CN101062975B - Aromatic polycarbonate resin, manufacturing method thereof, optical part molding material, and optical part - Google Patents

Abstract

The present invention relates to an aromatic polycarbonate resin having a 2,2-bis(4-hydroxyphenyl)adamantane compound or a 1,3- A repeating unit formed from the residue of a bis(4-hydroxyphenyl)adamantane compound, which is excellent in transparency, heat resistance, and mechanical strength, and has good moldability; Alkanes and carbonate-forming compounds react. Furthermore, the present invention relates to an aromatic polycarbonate resin material excellent in optical properties and the like, and an optical part obtained by molding the same.

Description

Aromatic polycarbonate resin, manufacturing method thereof, optical part molding material, and optical part

This patent application is a divisional application of the patent application with the application date of January 21, 2003, the application number 038027038, and the invention name "aromatic polycarbonate resin and its manufacturing method, optical part molding material and optical part".

technical field

The present invention consists of a first invention, a second invention, and a third invention. The first invention and the second invention relate to an aromatic polycarbonate resin and a method for producing the same, and more specifically, to transparency, heat resistance, and mechanical strength. An aromatic polycarbonate resin having excellent moldability and an efficient method for producing the same. In addition, the third invention relates to an optical component molding material and an optical component, and more specifically, relates to a substrate suitable for optical discs such as digital audio discs (digital audio discs), digital video discs (DVDs), and optical storage discs, for light receiving (pickup) Various lenses such as lenses, eyeglass lenses, contact lenses, and lens sheets, optical sheet substrates such as prisms, mirrors, optical fibers, liquid crystal displays, and portable key cards, light guides, reflective films, light diffusing sheets, polarizing sheets, and retardation sheets Optical parts molding materials that are molding raw materials for optical functional elements such as sheets, and optical parts formed by molding them.

Background technique

In the first and second inventions, aromatic polycarbonate resins are widely used as so-called engineering plastics in various industrial fields because they are excellent in properties such as transparency, heat resistance, and mechanical strength. As the aromatic polycarbonate resin, one produced by reacting 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A) with a carbonate-forming compound such as phosgene or diphenyl carbonate is generally used. Aromatic polycarbonate resin. Aromatic polycarbonate resins made of bisphenol A are often used as raw materials for electric and electronic devices, optical devices, and the like because they have a good balance between transparency, mechanical strength, and moldability. In recent years, the demand for miniaturization and weight reduction of these machines has been increasing. In order to meet such demands, it is necessary to develop products that further improve the heat resistance and the basic properties of the aromatic polycarbonate resin. Aromatic polycarbonate resin with improved properties such as mechanical strength.

Therefore, in order to meet this demand, attempts have been made to prepare aromatic polycarbonate resins with further improved heat resistance and mechanical strength by using compounds having various chemical structures as dihydric phenols, which are raw materials of aromatic polycarbonate resins. For example, Soobshch. Akad. Nauk Gruz. SSR (1977), 88 (3), 597-600 proposed an aromatic polycarbonate resin based on a bisphenol derivative of adamantane as a dihydric phenol. The adamantane skeleton is introduced into the structural unit of the aromatic polycarbonate polymer chain, so the aromatic polycarbonate resin has high heat resistance, but since it is easy to crystallize, it has insufficient solubility in solvents and poor moldability, Furthermore, there is a problem that the transparency of the molded product decreases. In addition, as a dihydric phenol, it has been proposed to use 1,1-bis(4-hydroxyphenyl)cyclohexane or 9,9'-bis(4-hydroxyphenyl)fluorene alone or in combination with bisphenol A as a raw material. aromatic polycarbonate resin. However, aromatic polycarbonate resins composed of these structural units containing dihydric phenol residues have higher heat resistance than aromatic polycarbonate resins using bisphenol A as raw materials, but are used in electrical and electronic equipment parts. Higher heat resistance is required in manufacturing processes such as Thus, when used as a raw material for electrical, electronic or optical equipment parts, the development of aromatic polycarbonate resins having higher transparency, heat resistance, mechanical strength and good moldability has been demanded.

An object of the first and second inventions is to provide an aromatic polycarbonate resin excellent in transparency, heat resistance, mechanical strength, and moldability, and a method for producing the same.

As for the third invention, various plastics have been proposed as optical part molding materials. The properties required for the optical parts molding material include heat resistance, impact resistance, mechanical strength, and optical properties. As materials satisfying these required properties, polymethyl methacrylate, 2,2-bis Engineering plastics such as polycarbonate, polyallylate, and polyethersulfone made from (4-hydroxyphenyl)propane.

Among these numerous optical parts, high transparency and extremely high heat resistance are sometimes required. For example, in liquid crystal display substrates, an active matrix method is often used, in which thin film transistors serving as switching elements are arranged in a matrix on a glass substrate for each pixel and driven. Therefore, in the manufacturing process of this liquid crystal display, when forming a thin film transistor on a substrate, it is necessary to form an electrical insulating film such as silicon nitride by a glow discharge evaporation method. Therefore, since the substrate of this liquid crystal display is made of glass, it is easily damaged by external impact such as dropping, so it is desired to use an engineering plastic substrate excellent in impact resistance. However, among these engineering plastics, for example, polymethyl methacrylate has insufficient heat resistance and impact resistance, and polycarbonate and polyallylate have insufficient heat resistance when forming an electrical insulating layer. In addition, polyethersulfone has high heat resistance, but has an amber color, and has a problem that optical anisotropy tends to occur even with a small molecular orientation.

Therefore, as such molding materials for optical parts, development of molding materials for optical parts having high heat resistance and excellent mechanical strength in addition to optical properties is desired.

An object of the third invention is to provide an optical component molding material excellent in optical properties, extremely high heat resistance, and excellent in mechanical strength, and an optical component molded therefrom.

Contents of the invention

I. First Invention

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, they have found that specific dihydric phenols having an adamantane skeleton and dihydric phenols having various chemical structures and carbonate-forming compounds The aromatic polycarbonate resin obtained by reaction can achieve the said object, and based on this knowledge, the 1st invention was completed.

That is, the gist of the first invention is as follows.

(1) An aromatic polycarbonate resin comprising a repeating unit (I-1) represented by the following general formula [I-1] and a repeating unit (I-2) represented by the following general formula [I-2] ) composition, the reduced viscosity [ _ηsp /c] measured at 20°C for a solution with dichloromethane as a solvent and a concentration of 0.5g/dL is more than 0.1dL/g,

In the formula [I-1], R ¹ represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl group, R ² represents a group selected from halogen atoms, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₆ -C ₁₂ aryl, C ₇ -C ₁₃ aryl-substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, m represents an integer of 0-4, n represents an integer of 0-14,

烷二基、2，8-

烷二基、取代或未取代的亚吡嗪基(pyrazylidene)、C₆-C₁₂的取代或未取代的亚芳基、或—C(CH₃)₂—ph—C(CH₃)₂—(式中，ph表示亚苯基)，p表示0-4的整数。In the formula [I-2], R ³ represents a group selected from a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, X represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —C( R ⁴ R ⁵ )—(wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted Cycloalkylene, 9,9'-fluorenylene, 1,8-

Alkanediyl, 2,8-

Alkanediyl, substituted or unsubstituted pyrazinyl (pyrazylidene), C ₆ -C ₁₂ substituted or unsubstituted arylene, or —C(CH ₃ ) ₂ —ph—C(CH ₃ ) ₂ — (wherein, ph represents a phenylene group), and p represents an integer of 0-4.

(2) The aromatic polycarbonate resin as described in (1) above, wherein the repeating unit (I-2) is represented by the following general formula [I-3],

R ³ , X, and p in formula [I-3] have the same meanings as R ³ , X, and p in general formula [I-2], respectively.

(3) The aromatic polycarbonate resin described in (1) or (2) above, wherein R ¹ in the general formula [I-1] is a C ₁ -C ₆ alkyl group.

(4) The aromatic polycarbonate resin described in any one of the above (1)-(3), wherein X in the general formula [I-2] is —C(R ⁴ R ⁵ )—(wherein, R ^4. R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene or 9,9'- Fluorenylene.

(5) The method for producing an aromatic polycarbonate resin as described in (1) above, characterized in that: 2,2-bis(4-hydroxyphenyl)adamantane represented by the following general formula [I-4] The compound reacts with a dihydric phenol represented by the following general formula [I-5] and a carbonate-forming compound,

In the formula [I-4], R ¹ represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl group, R ² represents a group selected from halogen atoms, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₆ -C ₁₂ aryl, C ₇ -C ₁₃ aryl-substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, m represents an integer of 0-4, n represents an integer of 0-14,

烷二基、2，8-

烷二基、取代或未取代的亚吡嗪基、C₆-C₁₂的取代或未取代的亚芳基、或—C(CH₃)₂—ph—C(CH₃)₂—(式中，ph表示亚苯基)，p表示0-4的整数。In the formula [I-5], R ³ represents a group selected from a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, X represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —C( R ⁴ R ⁵ )—(wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted Cycloalkylene, 9,9'-fluorenylene, 1,8-

Alkanediyl, 2,8-

Alkanediyl, substituted or unsubstituted pyrazinyl, C ₆ -C ₁₂ substituted or unsubstituted arylene, or —C(CH ₃ ) ₂ —ph—C(CH ₃ ) ₂ —(where , ph represents phenylene), and p represents an integer of 0-4.

(6) The method for producing an aromatic polycarbonate resin as described in (5) above, which uses a substance represented by the following general formula [I-6] as a dihydric phenol,

R ³ , X, and p in formula [I-6] have the same meanings as R ³ , X, and p in general formula [I-5], respectively.

(7) The method for producing an aromatic polycarbonate resin as described in (5) or (6) above, wherein R ¹ in the general formula [I-4] is a C ₁ -C ₆ alkyl group as 2 , 2-bis(4-hydroxyphenyl)adamantane compound.

