the divalent group Specific examples of the cycloalkyl group having 3 to 12 carbon atoms are the same as those exemplified for R ^{7 to} R ¹⁰ . Examples of the alkoxy group having 1 to 6 carbon atoms of R ^{15 to} R ¹⁷ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, Examples include various pentoxy groups. Examples of the aryloxy group having 6 to 12 carbon atoms of R ^{15 to} R ¹⁷ include a phenoxy group, a 2,6-dimethylphenoxy group, and a naphthyloxy group.

(B) (b-2) In the above general formula (5) of the repeating unit, R ²² and R ²³ are alkyl groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, preferably 6 to 12 carbon atoms, preferably Represents a group selected from an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, preferably a cycloalkyl group having 5 to 9 carbon atoms, and a halogen atom. s and t are integers of 0-3. Specific examples of R ²² and R ²³ include the same as those exemplified for R ^{7 to} R ¹⁰ in the general formula (3). In the general formula (5), when s and t are 2 or more, the plurality of R ²² and R ²³ may be the same or different.
Polycarbonate resin (II) has a reduced viscosity [η _sp / C] at 20 ° C. of a 0.5 g / deciliter solution containing methylene chloride as a solvent at 0.35 deciliter / g or more and less than 3.6 deciliter / g. And preferably 0.43 to 3.0 deciliter / g, more preferably 0.48 to 1.9 deciliter / g. When the reduced viscosity [η _sp / C] is 0.35 deciliter / g or more, this polycarbonate resin is used as a binder for a functional material, for example, when it is used for a photosensitive layer of an electrophotographic photoreceptor, printing durability. Is enough. In addition, when the reduced viscosity [η _sp / C] is less than 3.6 deciliter / g, for example, the coating viscosity does not become too high during the production of the photoreceptor, so that an operation for reducing the solid content concentration is unnecessary. Thus, there is an advantage that the productivity of the electrophotographic photosensitive member is not lowered and the solvent can be dried in a short time.
In the same manner as the polycarbonate resin (I), the polycarbonate resin (II) is added to the repeating unit (C).

（式中、Ｒ³ 〜Ｒ⁶ およびａ〜ｇは上記と同じである。）

(In the formula, R ^{3 to} R ⁶ and a to g are the same as above.)

0.1-20 mass% may be included in all repeating units. By including 0.1 to 20% by mass of the repeating unit represented by the general formula (2), the same advantages as those of the polycarbonate resin (I) can be obtained. The content of the repeating unit represented by the general formula (2) is preferably 0.5 to 10% by mass.
In addition, the polycarbonate resin of this invention may have other repeating units other than the said repeating unit in the range which does not interfere with the objective of this invention.

  There is no restriction | limiting in particular as a manufacturing method of polycarbonate resin (I) or polycarbonate resin (II) of this invention, It can manufacture by various methods according to a well-known method using a suitable monomer. The polycarbonate resin (I) having the repeating unit represented by the general formula (1) is, for example, the following general formula (6)

（式中、Ｒ¹ およびＲ² は上記と同じである。）

(In the formula, R ¹ and R ² are the same as above.)

It can manufacture by making the bisphenol compound (henceforth [X] component) represented by these and a carbonate ester-forming compound react. The polycarbonate resin (II) having the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) is, for example, the following general formula (7)

（式中、Ｒ⁷ 〜Ｒ¹⁰は上記と同じである。）
で表されるビスフェノール化合物（以下［Ｙ１］成分ともいう。）と、下記一般式（８）

(Wherein R ^{7 to} R ¹⁰ are the same as above)
A bisphenol compound (hereinafter also referred to as [Y1] component), and the following general formula (8):

（式中、Ｒ¹¹、Ｒ¹²、Ｘ、ｍおよびｎは上記と同じである。）

(Wherein R ¹¹ , R ¹² , X, m and n are the same as above).

It can manufacture by making the bisphenol compound (henceforth [Y2] component) represented by these and a carbonate ester-forming compound react. At this time, the molecular weight can be adjusted by changing the ratio of [Y1] and [Y2]. [Y2] / [Y1] (molar ratio) is usually about 1/100 to 100/1, and preferably 10/90 to 90/10.
. The polycarbonate resin (II) having the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (5) includes, for example, the above [Y1] component and the following general formula (9).

（式中、Ｒ²²、Ｒ²³、ｓおよびｔは上記と同じである。）

(In the formula, R ²² , R ²³ , s and t are the same as above.)

Can be produced by reacting a bisphenol compound (hereinafter also referred to as [Z] component) with a carbonate ester-forming compound. [Z] / [Y1] (molar ratio) is usually about 1/100 to 100/1, and preferably 10/90 to 90/10.
Specific examples of the bisphenol compound as the component [X] include 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (3-ethyl-4-hydroxyphenyl) cyclopentane, Examples include 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclopentane and 1,1-bis [4-hydroxy-3- (phenyl) phenyl] cyclopentane. In addition, the bisphenol compound of these [X] components may be used individually by 1 type, or may mix and use 2 or more types.

