JP2017019944A - Polycarbonate resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin excellent in scratch resistance, heat resistance, and organic solvent resistance.SOLUTION: The polycarbonate resin contains a repeating unit represented by formula (1) at a ratio of 30-100 mol% in the total repeating units, has a weight-average molecular weight of 40,000-80,000 as measured by a GPC method, and further has a pencil hardness of F or more as measured according to JIS K5600. (In the formula, Rand Reach independently represent a 1-6C alkyl group, and Rand Reach independently represent a hydrogen atom or a 1-6C alkyl group.)SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin suitable for production of products requiring scratch resistance and heat resistance. Among them, the present invention provides a molded article, a film, and a sheet, which are formed from a polycarbonate resin composed of a specific repeating unit and a polycarbonate resin composition, and have good scratch resistance, heat resistance, and organic solvent resistance. Is.

  Polycarbonate resin is a thermoplastic resin with excellent heat resistance, dimensional stability, impact resistance, and transparency, and is widely used as a constituent material for OA equipment, electrical / electronic parts, optical parts, building parts, automotive parts, etc. It has been. However, a molded article, film, or sheet formed from a polycarbonate resin has a problem that the surface is soft and easily damaged. In order to deal with such problems, a method of hard-coating the polycarbonate resin surface is known, but pinholes, cracks, repellency, yuzu are dependent on the wettability of the hard-coating paint to the polycarbonate resin and the environmental conditions of the hard-coating treatment. Since appearance defects such as skin and poor adhesion occur, productivity decreases due to an increase in the defect rate, resulting in an increase in cost. Therefore, it is desired to impart scratch resistance to the polycarbonate resin itself.

  Therefore, in order to improve the scratch resistance of the polycarbonate resin itself, it is disclosed to use a copolymerized polycarbonate resin containing a specific structural unit such as 1,1-bis (4-hydroxy-3-methylphenyl) propane. (Patent Document 1). However, it is a problem that these polycarbonate resins are inferior in heat resistance as compared with a general polycarbonate resin made of bisphenol A.

  In addition, the polycarbonate resin has a problem of poor chemical resistance to organic solvents. Copolymer polycarbonate resin using α, α′-bis (4-hydroxyphenyl) -1,3-diisopropylbenzene, phenol-terminated polyorganosiloxane or the like has already been disclosed for improving the organic solvent resistance ( Patent Documents 2 and 3). However, although these polycarbonate resins are excellent in organic solvent resistance, they have a problem that they are inferior in scratch resistance and heat resistance as compared with general polycarbonate resins.

  In order to improve the heat resistance of the polycarbonate resin, there is a method of copolymerizing a specific structural unit such as 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Patent Documents 4 and 5). These polycarbonate resins were not sufficient in scratch resistance and organic solvent resistance. Some of these polycarbonate resins have the same heat resistance as polycarbonate resins and have improved aqueous ammonia resistance (Patent Document 6), but the problem is poor organic solvent resistance. .

  On the other hand, a method for improving scratch resistance and organic solvent resistance by mixing other resin with polycarbonate resin is known. For example, a polyester resin (Patent Document 7), a polyolefin resin (Patent Document 8), an acrylic resin (Patent Document 9), a block copolymer (Patent Document 10), and the like are disclosed. However, when mixing different resins, compatibility becomes a problem. When the compatibility is not good, problems such as a decrease in transparency and peeling of a molded product are cited. Various methods for improving the compatibility are known, but there has never been a polycarbonate resin that satisfies scratch resistance, heat resistance, and organic solvent resistance.

JP 2011-105931 A JP 2003-192780 A JP 2007-112845 A JP-A-2-88634 Special table 2011-521024 gazette Special table 2012-520906 gazette JP 2002-275369 A JP 2007-291378 A JP 7-3104 A JP 2009-215560 A

  An object of the present invention is to provide a polycarbonate resin excellent in scratch resistance, heat resistance, and organic solvent resistance. Furthermore, the present invention provides a molded article, a film, and a sheet, which are formed from a polycarbonate resin composed of a specific repeating unit and a polycarbonate resin composition, which have good scratch resistance, heat resistance, and organic solvent resistance. It is in.

  As a result of intensive studies to solve the above problems, the present inventor has a scratch resistance and heat resistance in a copolymer polycarbonate resin having a specific repeating unit at a specific ratio and having a specific range of molecular weight. The present inventors have found that it is high and excellent in resistance to organic solvents, and have completed the present invention.