(8) The method for producing an aromatic polycarbonate resin described in any one of (5) to (7) above, wherein X in the general formula [I-5] is —C(R ⁴ R ⁵ )—( In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene or 9 , 9'-fluorenylidene species as dihydric phenols.

II. Second Invention

The inventors of the present invention have made intensive studies in order to solve the above-mentioned problems. As a result, they have found that the aromatic compounds obtained by reacting specific dihydric phenols having an adamantane skeleton and composed of phenyl groups having substituents and carbonate-forming compounds The second invention has been accomplished based on the knowledge that polycarbonate resin can achieve the above object.

That is, the gist of the second invention is as follows.

(1) Aromatic polycarbonate resin, which is composed of repeating units represented by the following general formula [II-1], and the ratio measured at 20°C in a solution with methylene chloride as a solvent and a concentration of 0.5g/dL Thick viscosity [η _sp /c] is above 0.1dL/g,

In the formula [II-1], R ¹ represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, m represents an integer of 1-4.

(2) The aromatic polycarbonate resin described in (1) above, wherein R ¹ in the general formula [II-1] is a C ₁ -C ₆ alkyl group.

(3) An aromatic polycarbonate resin consisting of a repeating unit (II-1) represented by the following general formula [II-2] and a repeating unit (II-2) represented by the following general formula [II-3] ) composition, the reduced viscosity [ _ηsp /c] measured at 20°C for a solution with dichloromethane as a solvent and a concentration of 0.5g/dL is more than 0.1dL/g,

In the formula [II-2], R ² represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, n represents an integer of 1-4,

烷二基、2，8-

烷二基、取代或未取代的亚吡嗪基、C₆-C₁₂的取代或未取代的亚芳基、或—C(CH₃)₂—ph—C(CH₃)₂—(式中，ph表示亚苯基)，p表示0-4的整数。In the formula [II-3], R ³ represents a group selected from a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, X represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —C( R ⁴ R ⁵ )—(wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted Cycloalkylene, 9,9'-fluorenylene, 1,8-

Alkanediyl, 2,8-

Alkanediyl, substituted or unsubstituted pyrazinyl, C ₆ -C ₁₂ substituted or unsubstituted arylene, or —C(CH ₃ ) ₂ —ph—C(CH ₃ ) ₂ —(where , ph represents phenylene), and p represents an integer of 0-4.

(4) The aromatic polycarbonate resin as described in (3) above, wherein the repeating unit (II-2) is represented by the following general formula [II-4],

In formula [II-4], R ³ , X, and p have the same meanings as R ³ , X, and p in general formula [II-3], respectively.

(5) The aromatic polycarbonate resin described in (3) or (4) above, wherein R ² in the general formula [II-2] is a C ₁ -C ₆ alkyl group.

(6) The aromatic polycarbonate resin described in any one of the above (3)-(5), wherein X in the general formula [II-3] is —C(R ⁴ R ⁵ )—(wherein, R ^4. R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene or 9,9'- Fluorenylene.

(7) The method for producing an aromatic polycarbonate resin as described in (1) above, wherein 1,3-bis(4-hydroxyphenyl)adamantine represented by the following general formula [II-5] is used Alkanes react with carbonate-forming compounds,

In the formula [II-5], R ¹ represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, m represents an integer of 1-4.

(8) The method for producing an aromatic polycarbonate resin as described in (7) above, wherein R ¹ in the general formula [II-5] is a C ₁ -C ₆ alkyl group as the 1,3-di (4-Hydroxyphenyl)adamantane compound.

(9) The method for producing an aromatic polycarbonate resin as described in (3) above, wherein 1,3-bis(4-hydroxyphenyl)adamantine represented by the following general formula [II-6] is used alkane compound and the dihydric phenol represented by the following general formula [II-7] react with a carbonate-forming compound,

In the formula [II-6], R ² represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, n represents an integer of 1-4,

In the formula [II-7], R ³ represents a group selected from a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, X represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —C( R ⁴ R ⁵ )—(wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted Cycloalkylene, 9,9'-fluorenylene, 1,8-cappedanediyl, 2,8-cappedanediyl, substituted or unsubstituted pyrazinylene, substitution of C ₆ -C ₁₂ or an unsubstituted arylene group, or —C(CH ₃ ) ₂ —ph—C(CH ₃ ) ₂ —(wherein, ph represents phenylene), and p represents an integer of 0-4.

(10) The method for producing an aromatic polycarbonate resin as described in (9) above, wherein ^R in the general formula [II-6] is a C ₁ -C ₆ alkyl group as the 1,3-di (4-Hydroxyphenyl)adamantane compounds.

(11) The method for producing an aromatic polycarbonate resin according to (9) or (10) above, which uses a dihydric phenol represented by the following formula [II-8],

In formula [II-8], R ³ , X, and p have the same meanings as R ³ , X, and p in general formula [II-7], respectively.

(12) The method for producing an aromatic polycarbonate resin according to any one of (9) to (11) above, wherein X in the general formula [II-7] is —C(R ⁴ R ⁵ )—( In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene or 9 , 9'-fluorenylidene species as dihydric phenols.

III. The third invention

The inventors of the present invention have made intensive studies in order to solve the above-mentioned problems. As a result, they have found that by using an aromatic polycarbonate resin having a repeating unit having a specific adamantane skeleton containing a 2,2-adamantyl group as an optical part molding material , the above objects can be achieved, and the third invention has been accomplished based on this knowledge.

That is, the gist of the third invention is as follows.

(1) A molding material for optical parts, which is composed of an aromatic polycarbonate resin consisting of repeating units represented by the following general formula [III-1], and using dichloromethane as a solvent , The reduced viscosity [η _sp /c] measured at 20°C for a solution with a concentration of 0.5g/dL is above 0.1dL/g,

In the formula [III-1], R ¹ and R ² each independently represent a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, C ₇ -C ₁₃ aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, R ³ represents a group selected from halogen atoms, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ Alkoxy group, C ₆ -C ₁₂ aryl group, C ₇ -C ₁₃ aryl substituted alkenyl group and C ₁ -C ₁₂ fluoroalkyl group, a, b represents an integer of 0-4, c represents an integer of 0-14.

(2) The optical part molding material described in (1) above, wherein R ¹ and R ² in the general formula [III-1] are C ₁ -C ₆ alkyl groups.

(3) An optical part molding material composed of an aromatic polycarbonate resin as described in (1) or (2) above, wherein the repeating unit is represented by the following general formula [III-2],

In formula [III-2], R ¹ , R ² , R ³ , a, b and c have the same properties as R ¹ , R ² , R ³ , a, b and c in general formula [III-1] respectively. mean.

(4) The optical part molding material described in (3) above, wherein R ¹ and R ² in the general formula [III-2] are C ₁ -C ₆ alkyl groups.

(5) A molding material for optical parts, which is composed of an aromatic polycarbonate resin composed of a repeating unit (III-1) represented by the following general formula [III-3] and the following general formula [III-3]: The repeating unit (III-2) composition shown in formula [III-4], and the reduced viscosity [ _ηsp /c] that measures at 20 ℃ with dichloromethane as solvent, the solution of concentration 0.5g/dL is 0.1 dL/g or more,

In the formula [III-3], R ⁴ and R ⁵ each independently represent a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, C ₇ -C ₁₃ aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, R ⁶ represents a group selected from halogen atoms, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ Alkoxy, C ₆ -C ₁₂ aryl, C ₇ -C ₁₃ aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, d, e represent 0-4 integers, f represents an integer of 0-14,

烷二基、2，8-烷二基、取代或未取代的亚吡嗪基、C₆-C₁₂的取代或未取代的亚芳基、—C(CH₃)₂—ph—C(CH₃)₂—(式中，ph表示亚苯基)、或下述式[III-5]或[III-6]，g、h分别表示0-4的整数，In the formula [III-4], R ⁷ and R ⁸ each independently represent a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ -C ₁₂ aryl group, C ₇ -C ₁₃ aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, X represents a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —C(R ⁹ R ¹⁰ )—(wherein, R ⁹ and R ¹⁰ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ Substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene, 1,8-

Alkanediyl, 2,8- Alkanediyl, substituted or unsubstituted pyrazinyl, C ₆ -C ₁₂ substituted or unsubstituted arylene, —C(CH ₃ ) ₂ —ph—C(CH ₃ ) ₂ —(where, ph represents phenylene), or the following formula [III-5] or [III-6], g, h represent an integer of 0-4 respectively,

In the formulas [III-5] and [III-6], R ¹¹ and R ¹² each independently represent a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ - C ₁₂ aryl group, C ₇ -C ₁₃ aryl-substituted alkenyl group and C ₁ -C ₁₂ fluoroalkyl group, i and j respectively represent an integer of 0-14.

(6) The optical part molding material described in (5) above, wherein R ⁴ and R ⁵ in the general formula [III-3] are C ₁ -C ₆ alkyl groups.

(7) The optical part molding material described in (5) or (6) above, wherein the repeating unit (III-2) is represented by the following general formula [III-7],

In formula [III-7], R ⁷ , R ⁸ , X, g, and h have the same meanings as R ⁷ , R ⁸ , X, g, and h in general formula [III-4], respectively.

(8) The optical part molding material described in any one of (5)-(7) above, wherein X in the general formula [III-4] is —C(R ⁹ R ¹⁰ )—(wherein, R ⁹ , R ¹⁰ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene or 9,9'-fluorene base.

(9) An optical part formed by molding the optical part molding material described in any one of (1) to (8) above.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will be described below.

I. First Invention

The first invention (hereinafter, sometimes simply referred to as "the present invention") relates to the repeating unit (I-1) represented by the above general formula [I-1] and the repeating unit (I-1) represented by the above general formula [I-2]. 2) Composition, an aromatic polycarbonate resin having a reduced viscosity [ _ηsp /c] of 0.1dL/g or more measured at 20°C in a solution with a concentration of 0.5g/dL in dichloromethane as a solvent.