  Specific examples of the bisphenol compound as the [Y1] component include 1,1-bis (4-hydroxyphenyl) cyclopentane in addition to the bisphenol as the [X] component. In addition, the bisphenol compound of these [Y1] components may be used individually by 1 type, or may mix and use 2 or more types.

  Specific examples of the bisphenol compound of the [Y2] component include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2 , 2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4- Hydroxyphenyl) octane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether, bis ( -Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2- (3-methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) -1-phenylethane, bis (3-methyl-4-hydroxyphenyl) Sulfide, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 4,4-biphenol 3,3′-dimethyl-4,4′-biphenol, 3,3′-diphenyl-4,4 ′ Biphenol, 3,3′-dichloro-4,4′-biphenol, 3,3′-difluoro-4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl- 4-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-) 5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -2-methylpropane, 1,1-bis (2-tert-butyl-4) -Hydroxy-5-methylphenyl) heptane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1-bis (2-tert-amyl-4) -Hydroxy-5-methylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3-chloro-4-) Hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro -4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibu Mo-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2, 2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, bis (3-fluoro-4-hydroxyphenyl) ether 3,3′-difluoro-4,4′-dihydroxybiphenyl, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2, 2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl-4-hydroxyphenyl) Nyl) cyclohexane, bis (3-phenyl-4-hydroxyphenyl) sulfone, 4,4 ′-(3,3,5-trimethylcyclohexylidene) diphenol, 4,4 ′-[1,4-phenylenebis ( 1-methylethylidene)] bisphenol, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, and the like.

  Among these bisphenol compounds, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1,1- Diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl) -4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 4,4-biphenol, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 4, 4 ′-(3,3,5-trimethylcyclohexylidene) diphenol, 4,4 ′-[1,4-phenylenebis (1-mes Ruechiriden)], such as bisphenol is preferable. In addition, the bisphenol compound of these [Y2] components may be used individually by 1 type, or may mix and use 2 or more types.

  Specific examples of the [Z] component bisphenol compound include 2,7-naphthalenediol, 2,6-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, and the like. In addition, the bisphenol compound of these [Z] components may be used individually by 1 type, or may mix and use 2 or more types.

Examples of the carbonate ester-forming compound (hereinafter also referred to as a carbonate precursor) include dihalogenated carbonyls such as phosgene, phosgene dimer, and phosgene trimer, and haloformates such as chloroformate.
Further, examples of the terminal terminator include p-tert-butylphenol, p-phenylphenol, p-cumylphenol, 2,3,3-tetrafluoropropanol, 2,2,3,3,4,4,5, Examples thereof include hydrofluoroalcohols such as 5-octafluoropentanol and 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol, and perfluorooctylphenol.
For example, when a dihalogenated carbonyl such as phosgene or a haloformate such as chloroformate is used as the carbonate precursor, this reaction can be carried out in an appropriate solvent using an acid acceptor (for example, alkali metal hydroxide or alkali metal carbonate). In the presence of a basic alkali metal compound such as a salt or an organic base such as pyridine).
Various alkali metal hydroxides and alkali metal carbonates can be used, but from an economical aspect, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are usually preferably used. The These are usually suitably used as an aqueous solution.

The proportion of the carbonate precursor used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate precursors, such as phosgene, the method of blowing this in a reaction system can be employ | adopted suitably.
Similarly, the use ratio of the acid acceptor may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excessive amount of acid acceptor relative to the total number of moles of dihydroxy compound to be used (usually 1 mole corresponds to an equivalent amount).
As said solvent, what is necessary is just to use various solvents, such as what is used in the case of known polycarbonate manufacture, individually or as a 2 or more types of mixed solvent. As typical examples, hydrocarbon solvents such as toluene and xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene can be preferably used.
In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used, and further, phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris. (4-hydroxyphenyl) -2-heptene, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis ( 2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxy) Nyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4-hydroxyphenylisopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid and the like are added to react. It can be performed.
If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite may be added.