（式中、Ｒ^１およびＲ^２は、各々独立して、炭素原子数１〜６のアルキル基を表す。Ｒ^３およびＲ^４は、各々独立して、水素原子または炭素原子数１〜６のアルキル基を表す。）
２．前記式（１）で表される繰り返し単位が下記式（２）で表される繰り返し単位であることを特徴とする前記１に記載のポリカーボネート樹脂。

（式中、Ｒ^３およびＲ^４は、前記式（１）と同義である。）
３．前記式（１）で表される繰り返し単位が１，１−ビス（４−ヒドロキシ−３−メチルフェニル）−３，３，５−トリメチルシクロヘキサンから誘導される繰り返し単位であることを特徴とする前記１に記載のポリカーボネート樹脂。
４．下記式（３）で表される繰り返し単位を含む前記１〜３のいずれかに記載のポリカーボネート樹脂。

（式（３）中、Ｗは、下記式（４）

または単結合からなる群より選択される少なくとも１種の二価の有機残基を表し、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８はそれぞれ独立して水素原子または炭素原子数１〜９の芳香族基を含んでもよいアルキル基または炭素原子数６〜１０のアリール基、または炭素原子数１〜６のアルコキシ基を表す。Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６はそれぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１０の炭化水素基、または芳香族基を表す。ｎは４〜７の整数である。）
５．前記式（３）で表される繰り返し単位が、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、α、α’−ビス（４−ヒドロキシフェニル）−１，３−ジイソプロピルベンゼンのいずれかから誘導される繰り返し単位であることを特徴とする前記４に記載のポリカーボネート樹脂。
６．前記式（３）で表される繰り返し単位が２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパンから誘導される繰り返し単位であることを特徴とする前記４に記載のポリカーボネート樹脂。
７．ガラス転移温度が１３５℃〜２００℃である前記１〜６に記載のポリカーボネート樹脂。
８．前記１〜７のいずれかに記載のポリカーボネート樹脂を成形して得られる成形品。
９．前記１〜７のいずれかに記載のポリカーボネート樹脂からなる自動車ランプレンズ、自動車内装部材、または自動車外装部材。
１０．前記１〜７のいずれかに記載のポリカーボネート樹脂からなる照明カバー、樹脂窓、または前面板。
１１．前記１〜７のいずれかに記載のポリカーボネート樹脂を成形して得られるなるフィルム又はシート。 That is, the present invention
1. The repeating unit represented by the following formula (1) is contained in a proportion of 30 to 100 mol% in all repeating units, the weight average molecular weight measured by GPC method is 40,000 to 80,000, and JIS Polycarbonate resin whose pencil hardness measured according to K5600 is F or more.

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom having 1 to 6 carbon atoms. Represents an alkyl group.)
2. 2. The polycarbonate resin as described in 1 above, wherein the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (2).

(In the formula, R ³ and R ⁴ have the same meanings as the formula (1).)
3. The repeating unit represented by the formula (1) is a repeating unit derived from 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane, 1. The polycarbonate resin according to 1.
4). The polycarbonate resin in any one of said 1-3 containing the repeating unit represented by following formula (3).

(In formula (3), W represents the following formula (4)

Or at least one divalent organic residue selected from the group consisting of a single bond, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an aromatic having 1 to 9 carbon atoms. Represents an alkyl group which may contain a group, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an aromatic group. Represent. n is an integer of 4-7. )
5. The repeating unit represented by the formula (3) is 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, α, α′-bis ( 4. The polycarbonate resin as described in 4 above, which is a repeating unit derived from any of 4-hydroxyphenyl) -1,3-diisopropylbenzene.
6). 5. The polycarbonate resin as described in 4 above, wherein the repeating unit represented by the formula (3) is a repeating unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane.
7). The polycarbonate resin according to 1 to 6, wherein the glass transition temperature is 135 ° C to 200 ° C.
8). A molded article obtained by molding the polycarbonate resin according to any one of 1 to 7 above.
9. An automobile lamp lens, an automobile interior member, or an automobile exterior member made of the polycarbonate resin according to any one of 1 to 7 above.
10. An illumination cover, a resin window, or a front plate made of the polycarbonate resin according to any one of 1 to 7 above.
11. A film or sheet obtained by molding the polycarbonate resin according to any one of 1 to 7 above.

  Since the polycarbonate resin according to the present invention has high scratch resistance and is excellent in heat resistance and organic solvent resistance, it is extremely useful for molded products, sheets and films.

<Polycarbonate resin>
The polycarbonate resin of the present invention is a polycarbonate resin having a repeating unit represented by the following formula (1).

（式中、Ｒ^１およびＲ^２は、各々独立して、炭素原子数１〜６のアルキル基を表す。Ｒ^３およびＲ^４は、各々独立して、水素原子または炭素原子数１〜６のアルキル基を表す。）

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom having 1 to 6 carbon atoms. Represents an alkyl group.)

Copolymer component in the polycarbonate resin of the present invention In the above (1), R ¹ and R ² are preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -A butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group and an isohexyl group, more preferably a methyl group. In cases other than the above, the pencil hardness is low and scratch resistance is poor, which is not preferable. R ³ and R ⁴ are preferably a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group, and more preferably a hydrogen atom. . A case other than the above is not preferable because the reactivity during the polymerization reaction is lowered and a resin having a sufficient molecular weight cannot be obtained.