In addition, in this aromatic polycarbonate resin, examples of the C ₁ -C ₆ alkyl group represented by R ¹ in the above general formula [I-1] include methyl, ethyl, n-propyl, isopropyl , n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, etc. In addition, examples of C ₁ -C ₆ alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy Oxygen, n-hexyloxy, etc. In addition, examples of C ₆ -C ₁₂ aryl groups include phenyl, biphenyl, triphenyl, naphthyl, etc., and examples of C ₇ -C ₁₃ aryl-substituted alkenyl groups include benzyl, phenylethyl, etc. base, styryl, cinnamyl, etc. In addition, examples of the C ₁ -C ₆ fluoroalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl and the like.

Among the various substituents represented by R ¹ in the general formula [I-1], a C ₁ -C ₆ alkyl group is preferable because of excellent heat resistance, and a methyl group is more preferable. In addition, among the above-mentioned various substituents, preferable ones include cyclohexyl, methoxy, phenyl, trifluoromethyl and the like. In addition, m in the general formula [I-1] may be 0, that is, a hydrogen atom, or may have 1 to 4 substituents described above. As for the m, it is more preferably 0-2.

In addition, examples of the halogen atom represented by R ² in the general formula [I-1] above include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In addition, examples of the C ₁ -C ₁₂ alkyl group represented by the formula R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyclohexyl, etc. In addition, examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy Oxygen, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc. In addition, examples of C ₆ -C ₁₂ aryl groups include phenyl, biphenyl, triphenyl, naphthyl, etc., and examples of C ₇ -C ₁₃ aryl-substituted alkenyl groups include benzyl, phenylethyl, etc. base, styryl, cinnamyl, etc. In addition, examples of the C ₁ -C ₁₂ fluoroalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl and the like. Among these various substituents, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, a trifluoromethyl group, etc. are mentioned as a preferable group. In addition, n in the general formula [I-1] may be 0, that is, only a hydrogen atom, or may have any number of substituents from 1 to 14.

In addition, in the aromatic polycarbonate resin, examples of the halogen atom represented by R ³ in the above general formula [I-2] include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In addition, examples of the C ₁ -C ₁₂ alkyl group represented by the formula R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyclohexyl, etc. In addition, examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy Oxygen, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc. In addition, examples of C ₆ -C ₁₂ aryl groups include phenyl, biphenyl, triphenyl, naphthyl, etc., and examples of C ₇ -C ₁₃ aryl-substituted alkenyl groups include benzyl, phenylethyl, etc. base, styryl, cinnamyl, etc. In addition, examples of the C ₁ -C ₁₂ fluoroalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl and the like. Among these various substituents, a methyl group, an ethyl group, a cyclohexyl group, a phenyl group, etc. are mentioned as a preferable group.

In addition, in this aromatic polycarbonate resin, examples of C ₁ -C ₆ alkyl groups represented by R ⁴ and R ⁵ in the above general formula [I-2] include methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl. Among these, a methyl group, an ethyl group, and a n-propyl group are mentioned as a preferable group. In addition, examples of the C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene group represented by X in the general formula [I-2] include cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene substituted or unsubstituted arylene groups such as C ₆ -C ₁₂ substituted or unsubstituted arylene groups include phenylene, biphenylene, 1,4-phenylene bis(1-methylethylene) group, 1 , 3-phenylene bis(1-methylethylene) group and the like.

Moreover, since this aromatic polycarbonate resin is excellent in heat resistance, mechanical strength, etc., it is preferable that the repeating unit (I-2) has the structural unit represented by general formula [I-3]. In addition, since the heat resistance is more excellent, it is preferable that the divalent group represented by X in the above-mentioned general formulas [I-2] and [I-3] be —C(R ⁴ R ⁵ )—(wherein, R ⁴ , R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene or 9,9'-alkylene Fluorenyl.

In addition, for the repeating unit (I-1) represented by the above general formula [I-1] and the repeating unit (I-2) represented by the above general formula [I-2] constituting the aromatic polycarbonate resin The content ratio is not particularly limited, and is expressed in molar ratio, preferably the content ratio of the repeating unit (I-1) relative to all the repeating units [(I-1)/((I-1)+(I-2)) ] in the range of 0.05-0.99. This is because when the molar ratio of the repeating unit (I-1) is less than 0.05, the molding processability is good but the degree of improvement in heat resistance is small, and when the molar ratio is greater than 0.99, exceptionally excellent heat resistance is exhibited, but Since the solubility to a solvent is low, molding processability may fall. The molar ratio of the repeating unit (I-1) relative to all the repeating units is particularly preferably 0.05 to 0.95 because heat resistance, mechanical strength, and moldability are well balanced.

In addition, while the aromatic polycarbonate resin of the present invention is composed of the above-mentioned repeating units (I-1) and (I-2), a solution with a concentration of 0.5 g/dL in dichloromethane was measured at 20°C The reduced viscosity [η _sp /c] is 0.1dL/g or more. The reason is that if the reduced viscosity is less than 0.1 dL/g, the heat resistance and mechanical strength of the aromatic polycarbonate resin cannot be sufficiently obtained. The reduced viscosity is further 0.3-3.0 dL/g, and is particularly suitable as a molding material for electric, electronic or optical devices.

Next, the aromatic polycarbonate resin of the present invention can be obtained by making the specific 2,2-bis(4-hydroxyphenyl)adamantane compound shown in the above general formula [I-4] and the above general formula [I-5] The method of reacting the shown dihydric phenols with a carbonate-forming compound is produced. In this case, it is possible to increase the molecular weight by performing interfacial polymerization in the presence of a polymerization solvent or an acid acceptor, a terminal terminator, or a catalyst, or by performing a transesterification reaction under reduced pressure to produce aromatic polycarbonate resin.

In addition, for the halogen atoms represented by R ¹ and R ² in the general formula [I-4], or alkyl, alkoxy, aryl, aryl-substituted alkenyl, and fluoroalkyl, the above-mentioned The same atom or group as those represented by R ¹ and R ² in the general formula [I-1]. Furthermore, as R ¹ in the general formula [I-4], it is more preferable to use a C ₁ -C ₆ alkyl group.

Examples of the 2,2-bis(4-hydroxyphenyl)adamantane compound represented by the general formula [I-4] include 2,2-bis(4-hydroxyphenyl)adamantane, 2,2- Bis(3-methyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-ethyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-n-propyl-4- Hydroxyphenyl) adamantane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-n-butyl-4-hydroxyphenyl)adamantane, 2 , 2-bis(3-isobutyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-tert Butyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-phenyl-4-hydroxyphenyl)adamantane Alkane, 2,2-bis(3-chloro-4-hydroxyphenyl)adamantane, 2,2-bis(3-bromo-4-hydroxyphenyl)adamantane, 2,2-bis(3,5- Dimethyl-4-hydroxyphenyl)adamantane, 2,2-bis(3,5-diethyl-4-hydroxyphenyl)adamantane, 2,2-bis(3,5-dichloro-4 -Hydroxyphenyl)adamantane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)adamantane, etc.

烷、2，8-二(4-羟苯基)

烷、1，8-二(3-甲基-4-羟苯基)

烷、1，8-二(4-羟基-3，5-二甲基苯基)

烷等二(羟苯基)

烷类；1，4-二[2-(4-羟苯基)-2-丙基]苯、1，3-二[2-(4-羟苯基)-2-丙基]苯等二[2-(4-羟苯基)-2-丙基]苯类等。In addition, specific examples of halogen atoms or alkyl groups represented by X and ^R in the general formula [I-5] include those atoms or groups represented by X and ^R in the general formula [I-2], respectively. same atoms or groups. Examples of dihydric phenols represented by the general formula [I-5] include 4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 3, 3'-dichloro-4,4'-dihydroxybiphenyl, 3,3'-dimethyl-4,4'-dihydroxybiphenyl, 3,3'-diphenyl-4,4'-bis Hydroxybiphenyl, 3,3'-dicyclohexyl-4,4'-dihydroxybiphenyl, 2,2'-dimethyl-4,4'-dihydroxybiphenyl, 3,3',5,5 '-Tetramethyl-4,4'-dihydroxybiphenyl and other 4,4'-dihydroxybiphenyls; bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, Bis(4-hydroxyphenyl)phenylmethane, bis(3-nonyl-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5 -Dibromo-4-hydroxyphenyl)methane, bis(3-chloro-4-hydroxyphenyl)methane, bis(3-fluoro-4-hydroxyphenyl)methane, bis(2-tert-butyl-4- Hydroxyphenyl) phenylmethane, two (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenyl) methane, two (2-hydroxy-4-methylphenyl) methane, two (2 -Hydroxy-4-methyl-6-tert-butylphenyl)methane, bis(2-hydroxy-4,6-dimethylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane , 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-methyl Phenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane, 2-(4-hydroxy-3-methylphenyl) -2-(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(2-tert-butyl-4-hydroxy-3-methylphenyl)ethane, 1-phenyl-1 , 1-bis(3-fluoro-4-hydroxyphenyl)ethane, 1,1-bis(2-hydroxy-4-methylphenyl)ethane, 2,2-bis(4-hydroxyphenyl) Propane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(2-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl) base) propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis( 3-phenyl-4-hydroxyphenyl) propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 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(4-hydroxy-3,5- Dimethylphenyl)propane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorobenzene base) propane, 2,2-bis(4-hydroxy-3,5-difluorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2- Bis(3-bromo-4-hydroxy-5-chlorophenyl)propane, 2,2-bis(4-hydroxyphenyl)-1,1,1,3, 3,3-hexafluoropropane, 2,2-bis(2-hydroxy-4-sec-butylphenyl)propane, 2,2-bis(2-hydroxy-4,6-dimethylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-(3-methyl-4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-methane 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)-2-methylpropane, 1,1-bis(2-butyl-4-hydroxy-5- Methylphenyl) butane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)butane, 1,1-bis(2-methyl-4-hydroxy-5 - tert-amylphenyl) butane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)butane, 2,2-bis(4-hydroxy-3,5-dibromophenyl ) butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylbutane, 3,3-bis( 4-Hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)heptane, 2,2-bis(2-tert-butyl -4-Hydroxy-5-methylphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)nonane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3- Methyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(3-cyclohexyl-4- Hydroxyphenyl) cyclohexane, 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl Two (hydroxyphenyl) alkanes such as 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; two (4-hydroxy Phenyl) ether, bis(3-fluoro-4-hydroxyphenyl) ether and other bis(4-hydroxyphenyl) ethers; bis(4-hydroxyphenyl)sulfide, bis(3-methyl-4- Bis(4-hydroxyphenyl)sulfides such as hydroxyphenyl)sulfide; bis(4-hydroxyphenyl)sulfoxide and bis(3-methyl-4-hydroxyphenyl)sulfoxide etc. Hydroxyphenyl) sulfoxides; bis(4-hydroxyphenyl)sulfone, bis(3-methyl-4-hydroxyphenyl)sulfone, bis(3-phenyl-4-hydroxyphenyl)sulfone and other bis( 4-hydroxyphenyl)sulfones; 4,4'-dihydroxybenzophenone and other bis(4-hydroxyphenyl)ketones; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9- Bis(3-methyl-4-hydroxyphenyl)fluorene, 9,9-bis(3-phenyl-4-hydroxyphenyl)fluorene and other bis(hydroxyphenyl)fluorenes; 4,4”-dihydroxy -Dihydroxy-p-terphenyls such as p-terphenyls; 4,4"'-dihydroxy-p-quaterphenyls and other dihydroxy-p-terphenyls; , 5-bis(4-hydroxyphenyl)-3,6-dimethylpyrazine, 2,5-bis(4-hydroxyphenyl)-2,6-diethylpyrazine and other bis(hydroxyphenyl ) pyrazines; 1,8-bis(4-hydroxyphenyl)