The reaction is usually carried out at a temperature in the range of about 0 to 150 ° C, preferably 5 to 40 ° C. The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure. Usually, it can be suitably performed at normal pressure or about the pressure of the reaction system. The reaction time is usually about 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. The reaction method may be any of continuous method, semi-continuous method, batch method and the like. In addition, what is necessary is just to select the said reaction conditions, the usage-amount of a molecular weight modifier, etc. appropriately, for example, in order to make the reduced viscosity [(eta) _sp / C] of the polycarbonate resin obtained into the said range. In some cases, the obtained polycarbonate resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain a predetermined reduced viscosity [ [eta] _sp / C] can also be obtained as a polycarbonate resin.
The obtained reaction product (crude product) can be recovered as a polycarbonate resin having a desired purity (purity) by performing various post-treatments such as known separation and purification methods.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[Example 1]
(1) Production of polycarbonate polymer In a solution prepared by dissolving 91.5 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 1) in 550 ml of a 9% by weight potassium hydroxide aqueous solution. While stirring by adding 250 ml of methylene chloride, phosgene gas was blown into this solution at a rate of 950 ml / min for 15 minutes while cooling. Next, the reaction solution was allowed to stand to separate an organic layer, and a methylene chloride solution of a polycarbonate oligomer having a polymerization degree of 2 to 4 and a molecular end of a chloroformate group was obtained.
After adding methylene chloride to 200 ml of this methylene chloride solution of the polycarbonate oligomer to a total volume of 450 ml, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 2) 15. 2 g mixed with 150 milliliters of 12% strength by weight aqueous potassium hydroxide solution was added, and 3.5 g of p-tert-butylphenol was added as a molecular weight regulator, and the mixture was vigorously stirred as a catalyst. 2 ml of a 7% strength by weight triethylamine aqueous solution was added and reacted at 28 ° C. with stirring for 1.5 hours.
After completion of the reaction, the reaction product is diluted with 1 liter of methylene chloride, then twice with 1.5 liters of water, once with 1 liter of 0.01 mol / liter hydrochloric acid, and then twice with 1 liter of water. After washing, the organic layer was put into methanol, and the precipitated solid was filtered and dried to obtain a polycarbonate polymer (PC-1). For the PC-1 obtained above, the reduced viscosity [η _sp / C] measured at 20 ° C. in a solution having a concentration of 0.5 g / deciliter using methylene chloride as a solvent (the following examples are also measured under the same conditions) is 0.54 deciliter / g. The reduced viscosity was measured with an automatic viscosity Ubbelohde improved viscometer (RM type) using an automatic viscosity measuring device VMR-042 manufactured by Rouai Co., Ltd. ^{From 1} H-NMR spectrum analysis, it was confirmed to be a polycarbonate resin composed of the following repeating units.

  The obtained PC-1 has the following formula as a substance having charge transfer functionality.

Using the hydrazone compound represented by formula (1), the dispersibility of the functional material, the wear resistance, and the solubility in a solvent were tested, and the resin performance was evaluated. A coating liquid was prepared by dissolving 0.5 g of polycarbonate (PC-1) and 0.5 g of the hydrazone compound in 10 ml of tetrahydrofuran. A part of this coating solution was applied onto a polyethylene terephthalate resin film with an applicator and dried to form a resin layer having a thickness of about 20 μm in which the functional material was dispersed. The abrasion resistance of this resin layer was evaluated using a Suga abrasion tester NUS-ISO-3 type (manufactured by Suga Test Instruments Co., Ltd.). The test condition was that the wear paper (containing alumina particles having a particle size of 3 μm) applied with a load of 4.9 N was brought into contact with the surface of the resin layer and reciprocated 2000 times to measure the mass loss. In addition, the coating solution prepared above was stored at 25 ° C. for 1 month, and it was confirmed whether or not insoluble matter, gel, etc. were generated. The results are shown in Table 1.

[Example 2]
Example 1 was the same as Example 1 except that 10.0 g of 4,4′biphenol was used instead of 15.2 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 2). Synthesis was carried out to obtain PC-2. The reduced viscosity [η _sp / C] of PC-2 was 0.61 deciliter / g. ^{From 1} H-NMR spectrum analysis, it was confirmed to be a copolymer polycarbonate resin composed of the following repeating units. Moreover, evaluation of obtained PC-2 was performed similarly to PC-1. The results are shown in Table 1.

Example 3
In Example 1, 10.0 g of 4,4 ′ biphenol instead of 15.2 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 2), and the following formula

Synthesis was carried out in the same manner as in Example 1 except that 1.0 g of the siloxane-containing bisphenol represented by the formula (II) was obtained to obtain PC-3. The reduced viscosity [η _sp / C] of PC-3 was 0.60 deciliter / g. ^{From 1} H-NMR spectrum analysis, it was confirmed to be a copolymer polycarbonate resin composed of the following repeating units. Moreover, evaluation of obtained PC-3 was performed similarly to PC-1. The results are shown in Table 1.