The polycarbonate resin of the present invention is a polycarbonate resin having a repeating unit represented by the above formula (1), the mole fraction of the repeating unit represented by the above formula (1) is 30 to 100 mol%, and 35 More preferably, it is -90 mol%, More preferably, it is 35-80 mol%, Most preferably, it is 50-80 mol%. If it is less than 30 mol%, the heat resistance and organic solvent resistance are lowered, which is not preferable.
The polycarbonate resin of the present invention preferably has a repeating unit represented by the following formula (3).

または単結合からなる群より選択される少なくとも１種の二価の有機残基を表し、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８はそれぞれ独立して水素原子または炭素原子数１〜９の芳香族基を含んでもよいアルキル基または炭素原子数６〜１０のアリール基、または炭素原子数１〜６のアルコキシ基を表す。Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６はそれぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１０の炭化水素基、または芳香族基を表す。ｎは４〜７の整数である。） (In formula (3), W represents the following formula (4)

Or at least one divalent organic residue selected from the group consisting of a single bond, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an aromatic having 1 to 9 carbon atoms. Represents an alkyl group which may contain a group, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an aromatic group. Represent. n is an integer of 4-7. )

Copolymer component in polycarbonate resin of the present invention In the above (3), R ⁵ and R ⁶ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group. Group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group and isohexyl group, more preferably methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, Most preferred is a methyl group. In cases other than the above, scratch resistance or organic solvent resistance is inferior, which is not preferable. R ⁷ and R ⁸ are preferably a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group, and more preferably a hydrogen atom. . A case other than the above is not preferable because the reactivity during the polymerization reaction is lowered and a resin having a sufficient molecular weight cannot be obtained.

  In the polycarbonate resin of the present invention, the molar fraction of the repeating unit represented by the above formula (3) is 70 to 0 mol%, more preferably 65 to 10 mol%, and further preferably 65 to 20 mol%. Preferably, it is most preferable in it being 50-20 mol%. When it exceeds 70 mol%, the scratch resistance becomes low or the heat resistance becomes low, which is not preferable.

<Production method of polycarbonate resin>
The polycarbonate resin of the present invention can be produced by reacting a dihydric phenol containing a dihydric phenol represented by the following formula (5) with a carbonate-forming compound such as phosgene.

(Bisphenol component (raw material monomer))
The raw material monomer used for the polycarbonate resin of this invention contains the compound represented by following formula (5).

（式中、Ｒ^１およびＲ^２は、各々独立して、炭素原子数１〜６のアルキル基を表す。Ｒ^３およびＲ^４は、各々独立して、水素原子または炭素原子数１〜６のアルキル基を表す。）

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom having 1 to 6 carbon atoms. Represents an alkyl group.)

  Examples of the specific bisphenol compound represented by the general formula (5) include 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane; -Bis (4-hydroxy-3-ethylphenyl) -3,3,5-trimethylcyclohexane; 1,1-bis (4-hydroxy-3-ethylphenyl) -3,3,5-trimethylcyclohexane; 1,1 -Bis (4-hydroxy-3-propylphenyl) -3,3,5-trimethylcyclohexane; 1,1-bis (4-hydroxy-3-butylphenyl) -3,3,5-trimethylcyclohexane; 1,1 -Bis (4-hydroxy-3-pentylphenyl) -3,3,5-trimethylcyclohexane; 1,1-bis (4-hydroxy-3-hexyl) Eniru) -3,3,5-bis (hydroxyaryl such trimethylcyclohexane) cycloalkane and the like. Among these, 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane (may be abbreviated as BisOC-TMC) is preferable. These dihydric phenols may be used alone or in combination of two or more.

The bisphenol represented by the formula (5) is preferably 30 to 100% of all bisphenols used, more preferably 35 to 90%, still more preferably 35 to 80 mol%, and 50 to 80%. Most preferred is the mole percent. If it is less than 30 mol%, the heat resistance and the organic solvent resistance are lowered, which is not preferable.
Although the raw material monomer used for the polycarbonate resin of this invention contains the monomer represented by the said Formula (5), it is more preferable when the monomer represented by following General formula (6) is further included.