Alkane, 2,8-bis(4-hydroxyphenyl)

Alkane, 1,8-bis(3-methyl-4-hydroxyphenyl)

Alkane, 1,8-bis(4-hydroxy-3,5-dimethylphenyl)

Alkanes and other bis(hydroxyphenyl)

Alkanes; 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, etc. [2-(4-Hydroxyphenyl)-2-propyl]benzene, etc.

In addition, among these various dihydric phenols, dihydric phenols represented by the general formula [I-6] are preferable, and dihydric phenols represented by X in the general formulas [I-5] and [I-6] are more preferably used. The valence group is —C(R ⁴ R ⁵ )—(wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene or 9,9'-fluorenylene dihydric phenols. Examples of dihydric phenols having this chemical structure include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4- Hydroxyphenyl) cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9, 9-bis(3-methyl-4-hydroxyphenyl)fluorene, etc.

In addition, as the above-mentioned carbonate-forming compound, various dihalogenated carbonyl groups such as phosgene, haloformates such as chloroformate, carbonate compounds, and the like can be used. When using a gaseous carbonate-forming compound such as phosgene, a method of blowing it into the reaction system is preferably employed. The usage ratio of this carbonate-forming compound can be adjusted so that it may correspond to the stoichiometric ratio (equivalent weight) of this reaction.

In addition, as the solvent used in this reaction, a solvent used in the usual production of aromatic polycarbonate resins can be used. Examples include aromatic hydrocarbon solvents such as toluene and xylene, dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1 , 2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, chlorobenzene and other halogenated hydrocarbons, acetophenone, etc. As a preferred example. These solvents may be used alone or in combination of two or more. In addition, two kinds of solvents that are not miscible with each other can also be used.

In addition, as the acid acceptor, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or their mixture. The use ratio of these acid acceptors, considering the stoichiometric ratio (equivalent) of the reaction, for example, per 1 mole of dihydric phenolic hydroxyl groups of raw materials, can use 1 equivalent or more than it, and preferably use 1-5 equivalents of acid acceptors. body.

In addition, monohydric phenols can be used as terminal terminators. For example, p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p-(perfluorononylphenyl)phenol, p-perfluorotert-butylphenol, 1-( p-Hydroxybenzyl) perfluorodecane, etc.

In addition, as a catalyst, tertiary amines such as triethylamine or quaternary ammonium salts are suitably used. In addition, a method of adding a small amount of antioxidants such as sodium sulfite or bisulfite to the reaction system can be used for reaction.

Secondly, the reaction conditions when adopting the interfacial polymerization method are: the reaction temperature is usually 0-150°C, preferably 5-40°C, and the reaction pressure can be any one of reduced pressure, normal pressure, and increased pressure, preferably at normal pressure or The reaction system is carried out under pressure of a certain degree. The reaction time is determined by the reaction temperature, and is about 0.5 minutes to 10 hours, preferably about 1 minute to 2 hours. In addition, this reaction can be carried out in any reaction mode of a continuous method, a semi-continuous method, or a batch method.

In addition, when the transesterification reaction is used, the reaction is carried out at 120-350° C. under reduced pressure. In this case, as the reaction progresses, the degree of reduced pressure is increased step by step, and finally the reduced pressure is reduced to below 1 Torr, and the generated phenols are extracted out of the reaction system. The reaction time can be 1-4 hours, and catalyst or antioxidant can be added as needed.

The aromatic polycarbonate resin thus obtained can be molded by the same method as thermoplastic resins such as known aromatic polycarbonate resins using bisphenol A as a raw material. In addition, various additives used in molding processing, such as heat stabilizers, antioxidants, light stabilizers, colorants, antistatic agents, lubricants, and mold release agents, can be formulated in appropriate amounts. In addition, the aromatic polycarbonate resin obtained in this way is excellent in transparency, heat resistance, and mechanical strength, so it is used as a It is very useful as a raw material for molding such as panels for display devices.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Embodiment 1-1]

2,2-bis(4-hydroxyphenyl)adamantane 45g and 1,1-bis(4-hydroxyphenyl)cyclohexane 25g are dissolved in 1360ml of potassium hydroxide aqueous solution of 2 specified concentrations, in the solution obtained While adding 700 ml of dichloromethane as a solvent and stirring, phosgene was blown into the liquid at a rate of 950 ml/min for 30 minutes under cooling. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, dichloromethane was added to 110 ml of the obtained dichloromethane solution to make the total amount 150 ml, and then 5 g of 1,1-bis(4-hydroxyphenyl)cyclohexane was dissolved in hydrogen at a predetermined concentration of 2 To the solution obtained in 50 ml of an aqueous potassium oxide solution, 0.2 g of p-tert-butylphenol was added as a molecular weight regulator. Then, while vigorously stirring the mixed solution, 1.0 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 1 liter of dichloromethane, and washed twice with 1.5 liters of water. Then, after washing with hydrochloric acid of a predetermined concentration of 0.05, further washing with 1 liter of water was performed twice. Then, the obtained organic phase was poured into methanol and purified by reprecipitation to obtain a powder of an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.6 dL/g at 20° C. in a solution having a concentration of 0.5 g/L in methylene chloride as a solvent. In addition, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

In addition, the glass transition temperature of this aromatic polycarbonate resin was measured and found to be 238° C., confirming that it has extremely high heat resistance. In addition, the dichloromethane solution of the aromatic polycarbonate resin was used to cast a film, and the resulting film was colorless and highly transparent.

[Embodiment 1-2]

75g of 2,2-bis(4-hydroxyphenyl)adamantane was dissolved in 1360ml of potassium hydroxide aqueous solution of 2 specified concentrations, and 700ml of solvent dichloromethane was added to the resulting solution while stirring, and 950ml of dichloromethane was added under cooling. Phosgene was blown into the liquid at a rate of 30 minutes per minute. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, dichloromethane was added to 110 ml of the obtained dichloromethane solution to make the total amount 150 ml, and 6 g of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene dissolved in 2 0.2 g of p-tert-butylphenol was then added to the solution obtained in 50 ml of aqueous potassium hydroxide solution of high concentration as a molecular weight regulator. Then, while vigorously stirring the mixed solution, 1.4 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 0.5 L of dichloromethane, and washed twice with 0.5 L of water. Then, after washing with hydrochloric acid of a predetermined concentration of 0.01, further washing with 0.5 liter of water was performed twice. Then, the obtained organic phase was poured into methanol and purified by reprecipitation to obtain a powder of an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.5 dL/g at 20° C. in a solution having a concentration of 0.5 g/L in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

In addition, the glass transition temperature of this aromatic polycarbonate resin was measured and found to be 282° C., confirming that it has extremely high heat resistance. In addition, the dichloromethane solution of the aromatic polycarbonate resin was used to cast a film, and the resulting film was colorless and highly transparent.

[Embodiment 1-3]

Dissolve 170 g of 1,1-bis(4-hydroxyphenyl)cyclohexane in 1530 ml of potassium hydroxide aqueous solution of 2 specified concentrations, add 900 ml of solvent dichloromethane to the resulting solution and stir, while cooling under cooling Phosgene was blown into the liquid at a rate of 950 ml/min for 30 minutes. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, dichloromethane was added to 110 ml of the obtained dichloromethane solution to make the total amount 150 ml, and 6 g of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane was added thereto. The obtained solution was dissolved in 50 ml of an aqueous potassium hydroxide solution having a predetermined concentration, and 0.2 g of p-tert-butylphenol was added thereto as a molecular weight modifier. Then, while vigorously stirring the mixed solution, 1.0 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 0.5 L of dichloromethane, and washed twice with 0.5 L of water. Then, after washing with hydrochloric acid of a predetermined concentration of 0.01, further washing with 0.5 liter of water was performed twice. Then, the obtained organic phase was poured into methanol and purified by reprecipitation to obtain a powder of an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.4 dL/g at 20° C. in a solution having a concentration of 0.5 g/L in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

In addition, the glass transition temperature of this aromatic polycarbonate resin was measured and found to be 207° C., confirming that it has extremely high heat resistance. In addition, the dichloromethane solution of the aromatic polycarbonate resin was used to cast a film, and the resulting film was colorless and highly transparent.