Example 4
In Example 1, 82.9 g of 1,1-bis (4-hydroxyphenyl) cyclopentane was used instead of 91.5 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 1). 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 2) was synthesized in the same manner as in Example 1 except that 10.0 g of 4,4′biphenol was used instead of 15.2 g. And PC-4 was obtained. The reduced viscosity [η _sp / C] of PC-2 was 0.65 deciliter / g. ^{From 1} H-NMR spectrum analysis, it was confirmed to be a copolymer polycarbonate resin composed of the following repeating units. Moreover, evaluation of obtained PC-4 was performed similarly to PC-1. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, 82.9 g of 1,1-bis (4-hydroxyphenyl) cyclopentane was used in place of 91.5 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 1). , Except that 13.7 g of 1,1-bis (4-hydroxyphenyl) cyclopentane was used instead of 15.2 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 2) Synthesis was carried out in the same manner as in Example 1 to obtain PC-5. The reduced viscosity [η _sp / C] of PC-5 was 0.52 deciliter / g.
The obtained PC-5 was evaluated in the same manner as PC-1, but since the solubility in tetrahydrofuran was low, the solvent was changed to methylene chloride for evaluation. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, 87.0 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used instead of 91.5 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 1). Example 1 except that 14.5 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used instead of 15.2 g of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane (component 2) Synthesis was performed in the same manner as above to obtain PC-6. The reduced viscosity [η _sp / C] of PC-6 was 0.57 deciliter / g. Evaluation of obtained PC-4 was performed similarly to PC-1. The results are shown in Table 1.

[Comparative Example 3]
The same evaluation as that of PC-1 was performed using Idemitsu Petrochemical polycarbonate A2200, but the solubility in tetrahydrofuran was low, so the evaluation was performed by changing the solvent to methylene chloride. The results are shown in Table 1.

溶解性○：塗工液を一ヶ月保管した後にもゲル化、白濁などが生じない。
溶解性×：塗工液を一ヶ月保管した後に、ゲル化、白濁などが発生。

Solubility ○: Gelation and cloudiness do not occur after storing the coating solution for one month.
Solubility x: Gelation, cloudiness, etc. occur after storing the coating solution for one month.

  The polycarbonate resin of the present invention is excellent in abrasion resistance and solubility in organic solvents, and is suitably used for applications in which substances having various functions are dispersed.

Claims (5)

The following general formula (1)

(In the formula, R ¹ and R ² represent a group selected from a methyl group, an ethyl group, a cyclohexyl group, and a phenyl group.)
A polycarbonate resin having a repeating unit represented by: The polycarbonate resin further has a reduced viscosity [η _sp / C] at 20 ° C. of a 0.5 g / deciliter solution containing methylene chloride as a solvent at 0.35 deciliter / g or more and less than 3.6 deciliter / g. The polycarbonate resin according to claim 1. Polycarbonate resin is further represented by the following general formula (2)

(Wherein R ^{3 to} R ⁶ represent an alkyl group having 1 to ⁶ carbon atoms, a to c are integers of 0 to 5, d to g are integers of 0 or more, and d + e + f + g is an integer of 3 to 100. is there.)
The polycarbonate resin of Claim 1 or 2 which contains 0.1-20 mass% of repeating units represented by these in all repeating units. (A) The following general formula (3)

(In the formula, R ^{7 to} R ¹⁰ represent a group selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a halogen atom. .)
A repeating unit represented by formula (B) (b-1):

[Wherein, R ¹¹ and R ¹² represent a group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a halogen atom. m and n are integers of 0-4. X is a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —CR ¹³ R ¹⁴ — (wherein R ¹³ and R ¹⁴ are a hydrogen atom, CF ₃ , substituted Or a group selected from an unsubstituted alkyl group having 1 to 12 carbon atoms and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.), A substituted or unsubstituted cycloalkylidene group having 5 to 11 carbon atoms A substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, a substituted or unsubstituted 9,9-fluorenylidene group, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, the following general formula

Wherein R ^{15 to} R ¹⁷ are a hydrogen atom, CF ₃ , a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon number And a group selected from an alkoxy group having 1 to 6 and an aryloxy group having 6 to 12 carbon atoms.)
A divalent group derived from natural terpenes represented by the formula:

(In the formula, R ^{18 to} R ²¹ represent the same groups as R ^{15 to} R ^17. )
The group chosen from C8-C16 alkylidene arylene alkylidene group represented by these is shown. ]
And (b-2) the following general formula (5)

(Wherein R ²² and R ²³ represent a group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a halogen atom. S and t is an integer of 0-3.)
And a reduced viscosity [η _sp / C] at 20 ° C. of a 0.5 g / deciliter solution having methylene chloride as a solvent and having at least one repeating unit selected from A polycarbonate resin characterized by being not less than 3.6 g / l and less than 3.6 deciliter / g. The polycarbonate resin further comprises (C) the following general formula (2)

(Wherein R ^{3 to} R ⁶ represent an alkyl group having 1 to ⁶ carbon atoms, a to c are integers of 0 to 5, d to g are integers of 0 or more, and d + e + f + g is an integer of 3 to 100. is there.)
The polycarbonate resin of Claim 4 which contains 0.1-20 mass% of repeating units represented by all the repeating units.