または単結合からなる群より選択される少なくとも１種の二価の有機残基を表し、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８はそれぞれ独立して水素原子または炭素原子数１〜９の芳香族基を含んでもよいアルキル基または炭素原子数６〜１０のアリール基、または炭素原子数１〜６のアルコキシ基を表す。Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５およびＲ^１６はそれぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１０の炭化水素基、または芳香族基を表す。ｎは４〜７の整数である。） (In the formula (6), W represents the following formula (7)

Or at least one divalent organic residue selected from the group consisting of a single bond, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an aromatic having 1 to 9 carbon atoms. Represents an alkyl group which may contain a group, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an aromatic group. Represent. n is an integer of 4-7. )

  Examples of the specific bisphenol compound represented by the general formula (6) include 2,2-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxy-3-methylphenyl). 2,2-bis (4-hydroxy-3-ethylphenyl) propane; 2,2-bis (4-hydroxy-3-propylphenyl) propane; 2,2-bis (4-hydroxy-3-butylphenyl) ) Propane; bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) octane 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-3-methylphenyl) phenylmethane 2,2-bis (4-hydroxy-1-methylphenyl) propane; bis (4-hydroxyphenyl) naphthylmethane; 1,1-bis (4-hydroxy-t-butylphenyl) propane; 4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-tetramethylphenyl) propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane; -Bis (4-hydroxy-3,5-tetrachlorophenyl) propane; bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-tetrabromophenyl) propane, 4,4'- Dihydroxyphenyl ethers; dihydroxyaryl ethers such as 4,4′-dihydroxy-3,3′-dimethylphenyl ether; Ters, 4,4′-dihydroxydiphenyl sulfide; dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide; 4,4′-dihydroxy- Dihydroxydiaryl sulfoxides such as 3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone; dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, 4,4 ′ Dihydroxydiphenyls such as dihydroxydiphenyl, 9,9-bis (4-hydroxyphenyl) fluorene; dihydroxydiarylfluorenes such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxy-3,3′-dimethylbenzophenone, 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenyldiol, 3,3′-dimethyl- 4,4′-biphenyldiol, α, α′-bis (4-hydroxyphenyl) -1,3-diisopropylben Zen, α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, and the like. Among them, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, or α, α′-bis (4-hydroxyphenyl) -1,3- Diisopropylbenzene is preferred, and 2,2-bis (4-hydroxy-3-methylphenyl) propane is more preferred. These dihydric phenols may be used alone or in combination of two or more.

  The polycarbonate resin of the present invention may be copolymerized with other diol components to such an extent that the properties of the resin composition are not impaired. Other diol components include hydroquinone, resorcinol, orcinol, 2,2-bis (4-hydroxyphenyl) norbornene, 1,3-bis (4-hydroxyphenyl) adamantane; 2,2-bis (4-hydroxyphenyl) adamantane 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2 , 3-dioxapentaene bisphenoxyethanol fluorene and the like.

(Production method)
In the production method of the polycarbonate resin of the present invention, a method known per se can be adopted, and the interface method will be described below as an example.
In the polycarbonate production method of the interface method (phosgene method), phosgene is mainly used as a carbonate raw material. In the interfacial method, bisphenol and phosgene are usually reacted with an acid binder such as an alkali metal or alkaline earth metal hydroxide and a polycarbonate in the presence of an inert organic solvent. In the reaction, a condensation catalyst or an arbitrary chain terminator can be added as necessary. Suitable chain terminators include various monophenols such as conventional phenols, as well as C1-C14 alkylphenols such as cumylphenol, isooctylphenol, pt-butylphenol and p-cresol, and p-chloro. Mention may be made of halogenated phenols such as phenol and 2,4,6-tribromophenol. Of these, phenol, cumylphenol, isooctylphenol and pt-butylphenol are suitable chain terminators. The amount of the chain terminator used varies depending on the molecular weight of the target polycarbonate, but is usually used in an amount of 0.5 to 10% by weight based on the amount of diol in the aqueous phase.

  The organic phase in the method of the present invention dissolves reaction products such as phosgene and carbonate oligomers (hereinafter simply referred to as oligomers) and polycarbonate at the reaction temperature and reaction pressure, but is not compatible with water. It is necessary to include any inert organic solvent that does not form a solution with water. Typical inert organic solvents include aliphatic hydrocarbons such as hexane and n-heptane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane and 1,2-dichloroethylene. Chlorinated aliphatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene and chlorotoluene, and other substituted aromatic carbons such as nitrobenzene and acetophenone Hydrogen is mentioned. Among these, chlorinated hydrocarbons such as methylene chloride or chlorobenzene are particularly preferably used. These inert organic solvents can be used alone or as a mixture with other solvents.

  The aqueous phase in the method of the present invention needs to contain at least three components of water, bisphenol and alkali metal hydroxide. In the aqueous phase, bisphenol reacts with alkali metal hydroxides such as sodium hydroxide or potassium hydroxide to produce water soluble alkali metal salts. Therefore, in the raw material adjustment tank, the bisphenol melt is gradually charged into a preliminarily prepared aqueous solution of alkali metal to produce an alkali metal salt. The molar ratio of diol and alkali metal in the aqueous phase is usually preferably from 1: 1.8 to 1: 4.5, more preferably from 1: 2.0 to 1: 3.5. When preparing such an aqueous solution, the temperature is 20 ° C. or higher, preferably 30 to 40 ° C., but if it is too high, oxidation of bisphenol occurs, so that the necessary minimum temperature is set and an inert gas atmosphere is suitable. Is purged with nitrogen for an appropriate time, preferably 5 to 30 minutes, and a small amount of a reducing agent such as hydrosulfite is preferably added.