[Comparative Example 1-1]

In Example I-2, instead of 6 g of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene added later, 5 g of 2,2-bis(4-hydroxyphenyl)adamantane was added Outside, all the other are identical with embodiment 1-2.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.5 dL/g at 20° C. in a solution having a concentration of 0.5 g/L in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

In addition, the glass transition temperature of this aromatic polycarbonate resin was measured to be 298° C., and it was confirmed that it has extremely high heat resistance. However, when the dichloromethane solution of the aromatic polycarbonate resin is used for casting and forming a film, the resulting film is whitened due to the generation of crystals, and thus has low transparency.

II. Second Invention

[ An aromatic polycarbonate resin in which η _sp /c] is 0.1 dL/g or more.

In addition, in this aromatic polycarbonate resin, examples of the halogen atom represented by R ¹ in the general formula [II-1] above include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In addition, as the C ₁ -C ₆ alkyl group represented by R ¹ in the formula, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl , n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, etc. In addition, examples of C ₁ -C ₆ alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy Oxygen, n-hexyloxy, etc. In addition, examples of C ₆ -C ₁₂ aryl groups include phenyl, biphenyl, triphenyl, and naphthyl, and examples of C ₇ -C ₁₃ aryl-substituted alkenyl groups include benzyl and phenethyl groups. , Styryl, Cinnamyl, etc. In addition, examples of the C ₁ -C ₆ fluoroalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl and the like. In addition, m in the general formula [II-1] may be 1-4, more preferably 1-2. In addition, when m is 2 or more, each R ¹ may be the same or different.

Furthermore, since the aromatic polycarbonate resin of the present invention is excellent in heat resistance, it is particularly preferable that R ¹ in the general formula [II-1] is a C ₁ -C ₆ alkyl group.

In addition, the copolymerization-type aromatic polycarbonate resin of the present invention is composed of the repeating unit (II-1) represented by the above general formula [II-2] and the repeating unit (II-2) represented by the above general formula [II-3]. ) composition, an aromatic polycarbonate resin having a reduced viscosity [η _sp /c] of 0.1 dL/g or more measured at 20°C in a solution with a concentration of 0.5 g/dL in dichloromethane as a solvent.

In addition, in this aromatic polycarbonate resin, as a halogen atom, an alkyl group, ^an alkoxy group, an aryl group, an aryl-substituted alkenyl group, or a fluoroalkyl group represented by R of the general formula [II-2], Examples thereof include the same atoms or groups as those represented by R ¹ in the general formula [II-1] above. In addition, n in the general formula [II-2] may be 1-4, more preferably 1-2. Furthermore, an aromatic polycarbonate resin containing an alkyl group having C ₁ -C ₆ as a repeating unit (II-1) of R ² in the general formula [II-2] is preferable because of excellent heat resistance.

In addition, as the halogen atom represented by R in the general formula [II-3], a fluorine atom, a chlorine atom, a bromine atom or ^an iodine atom can be mentioned, and as a C ₁ -C ₁₂ alkyl group, a methyl group, an ethyl group, a n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl Alkyl, n-dodecyl, cyclopentyl, cyclohexyl, etc. In addition, examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy Oxygen, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc. In addition, examples of C ₆ -C ₁₂ aryl groups include phenyl, biphenyl, triphenyl, naphthyl, etc., examples of C ₇ -C ₁₃ aryl-substituted alkenyl groups include benzyl, benzene Ethyl, styryl, cinnamyl, etc. In addition, examples of the C ₁ -C ₁₂ fluoroalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl and the like. Among these various substituents, preferable examples include methyl, ethyl, methoxy, ethoxy, phenyl, and trifluoromethyl. In addition, p in the general formula [II-3] may be 0, that is, only a hydrogen atom, or may have any number of 1-4 substituents.

烷二基、2，8-

烷二基、取代或未取代的亚吡嗪基、C₆-C₁₂的取代或未取代的亚芳基、或—C(CH₃)₂—ph—C(CH₃)₂—(式中，ph表示亚苯基)，其中，由于耐热性优异，因此优选—C(R⁴R⁵)—(式中，R⁴、R⁵各自独立地表示氢原子、C₁-C₆的烷基、苯基或三氟甲基)、C₆-C₁₂的取代或未取代的亚环烷基、9，9’-亚芴基。In addition, examples of X in the general formula [II-3] include a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —C(R ⁴ R ⁵ )— (wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene, 1,8-

Alkanediyl, 2,8-

Alkanediyl, substituted or unsubstituted pyrazinyl, C ₆ -C ₁₂ substituted or unsubstituted arylene, or —C(CH ₃ ) ₂ —ph—C(CH ₃ ) ₂ —(where , ph represents phenylene), among them, due to excellent heat resistance, it is preferable to —C(R ⁴ R ⁵ )—(wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, a C ₁ -C ₆ alkane group, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene.

Here, for —C(R ⁴ R ⁵ )— represented by the above-mentioned X, the C ₁ -C ₆ alkyl group represented by the R ⁴ and R ⁵ can be the same as the C ₁ -C ₆ alkyl group represented by the above R ¹ group. In addition, examples of the C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene group represented by X include cyclopentylene, cyclohexylene, 3,3,5-trimethylcyclohexylene, cycloheptylene C ₆ -C ₁₂ substituted or unsubstituted arylene groups include phenylene, biphenylene, 1,4-phenylene bis(1-methylethylene base) group, 1,3-phenylene bis(1-methylethylene) group.

In addition, since the repeating unit (II-2) constituting the aromatic polycarbonate resin is excellent in heat resistance and mechanical strength, it is preferable to have a structure containing a p-phenylene group represented by the general formula [II-4].

Next, there is no particular limitation on the content ratio of the repeating unit (II-1) and the repeating unit (2) constituting the copolymerization type aromatic polycarbonate resin. It is expressed in molar ratio, preferably the repeating unit (1) is relative to The content ratio [(II-1)/((II-1)+(II-2))] of all repeating units is in the range of 0.05-0.99. This is because when the molar ratio of the repeating unit (II-1) is less than 0.05, the formability is good but the degree of improvement in heat resistance is small, and when the molar ratio is greater than 0.99, excellent heat resistance is exhibited, but the solvent The solubility is low and the formability is reduced. The molar ratio of the repeating unit (II-1) to all the repeating units is more preferably 0.05 to 0.95 because heat resistance, mechanical strength, and formability are well balanced.

In addition, the aromatic polycarbonate resin of the present invention has a reduced viscosity [η _sp /c] of 0.1 dL/g or more measured at 20° C. in a solution having a concentration of 0.5 g/dL in methylene chloride as a solvent. The reason is that if the reduced viscosity is less than 0.1 dL/g, the heat resistance and mechanical strength of the aromatic polycarbonate resin cannot be sufficiently obtained. The reduced viscosity is further 0.3-3.0 dL/g, and is particularly suitable as a molding material for electrical, electronic or optical devices.

Next, the aromatic polycarbonate resin of the present invention can be produced by reacting a 1,3-bis(4-hydroxyphenyl)adamantane compound represented by the above general formula [II-5] with a carbonate-forming compound . In addition, the aromatic polycarbonate resin of the copolymerization type can be obtained by making the 1,3-di(4-hydroxyphenyl)adamantane compound represented by the above-mentioned general formula [II-6] and the compound represented by the general formula [II-7] It is produced by reacting dihydric phenols with carbonate-forming compounds. When carrying out these reactions, the aromatic polycarbonate resin can be produced by a method of interfacial polymerization in the presence of a polymerization solvent or an acid acceptor, a terminal terminator, or a catalyst, or a method of transesterification under reduced pressure.

In addition, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryl-substituted alkenyl groups, and fluoroalkyl groups represented by R ¹ -R ⁶ in the general formulas [II-5] and [II-6] include the same atoms or groups as those represented by R ¹ in the above general formula [II-1], respectively. Here, examples of 1,3-bis(4-hydroxyphenyl)adamantane compounds represented by the general formulas [II-5] and [II-6] include 1,3-bis(3-chloro-4 -Hydroxyphenyl)adamantane, 1,3-bis(3-bromo-4-hydroxyphenyl)adamantane, 1,3-bis(3-fluoro-4-hydroxyphenyl)adamantane, 1,3- Bis(3-methyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-ethyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-n-propyl-4- Hydroxyphenyl) adamantane, 1,3-bis(3-isopropyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-n-butyl-4-hydroxyphenyl)adamantane, 1 , 3-bis(3-isobutyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-sec-butyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-tert Butyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-n-pentyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-n-hexyl-4-hydroxyphenyl) Adamantane, 1,3-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-methoxy-4-hydroxyphenyl)adamantane, 1,3-bis( 3-ethoxy-4-hydroxyphenyl)adamantane, 1,3-bis(3-phenyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-benzyl-4-hydroxybenzene base) adamantane, 1,3-bis(3-naphthyl-4-hydroxyphenyl)adamantane, 1,3-bis(3-tetrafluoromethyl-4-hydroxyphenyl)adamantane, 1,3 -bis(3,5-dichloro-4-hydroxyphenyl)adamantane, 1,3-bis(3,5-dibromo-4-hydroxyphenyl)adamantane, 1,3-bis(3,5 -Difluoro-4-hydroxyphenyl)adamantane, 1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane, 2,2-bis(3,5-diethyl- 4-hydroxyphenyl)adamantane, 1,3-bis(3,5-dimethoxy-4-hydroxyphenyl)adamantane, 1,3-bis(3,5-diethoxy-4- Hydroxyphenyl) adamantane, etc.

In addition, for the halogen atom or alkyl, alkoxy, aryl, aryl-substituted alkenyl, fluoroalkyl represented by X and ^R in the above-mentioned general formula [II-7], can enumerate respectively and above-mentioned general formula In [II-3], the atoms or groups represented by X and R ³ are the same as those atoms or groups. As the dihydric phenol represented by this general formula [II-7], the exemplary compound of the dihydric phenol represented by general formula [I-5] in 1st invention is suitable.

Moreover, the dihydric phenol represented by the said general formula [II-8] is used suitably as a dihydric phenol used for manufacture of the aromatic polycarbonate resin of this invention. In addition, as the dihydric phenol, if X in the above general formulas [II-7] and [II-8] is used—C(R ⁴ R ⁵ )—(wherein, R ⁴ and R ⁵ each independently represent Hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene dihydric phenol, Since an aromatic polycarbonate resin excellent in heat resistance, mechanical strength, etc. can be obtained, it is preferable. As dihydric phenols having this chemical structure, for example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)butane, -Hydroxyphenyl) cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9 , 9-bis(3-methyl-4-hydroxyphenyl)fluorene, etc.

In addition, as the above-mentioned carbonate-forming compound, the carbonate-forming compound listed in the first invention is suitable, and when a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system is suitably employed.

As the solvent used in this reaction, solvents used in general production of aromatic polycarbonate resins can be used, and the solvents listed in the first invention are suitable. These solvents may be used alone or in combination of two or more. In addition, two kinds of solvents that are not miscible with each other can also be used.

In addition, as for the acid acceptor, terminal terminator and catalyst, those described in the first invention are suitable.

In addition, the reaction conditions in the case of using the interfacial polymerization method or the reaction conditions in the case of using the transesterification reaction are also suitable as those described in the first invention.

The molding process of the aromatic polycarbonate resin obtained in this way and various additives used at this time are also applicable to those described in the first invention.

The aromatic polycarbonate resin obtained in this way is excellent in transparency, heat resistance, and mechanical strength, so it is used as a It is very useful as a raw material for molding such as panels for machines.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Example II-1]

Dissolve 170 g of 1,1-bis(4-hydroxyphenyl)cyclohexane in 1530 ml of potassium hydroxide aqueous solution of 2 specified concentrations, add 900 ml of solvent dichloromethane to the resulting solution and stir, while cooling under cooling Phosgene was blown into the liquid at a rate of 950 ml/min for 30 minutes. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, dichloromethane was added to 110 ml of the obtained dichloromethane solution to make the total amount 150 ml, and then 5.5 g of 1,3-bis(4-hydroxyphenyl)adamantane was dissolved in hydrogen at a predetermined concentration of 2 To the solution obtained in 50 ml of an aqueous potassium oxide solution, 0.2 g of p-tert-butylphenol was added as a molecular weight regulator. Then, while vigorously stirring the mixed solution, 1.0 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 0.5 L of dichloromethane, and washed twice with 0.5 L of water. Then, after washing with 0.5 liter of hydrochloric acid of a predetermined concentration of 0.01, further washing with 0.5 liter of water was performed twice. Then, the obtained organic phase was poured into methanol for reprecipitation and purification to obtain an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.4 dL/g at 20° C. in a solution having a concentration of 0.5 g/dL in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

In addition, the glass transition temperature of this aromatic polycarbonate resin was measured to be 189° C., and it was confirmed that it has extremely high heat resistance. In addition, the dichloromethane solution of the aromatic polycarbonate resin was used to cast a film, and the resulting film was colorless and highly transparent.

[Example II-2]

Except using 6 g of 1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane instead of the raw material 1,3-bis(4-hydroxyphenyl)adamantane used in Example II-1 Except, all the other are identical with embodiment II-1.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.5 dL/g at 20° C. in a solution having a concentration of 0.5 g/dL in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

In addition, the glass transition temperature of this aromatic polycarbonate resin was measured to be 196° C., and it was confirmed that it has extremely high heat resistance. In addition, the dichloromethane solution of the aromatic polycarbonate resin was used to cast a film, and the resulting film was colorless and highly transparent.

[Example II-3]

170g of 2,2-bis(4-hydroxyphenyl)propane was dissolved in 1530ml of potassium hydroxide aqueous solution of 2 specified concentrations, and 900ml of solvent dichloromethane was added to the resulting solution while stirring, and the mixture was cooled with 950ml/ Phosgene was blown into the liquid in proportions of 30 minutes. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, dichloromethane was added to 110 ml of the obtained dichloromethane solution so that the total amount was 150 ml, and 5.5 ml of 1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane was added thereto. g was dissolved in 50 ml of an aqueous solution of potassium hydroxide having a predetermined concentration of 2, and then 0.2 g of p-tert-butylphenol was added as a molecular weight regulator. Then, while vigorously stirring the mixed solution, 1.0 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 0.5 L of dichloromethane, and washed twice with 0.5 L of water. Then, after washing with 0.5 liter of hydrochloric acid of a predetermined concentration of 0.01, further washing with 0.5 liter of water was performed twice. Then, the obtained organic phase was poured into methanol for reprecipitation and purification to obtain an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.4 dL/g at 20° C. in a solution having a concentration of 0.5 g/dL in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

In addition, the glass transition temperature of this aromatic polycarbonate resin was measured to be 170° C., and it was confirmed that it has extremely high heat resistance. In addition, the dichloromethane solution of the aromatic polycarbonate resin was used to cast a film, and the resulting film was colorless and highly transparent.

[Comparative Example II-1]

An aromatic polycarbonate resin was produced by a known interfacial polymerization method using only 1,1-bis(4-hydroxyphenyl)cyclohexane as a raw material of dihydric phenol.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.4 dL/g at 20° C. in a solution having a concentration of 0.5 g/dL in methylene chloride as a solvent. It was confirmed that the chemical structure of this aromatic polycarbonate resin consisted of the following repeating units.

In addition, when the glass transition temperature of this aromatic polycarbonate resin was measured, it was 170°C.

III. The third invention

The optical part molding material of the present invention is composed of the following aromatic polycarbonate resin: composed of repeating units represented by the above general formula [III-1] or the above general formula [III-2] and using dichloromethane as a solvent, concentration An aromatic polycarbonate resin whose reduced viscosity [ _ηsp /c] of a solution of 0.5g/dL measured at 20°C is 0.1dL/g or more, or a repeating unit represented by the above general formula [III-3] ( III-1) and the repeating unit (III-2) represented by the general formula [III-4] or general formula [III-7], with dichloromethane as the solvent and a solution with a concentration of 0.5g/dL measured at 20°C An aromatic polycarbonate resin having a reduced viscosity [η _sp /c] of 0.1 dL/g or more.

In addition, in the above-mentioned general formula [III-1] or the above-mentioned general formula [III-2] which are structural units of the aromatic polycarbonate resin, examples of the halogen atoms represented by R ¹ and R ² include fluorine atoms, chlorine atom, bromine atom or iodine atom. In addition, examples of the C ₁ -C ₆ alkyl group represented by R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl base, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, etc. In addition, examples of the C ₁ -C ₆ alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butyl Oxygen, n-pentyloxy, n-hexyloxy, etc. In addition, examples of the C ₆ -C ₁₂ aryl group include phenyl, biphenyl, naphthyl, etc., and examples of the C ₇ -C ₁₃ aryl-substituted alkenyl group include benzyl, phenethyl, styrene base, cinnamon base, etc. In addition, examples of the C ₁ -C ₁₂ fluoroalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl and the like. In addition, a and b may be 0, that is, only hydrogen atoms, or may have 1-4 substituents, preferably 1-2.

In addition, the aromatic polycarbonate resin in which R ¹ and R ² in the general formula [III-1] or general formula [III-2] are C ₁ -C ₆ alkyl groups is excellent in heat resistance, so it is preferable Used as a molding material for optical parts. Among the C ₁ -C ₆ alkyl groups, methyl is more preferred.

In addition, in the above-mentioned general formula [III-1], examples of the halogen atom represented by R ³ include the same halogen atoms as those for the above-mentioned R ¹ and R ² . In addition, examples of the C ₁ -C ₁₂ alkyl group represented by R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- Pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyclohexyl, etc. In addition, examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butyl Oxygen, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, etc. In addition, examples of the C ₆ -C ₁₂ aryl group include phenyl, biphenyl, naphthyl, etc., and examples of the C ₇ -C ₁₃ aryl-substituted alkenyl group include benzyl, phenethyl, styrene base, cinnamon base, etc. In addition, examples of the C ₁ -C ₁₂ fluoroalkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl and the like. Among these various substituents, methyl, ethyl, methoxy, ethoxy, phenyl, and trifluoromethyl are particularly preferred. In addition, c may be 0, that is, only a hydrogen atom, or may have 1-14 substituents.

In addition, examples of halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryl-substituted alkenyl groups, and fluoroalkyl groups represented by R ⁴ , R ⁵ , and R ⁶ in the general formula [III-3] include: Atoms or groups represented by the above R ¹ , R ² , and R ³ are the same as the atoms or groups.

烷二基、2，8-盖烷二基、取代或未取代的亚吡嗪基、C₆-C₁₂的取代或未取代的亚芳基、—C(CH₃)₂—ph—C(CH₃)₂—(式中，ph表示亚苯基)、通式[III-5]或通式[III-6]表示的取代或未取代的金刚烷基。此外，作为该通式[III-5]和通式[III-6]中R¹¹、R¹²表示的卤素原子、烷基、烷氧基、芳基、芳基取代链烯基、氟代烷基，可以列举分别与上述R³表示的原子或基团相同的原子或基团。此外，i、j可以为0，也可以具有1-14的取代基。In addition, examples of the halogen atom, alkyl group, alkoxyl group, aryl group, aryl-substituted alkenyl group, and fluoroalkyl group represented by R ⁷ and R ⁸ in the general formula [III-4] include the above-mentioned R ³ Atoms or groups that represent the same atom or group. In addition, examples of X in the general formula [III-4] include a single bond, —O—, —CO—, —S—, —SO—, —SO ₂ —, —C(R ⁹ R ¹⁰ )— (wherein, R ⁹ and R ¹⁰ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene, 1,8-

Alkanediyl, 2,8-cappediyl, substituted or unsubstituted pyrazinyl, C ₆ -C ₁₂ substituted or unsubstituted arylene, —C(CH ₃ ) ₂ —ph—C( CH ₃ ) ₂ —(wherein, ph represents phenylene), a substituted or unsubstituted adamantyl group represented by general formula [III-5] or general formula [III-6]. In addition, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryl-substituted alkenyl groups, fluoroalkanes represented by R ¹¹ and R ¹² in the general formula [III-5] and general formula [III-6] The group includes the same atom or group as the atom or group respectively represented by the above-mentioned R ³ . In addition, i and j may be 0, and may have 1-14 substituents.