  In the method of the present invention, the condensation catalyst is supplied after the contact between bisphenol and phosgene. However, in some cases, the condensation catalyst may be supplied prior to the contact with phosgene. The condensation catalyst can be arbitrarily selected from many condensation polymerization catalysts used in the two-phase interfacial condensation method. Suitable polycondensation catalysts include, for example, trialkylamines, N-ethylpyrrolidone, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine and N-isopropylmorpholine, with triethylamine being particularly suitable. is there.

Phosgene is used in liquid or gaseous form. The Cl ₂ concentration in this raw material phosgene is 10 ppm or less, preferably 5 ppm or less, more preferably 1 ppm or less. The removal method of Cl ₂ in the raw material phosgene includes adsorption removal of Cl ₂ by activated carbon or the like, separation removal by distillation using a boiling point difference, etc., and any method may be used. However, in the case of distillation removal, since the removal order is a very low numerical value, it is disadvantageous in that it requires a considerable number of distillation stages, and it can be said that adsorption removal is more advantageous. The preferred amount of phosgene is influenced by the reaction conditions, particularly the reaction temperature and the concentration of the alkali metal salt of bisphenol in the aqueous phase, but is usually 1-2, preferably 1 in terms of moles of phosgene per mole of bisphenol. 0.05 to 1.5. If this ratio is too large, the amount of unreacted phosgene increases and the economy is extremely deteriorated. On the other hand, if it is too small, the CO group is insufficient, and proper molecular weight extension cannot be performed, which is not preferable.

  The concentration of the oligomer in the organic phase at the stage of obtaining the oligomer may be in the range where the obtained oligomer is soluble, and specifically, it is about 10 to 40% by weight. Moreover, it is preferable that the ratio of an organic phase is 0.2-1.0 (volume ratio) with respect to the alkali metal salt aqueous solution of bisphenol, ie, an aqueous phase. The specific viscosity (ηsp) of the oligomer obtained under such condensation conditions is preferably about 0.10 to 0.30, more preferably 0.15 to 0.25, but is not limited to this specific viscosity. .

  The oligomer thus obtained is converted into a high-molecular polycarbonate under polycondensation conditions according to a conventional method. The polycondensation reaction for polymerizing is preferably carried out in the following embodiment. First, the organic phase in which the oligomer is dissolved is separated from the aqueous phase, and if necessary, the above-mentioned inert organic solvent is added to adjust the concentration of the oligomer. That is, the amount of the solvent is adjusted so that the concentration of the polycarbonate in the organic phase obtained after the polycondensation reaction is 5 to 30% by weight. Thereafter, an aqueous phase containing water and an alkali metal hydroxide is newly added, and in order to further adjust the polycondensation conditions, the above-mentioned condensation catalyst is preferably added, and the desired weight is determined according to the two-phase interfacial condensation method. Complete the condensation. The ratio of the organic phase to the aqueous phase at the time of polycondensation is preferably about volume ratio of organic phase: aqueous phase = 1: 0.2-5.

  The polycarbonate resin of the present invention is preferably highly purified. In the present invention, in the method for producing a purified polycarbonate solution, after washing the crude polycarbonate solution after completion of the polycondensation reaction by the interfacial polycondensation method, the crude polycarbonate solution containing the washing water is subjected to stationary separation or centrifugation to obtain an aqueous phase. And an organic phase containing polycarbonate. In general, as the washing water, water or alkaline water is used to remove unreacted monomers, acidic water is used to remove the catalyst and alkali, and pure water is used to remove salts and alkali. In that case, it is preferable to filter the organic phase containing the said polycarbonate using the filtration filter with a hole diameter of 0.2-50 micrometers.

<Weight average molecular weight>
The weight average molecular weight of the polycarbonate resin of the present invention is 40,000 to 80,000, preferably 40,000 to 70,000, and more preferably 40,000 to 60,000. When the weight average molecular weight is less than 40,000, the organic solvent resistance and mechanical strength of the molded article or film using the polycarbonate resin are undesirably low, and when it exceeds 80,000, the moldability is unfavorably deteriorated.
For the evaluation of the molecular weight of the polycarbonate resin, the relative solution viscosity defined in ISO1628-1 / -4 is also used. The polycarbonate resin of the present invention having a weight average molecular weight of 40,000 to 80,000 falls within the range of the relative solution viscosity of 1.35 to 1.50 depending on the monomer constitutional unit and the composition ratio in the polycarbonate resin. .