Here, examples of the C ₁ -C ₆ alkyl group represented by R ⁹ and R ¹⁰ include the same groups as those described above for R ¹ and R ² . In addition, examples of the C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene group represented by X include cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene. As C ₆ -C The substituted or unsubstituted arylene group of ₁₂ includes phenylene, biphenylene, naphthylene, 1,4-phenylene bis(1-methylethylene) group, 1,3- Phenylbis(1-methylethylene) group and the like. In addition, g and h in the general formula [III-4] may be 0, or may have 1-4 substituents.

In addition, since it is excellent in optical properties, heat resistance, and mechanical strength, it is preferable that X in the general formula [III-4] is —C(R ⁹ R ¹⁰ )—(wherein, R ⁹ and R ¹⁰ each independently represent hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl), C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene.

Moreover, since this aromatic polycarbonate resin is also excellent in heat resistance, mechanical strength, etc., it is preferable that the repeating unit (III-2) has the structural unit represented by general formula [III-7].

In addition, there is no particular limitation on the content ratio of the repeating unit (III-1) and the repeating unit (III-2) constituting the aromatic polycarbonate resin, and the repeating unit (III-1) is preferably expressed in molar ratio. The content ratio [(III-1)/((III-1)+(III-2))] to all the repeating units is in the range of 0.05-0.99. This is because when the molar ratio of the repeating unit (III-1) is less than 0.05, moldability may be good but the degree of improvement in heat resistance may be small, and when the molar ratio exceeds 0.99, exceptionally excellent heat resistance is exhibited, However, moldability may be reduced. In the case of the copolymerized aromatic polycarbonate resin, since heat resistance, mechanical strength, and formability are well balanced, it is particularly preferable that the molar ratio of the repeating unit (III-1) to all repeating units is 0.05. -0.95.

In addition, the aromatic polycarbonate resin used in the optical part molding material of the present invention has a reduced viscosity [η _sp /c] of 0.1 dL measured at 20°C in a solution with a concentration of 0.5 g/dL in dichloromethane. /g or more. The reason is that if the reduced viscosity is less than 0.1 dL/g, the heat resistance and mechanical strength of the aromatic polycarbonate resin cannot be sufficiently obtained, and the properties required as a molding material for optical parts cannot be fully satisfied. The reduced viscosity of the aromatic polycarbonate resin is further 0.3-3.0 dL/g, and is particularly suitable as a molding material for optical machine parts.

Next, the aromatic polycarbonate resin used in the present invention can be produced by reacting a 2,2-bis(hydroxyphenyl)adamantane compound alone or with a dihydric phenol and a carbonate-forming compound. In this case, it can be produced by a method of performing an interfacial polymerization method in the presence of a polymerization solvent or an acid acceptor, a terminal terminator, or a catalyst, or a method of performing a transesterification reaction under reduced pressure.

In addition, examples of the adamantane compound used for producing the aromatic polycarbonate resin include 2,2-bis(4-hydroxyphenyl)adamantane, 2,2-bis(3-hydroxyphenyl)adamantane , 2,2-bis(3-chloro-4-hydroxyphenyl)adamantane, 2,2-bis(3-bromo-4-hydroxyphenyl)adamantane, 2,2-bis(3-fluoro-4 -Hydroxyphenyl) adamantane, 2,2-bis(3-methyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-ethyl-4-hydroxyphenyl)adamantane, 2, 2-bis(3-n-propyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-n-butyl Base-4-hydroxyphenyl)adamantane, 2,2-bis(3-isobutyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl) Adamantane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-n-pentyl-4-hydroxyphenyl)adamantane, 2,2-bis (3-n-hexyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-methoxy-4-hydroxy Phenyl)adamantane, 2,2-bis(3-ethoxy-4-hydroxyphenyl)adamantane, 2,2-bis(3-phenyl-4-hydroxyphenyl)adamantane, 2,2 -bis(3-benzyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-naphthyl-4-hydroxyphenyl)adamantane, 2,2-bis(3-tetrafluoromethyl- 4-hydroxyphenyl)adamantane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)adamantane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl) Adamantane, 2,2-bis(3,5-difluoro-4-hydroxyphenyl)adamantane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane, 2, 2-bis(3,5-diethyl-4-hydroxyphenyl)adamantane, 2,2-bis(3,5-dimethoxy-4-hydroxyphenyl)adamantane, 2,2-bis (3,5-diethoxy-4-hydroxyphenyl)adamantane and the like. These 2,2-bis(hydroxyphenyl)adamantane compounds may be used in combination of two or more.

烷类；二[2-(4-羟苯基)-2-丙基]苯类等，此外，可以列举1，3-二(4-羟苯基)金刚烷、1，3-二(3-氯-4-羟苯基)金刚烷、1，3-二(3-甲基-4-羟苯基)金刚烷等。In addition, examples of dihydric phenols used in the production of the aromatic polycarbonate resin include 4,4'-dihydroxybiphenyls;bis(hydroxyphenyl)alkanes; bis(4- hydroxyphenyl) ethers; bis(4-hydroxyphenyl)sulfides; bis(4-hydroxyphenyl)sulfoxides; bis(4-hydroxyphenyl)sulfones; bis(4-hydroxyphenyl) Ketones; Bis(hydroxyphenyl)fluorenes; Dihydroxy-p-terphenyls; Dihydroxy-p-quaterphenyls; Bis(hydroxyphenyl)pyrazines; Bis(hydroxyphenyl)

alkanes; bis[2-(4-hydroxyphenyl)-2-propyl]benzenes, etc., in addition, 1,3-bis(4-hydroxyphenyl)adamantane, 1,3-bis(3 -chloro-4-hydroxyphenyl)adamantane, 1,3-bis(3-methyl-4-hydroxyphenyl)adamantane, and the like.

In addition, as the above-mentioned carbonate-forming compound, the carbonate-forming compound listed in the first invention is suitable, and when a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system is suitable.

As the solvent used in this reaction, solvents generally used in the production of aromatic polycarbonate resins can be used, and the solvents listed in the first invention are suitable. These solvents may be used alone or in combination of two or more. In addition, two kinds of solvents that are not miscible with each other can also be used.

In addition, for the acid acceptor, terminal terminator and catalyst, those described in the first invention are suitable.

In addition, the reaction conditions in the case of using the interfacial polymerization method or the reaction conditions in the case of using the transesterification reaction are also suitable as those described in the first invention.

For the molding process of the thus obtained optical component molding material made of aromatic polycarbonate resin and various additives used at this time, those described in the first invention are suitable.

The optical part molding material of the present invention has excellent transparency, and excellent heat resistance, mechanical strength and dimensional stability, so it is used as a digital audio disc (digital audio disc), digital video disc (DVD), optical storage disc, etc. Optical disc substrates, light receiving lenses, spectacle lenses, contact lenses, lens sheets and other lenses, optical substrates such as prisms, mirrors, optical fibers, liquid crystal displays, and portable key cards, light guides, reflective films, and light diffusion sheets , Polarizer, retardation film and other optical functional components molding raw materials, very useful.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Example III-1]

(1) Manufacture of molding materials for optical parts

2,2-bis(4-hydroxyphenyl)adamantane 45g and 1,1-bis(4-hydroxyphenyl)cyclohexane 25g are dissolved in 1360ml of potassium hydroxide aqueous solution of 2 specified concentrations, in the solution obtained While adding 700 ml of dichloromethane as a solvent and stirring, phosgene was blown into the liquid at a rate of 950 ml/min for 30 minutes under cooling. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, after dichloromethane was added to 110 ml of the obtained dichloromethane solution to make the total amount 150 ml, 5 g of 1,1-bis(4-hydroxyphenyl)cyclohexane was dissolved in 2 hydrogen chloride solution of a predetermined concentration. To the solution obtained in 50 ml of aqueous potassium solution, 0.2 g of p-tert-butylphenol was added as a molecular weight modifier. Then, while vigorously stirring the mixed solution, 1.0 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 1 liter of dichloromethane, and washed twice with 1.5 liters of water. Then, after washing with hydrochloric acid of a predetermined concentration of 0.05, further washing with 1 liter of water was performed twice. Then, the obtained organic phase was poured into methanol and purified by reprecipitation to obtain a powder of an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.6 dL/g at 20° C. in a solution having a concentration of 0.5 g/L in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

(2) Evaluation of molding materials for optical parts

Dissolve the aromatic polycarbonate resin prepared in (1) above in dichloromethane, cast the solution with a concentration of 20% by mass on a glass substrate, and leave it at room temperature for more than half a day to form on the glass substrate. The film on the substrate is peeled off from the glass substrate. Then, the film was heated at 70° C. for 24 hours and then at 100° C. for 12 hours in a decompression desiccator to obtain a transparent film with a thickness of 0.1 mm.

(2-1) Heat resistance

The aromatic polycarbonate resin film prepared above was heated from 25°C to 350°C at a rate of 10°C/min under nitrogen flow (20mL/min) using DSC220 manufactured by Seiko Electronics Co., Ltd., and then quenched immediately to eliminate The thermal history of the sample, and then measure the glass transition temperature according to JIS K7121 at the same heating rate. As a result, the glass transition temperature of this aromatic polycarbonate resin was 238°C.

(2-2) Transparency

A test piece with a length of 40 mm x a width of 40 mm was cut out from the aromatic polycarbonate resin film prepared above, and the haze value (%) of the test piece was measured using a haze meter HGM-2DP manufactured by Suga Testing Instrument Co., Ltd. As a result, the haze value of the aromatic polycarbonate resin film was 0.3%.

(2-3) Optical path difference

Cut out a test piece with a length of 40 mm × a width of 40 mm from the above-mentioned prepared aromatic polycarbonate resin film, and use a micropolarization spectrophotometer to measure the temperature of the test piece at a wavelength of 515 nm by a rotating polarizer method (Semonalumon method). Phase difference. As a result, the retardation of this aromatic polycarbonate resin film was 4 nm.

(2-4) Refractive index

A test piece having a length of 20 mm×a width of 10 mm was cut out from the aromatic polycarbonate resin film prepared above, and the refractive index of the test piece was measured using an Atago refractometer. As a result, the refractive index of the aromatic polycarbonate resin film was 1.584.

[Example III-2]

(1) Manufacture of molding materials for optical parts

75g of 2,2-bis(4-hydroxyphenyl)adamantane was dissolved in 1360ml of potassium hydroxide aqueous solution of 2 specified concentrations, and 700ml of solvent dichloromethane was added to the resulting solution while stirring, and 950ml of dichloromethane was added under cooling. Phosgene was blown into the liquid at a rate of 30 minutes per minute. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, dichloromethane was added to 110 ml of the obtained dichloromethane solution to make the total amount 150 ml, and 6 g of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene dissolved in a concentration of 2 The solution obtained in 50 ml of aqueous potassium hydroxide solution was then added with 0.2 g of p-tert-butylphenol as a molecular weight regulator. Then, while vigorously stirring the mixed solution, 1.4 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 0.5 L of dichloromethane, and washed twice with 0.5 L of water. Then, after washing with hydrochloric acid of a predetermined concentration of 0.01, further washing with 0.5 liter of water was performed twice. Then, the obtained organic phase was poured into methanol and purified by reprecipitation to obtain a powder of an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.5 dL/g at 20° C. in a solution having a concentration of 0.5 g/L in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

(2) Evaluation of molding materials for optical parts

Regarding the aromatic polycarbonate resin prepared in the above (1), evaluation of the aromatic polycarbonate resin film was carried out in the same manner as in (III-2) of Example III-1. The results are shown in Table III-1.

[Example III-3]

Dissolve 170 g of 1,1-bis(4-hydroxyphenyl)cyclohexane in 1530 ml of potassium hydroxide aqueous solution of 2 specified concentrations, add 900 ml of solvent dichloromethane to the resulting solution and stir, while cooling under cooling Phosgene was blown into the liquid at a rate of 950 ml/min for 30 minutes. Then, the reaction solution was left to stand and separated to obtain a dichloromethane solution of an oligomer having a degree of polymerization of 2-5 and a chloroformate group at a molecular end in the organic layer.

Then, dichloromethane was added to 110 ml of the obtained dichloromethane solution to make the total amount 150 ml, and 6 g of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane was added thereto to dissolve it. To the solution obtained in 50 ml of an aqueous potassium hydroxide solution having a prescribed concentration of 2, 0.2 g of p-tert-butylphenol was added as a molecular weight modifier. Then, while vigorously stirring the mixed solution, 1.0 ml of a 7% triethylamine aqueous solution was added as a catalyst, and the mixture was reacted at 25° C. for 1.5 hours while stirring.

After the reaction, the obtained reaction product was diluted with 0.5 L of dichloromethane, and washed twice with 0.5 L of water. Then, after washing with hydrochloric acid of a predetermined concentration of 0.01, further washing with 0.5 liter of water was performed twice. Then, the obtained organic phase was poured into methanol and purified by reprecipitation to obtain a powder of an aromatic polycarbonate resin.

The aromatic polycarbonate resin obtained here had a reduced viscosity [η _sp /c] of 0.4 dL/g at 20° C. in a solution having a concentration of 0.5 g/L in methylene chloride as a solvent. Furthermore, as a result of confirming the structure of the aromatic polycarbonate resin by ¹ H-NMR spectroscopic analysis, it was confirmed that the chemical structure consisted of the following repeating units.

(2) Evaluation of molding materials for optical parts

Regarding the aromatic polycarbonate resin prepared in the above (1), evaluation of the aromatic polycarbonate resin film was carried out in the same manner as in (2) of Example III-1. The results are shown in Table III-1.

[Comparative Example III-1]

Except for the use of aromatic polycarbonate resin (reduced viscosity [η _sp /c] = 0.5dL/g) produced by known interfacial polymerization method using 2,2-bis(4-hydroxyphenyl)propane as a raw material In addition, the film was prepared by the same casting method as in Example III-1. Regarding the aromatic polycarbonate resin prepared here, evaluation was performed on the aromatic polycarbonate resin film in the same manner as in (2) of Example III-1. The results are shown in Table III-1 (in the table, "Example III-1" is referred to as "Example 1" for the sake of convenience. The same applies to other Examples and Comparative Examples).

Form III-1

Thickness (mm) Glass transition temperature (°C) Optical path difference (nm) Haze value (%) Refractive index Example 1 0.1 238 4 0.3 1.584 Example 2 0.1 282 3 0.2 1.590 Example 3 0.1 207 5 0.2 1.578 Comparative example 1 0.1 145 11 0.3 1.585

Industrial field of application

According to the present invention, it is possible to provide an aromatic polycarbonate resin excellent in transparency, heat resistance, and mechanical strength and good moldability, an efficient production method thereof, and an optical part excellent in optical characteristics, high heat resistance, and mechanical strength Molding materials and optical parts obtained by molding them.

Claims (12)

1. Aromatic polycarbonate resin, which is composed of repeating units represented by the following general formula [II-1], and the reduced viscosity of a solution with a concentration of 0.5g/dL in dichloromethane as a solvent measured at 20°C [η _sp /c] is 0.1dL/g or more,

In the formula [II-1], R ¹ represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, m represents an integer of 1-4. 2. The aromatic polycarbonate resin according to claim 1, wherein R ¹ in the general formula [II-1] is a C ₁ -C ₆ alkyl group. 3. An aromatic polycarbonate resin comprising a repeating unit (II-1) represented by the following general formula [II-2] and a repeating unit (II-2) represented by the following general formula [II-3] Composition, the reduced viscosity [η _sp /c] of a solution with a concentration of 0.5g/dL in dichloromethane as a solvent measured at 20°C is 0.1dL/g or more,

In the formula [II-2], R ² represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, n represents an integer of 1-4,

In the formula [II-3], R ³ represents a group selected from a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, X represents a single bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -C( R ⁴ R ⁵ )-, C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene, 1,8- Alkanediyl, 2,8- Alkanediyl, substituted or unsubstituted pyrazinyl, C ₆ -C ₁₂ substituted or unsubstituted arylene, or -C(CH ₃ ) ₂ -ph-C(CH ₃ ) ₂ -, p represents An integer of 0-4, wherein in the formula -C(R ⁴ R ⁵ )-, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl, and Wherein in the formula -ph-C(CH ₃ ) ₂ -, ph represents phenylene. 4. The aromatic polycarbonate resin according to claim 3, wherein the repeating unit (II-2) is represented by the following general formula [II-4],

In formula [II-4], R ³ , X, and p have the same meanings as R ³ , X, and p in general formula [II-3], respectively. 5. The aromatic polycarbonate resin according to claim 3 or 4, wherein R ² in the general formula [II-2] is a C ₁ -C ₆ alkyl group. 6. The aromatic polycarbonate resin according to claim 3, wherein X in the general formula [II-3] is -C(R ⁴ R ⁵ )-, C ₆ -C ₁₂ substituted or unsubstituted subrings Alkyl or 9,9'-fluorenylene, wherein in the formula -C(R ⁴ R ⁵ )-, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or Trifluoromethyl. 7. the manufacture method of aromatic polycarbonate resin described in claim 1 is characterized in that: make the 1,3-two (4-hydroxyphenyl) adamantane compound shown in following general formula [II-5] react with carbonate-forming compounds,

In the formula [II-5], R ¹ represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, m represents an integer of 1-4. 8. the manufacture method of aromatic polycarbonate resin described in claim 7, it uses general formula [II-5] in R ¹ is the material of C ₁ -C ₆ alkyl as 1,3-bis(4 -Hydroxyphenyl)adamantane compounds. 9. the manufacture method of aromatic polycarbonate resin described in claim 3 is characterized in that: make the 1,3-two (4-hydroxyphenyl) adamantane compounds shown in following general formula [II-6] With the dihydric phenol shown in following general formula [II-7] and carbonate formation property compound reaction,

In the formula [II-6], R ² represents a group selected from a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₆ fluoroalkyl groups, n represents an integer of 1-4,

In the formula [II-7], R ³ represents a group selected from a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, a C ₆ -C ₁₂ aryl group, a C ₇ -C ₁₃ Aryl substituted alkenyl and C ₁ -C ₁₂ fluoroalkyl groups, X represents a single bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -C( R ⁴ R ⁵ )-, C ₆ -C ₁₂ substituted or unsubstituted cycloalkylene, 9,9'-fluorenylene, 1,8-

Alkanediyl, 2,8- Alkanediyl, substituted or unsubstituted pyrazinyl, C ₆ -C ₁₂ substituted or unsubstituted arylene, or -C(CH ₃ ) ₂ -ph-C(CH ₃ ) ₂ -, p represents An integer of 0-4, wherein in the formula -C(R ⁴ R ⁵ )-, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl, and Wherein in the formula -ph-C(CH ₃ ) ₂ -, ph represents phenylene. 10. the manufacture method of aromatic polycarbonate resin described in claim 9, it uses general formula [II-6] in R ² is C ₁ -C ₆ alkyl material as 1,3-bis(4 -Hydroxyphenyl)adamantane compounds. 11. The method for producing an aromatic polycarbonate resin according to claim 9 or 10, which uses a substance represented by the following general formula [II-8] as a dihydric phenol,

In formula [II-8], R ³ , X, and p have the same meanings as R ³ , X, and p in general formula [II-7], respectively. 12. The method for producing an aromatic polycarbonate resin according to claim 9, wherein X in the general formula [II-7] is -C(R ⁴ R ⁵ )-, C ₆ -C ₁₂ substituted or unsubstituted A substituted cycloalkylene or 9,9'-fluorenylene group is a dihydric phenol, wherein in the formula -C(R ⁴ R ⁵ )-, R ⁴ and R ⁵ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or trifluoromethyl.