<Glass transition temperature>
The glass transition temperature of the polycarbonate resin of the present invention is preferably 135 ° C to 200 ° C, more preferably 140 ° C to 200 ° C. The glass transition temperature is measured at a heating rate of 20 ° C./min. When the glass transition temperature is less than 135 ° C., the heat resistance of the molded article or film using the polycarbonate resin is insufficient, and when it exceeds 200 ° C., the moldability is deteriorated.

<Pencil hardness>
The pencil hardness measured in accordance with JIS K5600 at a thickness of 2 mm part of the plate on which the polycarbonate resin of the present invention is molded is F or higher, preferably H or higher, and more preferably 2H or higher. When the pencil hardness is less than F, the surface of a molded article or film using the polycarbonate resin is liable to be damaged.

<Organic solvent resistance>
The organic solvent resistance of the polycarbonate resin of the present invention is an evaluation of resistance to a neutral organic solvent. Specifically, a 0.1 mm thick film of the obtained polycarbonate resin was prepared, and 1 ml each of acetonitrile, xylene, cyclohexanone, chlorobenzene, and methyl ethyl ketone (hereinafter sometimes abbreviated as MEK) was dropped for 24 hours. After leaving it to stand, the solvent was wiped clean, and the change before and after the solvent was dropped was visually judged. When the shape is slightly deformed, the evaluation is preferable, and when the shape is not changed at all, it is more preferable. In the case of whitening, the organic solvent resistance becomes insufficient, which is not preferable.

<Molded product, film or sheet>
The aromatic polycarbonate resin of the present invention is molded and processed by any method such as an injection molding method, compression molding method, injection compression molding method, melt film forming method, casting method, etc., and includes an illumination cover, a signboard, a water tank, a resin window, In addition to transparent members such as front plates, optical parts such as light guide plates, diffuser plates, ride guides, optical lenses, and optical films, protective films, plastic substrates, front plates, display devices, and other electrical and electronic components, lamp lenses It can be used as a member requiring scratch resistance, heat resistance, and organic solvent resistance, such as automobile parts such as interior members and exterior members, and further OPC binders, housings, and trays. In particular, it is useful as an automobile member such as a lamp lens, an interior member, and an exterior material, or as a transparent member such as a lighting cover, a resin window, and a front plate.

<Additives>
In order to give various properties to the polycarbonate resin of the present invention within a range not impairing the object of the present invention, various additives may be added to form a resin composition. Additives include mold release agents, heat stabilizers, UV absorbers, bluing agents, antistatic agents, flame retardants, heat ray shielding agents, fluorescent dyes (including fluorescent whitening agents), pigments, light diffusing agents, reinforcing fillers Other resins and elastomers can be blended.

  As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester, partial ester or total ester of polyhydric alcohol and fatty acid. Specific examples of the monohydric alcohol, saturated fatty acid and ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like. Stearyl stearate is preferred. As partial ester or total ester of polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, All or partial esters of dipentaerythritol such as pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. Can be mentioned. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferable, and stearic acid monoglyceride and pentaerythritol tetrastearate are more preferable.

  Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer. Examples of phosphorus heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) Phosphite, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate, [1,1-biphenyl] -4,4-diylbis [bis (2,4-di-tert-butylphenoxy) phosphine], 3,9 -Bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane is preferred, tris (2,4-di-tert-butylphenyl) Phosphite, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propyl Acid stearyl, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10 Tetoraokisa 3,9-diphosphaspiro [5.5] undecane is preferred.

Examples are shown below, but the embodiments of the present invention will be described more specifically. The present invention is not limited to the examples shown below unless it is contrary to the spirit of the present invention.
The evaluation was performed by the following method.

(1) Copolymer composition ratio: 10 mg of the obtained polycarbonate resin was dissolved in 0.6 ml of deuterated chloroform, and proton NMR spectrum was measured with JNM-AL400 manufactured by JEOL Ltd. The composition ratio (unit: mol%) of the repeating unit was calculated from the integral ratio of the spectrum derived from each repeating unit.

(2) Weight average molecular weight: 10 mg of the obtained polycarbonate resin was dissolved in 5 ml of chloroform, and the weight average molecular weight was measured using a GPC (gel permeation chromatography) apparatus under the following conditions.
Equipment: GPC system (HLC8220) manufactured by Tosoh Corporation
Detector: CH-2 (UV wavelength 254 nm)
Column; Tsk-gel SuperHZ4000 + 3000 + 2000
Standard material: Tosoh standard polystyrene Eluent: Chloroform, 0.35 ml / min

(3) Relative solution viscosity: The obtained polycarbonate resin was dried at 100 ° C. for 12 hours or more and then measured according to ISO 1628-4.

(4) Glass transition temperature: 15 mg of the obtained polycarbonate resin was used, and DSC-60A manufactured by Shimadzu Corporation was used, under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min), and the heating rate: 20 ° C./min. The glass transition temperature was measured under the following conditions.

(5) Pencil hardness (scratch resistance): A 2 cm thick molded article of the obtained polycarbonate resin was produced at a cylinder temperature of 300 ° C. using a J75EIII injection molding machine manufactured by Nippon Steel Co., Ltd. and conformed to JIS K5600. The pencil hardness was measured.

(6) Organic solvent resistance: A 0.1 mm thick film of the obtained polycarbonate resin was prepared, and 1 ml each of acetonitrile, xylene, cyclohexanone, chlorobenzene and methyl ethyl ketone (MEK) was dropped and left for 24 hours. Was wiped cleanly, and the change before and after the dropping of the solvent was visually determined. The evaluation was as follows: ○: no change, ▲: shape deformed, x: whitening. When the shape is slightly deformed (▲), it is preferable for evaluation, and when the shape is completely unchanged (◯) is more preferable. When whitening (x), the organic solvent resistance becomes insufficient, which is not preferable.

[Example 1]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was placed in a nitrogen atmosphere by purging with nitrogen, and then charged with 592 parts of a 48% aqueous sodium hydroxide solution and 2,909 parts of ion-exchanged water. 486 parts of bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as BisOC-TMC), 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, after dissolving 82 parts of Bis-A) and 1.1 parts of hydrosulfite, 1,984 parts of methylene chloride was added. Subsequently, the reaction vessel was purged with nitrogen for 10 minutes, and then 240 parts of phosgene was blown in at about 18 to 21 ° C. over about 60 minutes with stirring. After completion of the phosgene blowing, 74 parts of 48% aqueous sodium hydroxide and 81 parts of p-tert-butylphenol were added, stirring was resumed, 0.5 parts of triethylamine was added after emulsification, and the mixture was further stirred at 20 to 27 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product was diluted with methylene chloride at room temperature and washed with water, then acidified with hydrochloric acid and washed with water. Washing with pure water was repeated until the conductivity of the aqueous phase was substantially the same as that of ion-exchanged water, to obtain a methylene chloride solution of polycarbonate resin. Next, it is dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride, and then the liquid-containing flakes are pulverized and dried to obtain a powdery polycarbonate resin. Obtained. The powdery polycarbonate resin was vacuum-dried at 120 ° C. for 4 hours, and then added with tris (2,4-di-tert-butylphenyl) phosphite 0.050% based on the weight of the resulting resin composition, Pelletization was performed using a vented φ30 mm single screw extruder. The weight average molecular weight of the obtained polycarbonate resin was 56,700, the relative solution viscosity was 1.361, and the glass transition temperature was 188 ° C. Table 1 shows the weight average molecular weight, glass transition temperature, and characteristics of the molded article of the polycarbonate resin.

[Example 2]
Polymerization was performed in the same manner as in Example 1 except that 426 parts of BisOC-TMC and 123 parts of Bis-A were used, and pelletization was performed. The obtained polycarbonate resin had a weight average molecular weight of 58,800, a relative solution viscosity of 1.381, and a glass transition temperature of 185 ° C. Table 1 shows the weight average molecular weight, glass transition temperature, and characteristics of the molded article of the polycarbonate resin.

[Example 3]
Polymerization was performed in the same manner as in Example 1 except that 304 parts of BisOC-TMC and 205 parts of Bis-A were used, and pelletization was performed. The obtained polycarbonate resin had a weight average molecular weight of 44,700, a relative solution viscosity of 1.366, and a glass transition temperature of 173 ° C. Table 1 shows the weight average molecular weight, glass transition temperature, and characteristics of the molded article of the polycarbonate resin.

[Example 4]
Polymerization was performed in the same manner as in Example 1 except that 213 parts of BisOC-TMC and 267 parts of Bis-A were used, and pelletization was performed. The weight average molecular weight of the obtained polycarbonate resin was 52,500, the relative solution viscosity was 1.361, and the glass transition temperature was 163 ° C. Table 1 shows the weight average molecular weight, glass transition temperature, and characteristics of the molded article of the polycarbonate resin.

[Example 5]
Polymerization and pelletization were carried out in the same manner as in Example 1 except that Bis-A was 92 parts of 4,4-bis (4-hydroxy-3-methylphenyl) propane (hereinafter sometimes abbreviated as Bis-C). Was carried out. The weight average molecular weight of the obtained polycarbonate resin was 56,600, the relative solution viscosity was 1.361, and the glass transition temperature was 181 ° C. Table 1 shows the weight average molecular weight, glass transition temperature, and characteristics of the molded article of the polycarbonate resin.

[Example 6]
Polymerization was performed in the same manner as in Example 1 except that BisOC-TMC was 304 parts and Bis-A was Bis-C230 parts, and pelletization was performed. The weight average molecular weight of the obtained polycarbonate resin was 49,500, the relative solution viscosity was 1.366, and the glass transition temperature was 156 ° C. Table 1 shows the weight average molecular weight, glass transition temperature, and characteristics of the molded article of the polycarbonate resin.

[Example 7]
Polymerization was performed in the same manner as in Example 1 except that 213 parts of BisOC-TMC and 299 parts of Bis-A were added to Bis-C, and pelletization was performed. The weight average molecular weight of the obtained polycarbonate resin was 47,200, the relative solution viscosity was 1.376, and the glass transition temperature was 146 ° C. Table 1 shows the weight average molecular weight, glass transition temperature, and characteristics of the molded article of the polycarbonate resin.

[Comparative Example 1]
Polymerization was performed in the same manner as in Example 1 except that BisOC-TMC was 122 parts and Bis-A was 328 parts, and pelletization was performed. The weight average molecular weight of the obtained polycarbonate resin was 58,300, the relative solution viscosity was 1.450, and the glass transition temperature was 163 ° C. The weight average molecular weight, glass transition temperature, and properties of the molded article of the polycarbonate resin are shown in Table 2.

[Comparative Example 2]
Polymerization was carried out in the same manner as in Example 1 except that 426 parts of BisOC-TMC, 123 parts of Bis-A, and 203 parts of p-tert-butylphenol were used, and pelletization was carried out. The obtained polycarbonate resin had a weight average molecular weight of 25,500, a relative solution viscosity of 1.214, and a glass transition temperature of 181 ° C. The weight average molecular weight, glass transition temperature, and properties of the molded article of the polycarbonate resin are shown in Table 2.

[Comparative Example 3]
Polymerization was performed in the same manner as in Example 1 except that 213 parts of BisOC-TMC, 299 parts of Bis-C and 205 parts of p-tert-butylphenol were used, and the process up to pelletization was performed. The weight average molecular weight of the obtained polycarbonate resin was 21,200, the relative solution viscosity was 1.211, and the glass transition temperature was 142 ° C. The weight average molecular weight, glass transition temperature, and properties of the molded article of the polycarbonate resin are shown in Table 2.

[Comparative Example 4]
Except that BisOC-TMC is 433 parts of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter may be abbreviated as Bis-TMC), and Bis-A is 83 parts. Polymerization was carried out in the same manner as in Example 1, and pelletization was carried out. The obtained polycarbonate resin had a weight average molecular weight of 52,300, a relative solution viscosity of 1.376, and a glass transition temperature of 223 ° C. The weight average molecular weight, glass transition temperature, and properties of the molded article of the polycarbonate resin are shown in Table 2.

[Comparative Example 5]
Polymerization was performed in the same manner as in Example 1 except that Bis-TMC was changed to Bis-TMC433 and Bis-A was changed to Bis-C93, and pelletization was performed. The weight average molecular weight of the obtained polycarbonate resin was 48,000, the relative solution viscosity was 1.365, and the glass transition temperature was 218 ° C. The weight average molecular weight, glass transition temperature, and properties of the molded article of the polycarbonate resin are shown in Table 2.

[Comparative Example 6]
Polymerization was performed in the same manner as in Example 1 except that BisOC-TMC was changed to Bis-C459 parts and Bis-A was changed to 0 parts, and pelletization was performed. The weight average molecular weight of the obtained polycarbonate resin was 46,800, the relative solution viscosity was 1.357, and the glass transition temperature was 120 ° C. The weight average molecular weight, glass transition temperature, and properties of the molded article of the polycarbonate resin are shown in Table 2.

[Comparative Example 7]
Polymerization was carried out in the same manner as in Example 1 except that BisOC-TMC was 0 parts and Bis-A was 409 parts, and pelletization was carried out. The weight average molecular weight of the obtained polycarbonate resin was 45,300, the relative solution viscosity was 1.366, and the glass transition temperature was 145 ° C. The weight average molecular weight, glass transition temperature, and properties of the molded article of the polycarbonate resin are shown in Table 2.

  Examples 1 to 7 shown in the table have high scratch resistance of pencil hardness of H to 3H and heat resistance of glass transition temperature of 135 ° C. or higher, and representative examples include acetonitrile, xylene, cyclohexanone, Although chlorobenzene and methyl ethyl ketone (MEK) have been shown, they are excellent in organic solvent resistance and can be usefully used as molded articles and films. On the other hand, Comparative Example 1 is heat resistant at a glass transition temperature of 135 ° C. or higher, and the pencil hardness is F, but is inferior in organic solvent resistance. Comparative Examples 2 and 3 have high scratch resistance and heat resistance, but are inferior in organic solvent resistance. Although Comparative Example 4 has very high heat resistance, the pencil hardness is inferior to B and scratch resistance, and is also inferior to organic solvent resistance. Moreover, although the comparative example 5 has heat resistance, pencil hardness is not high in HB and scratch resistance, and it is inferior to organic solvent resistance. Comparative Example 6 has a high pencil hardness of 2H and good organic solvent resistance, but has a low glass transition temperature and poor heat resistance. Comparative Example 7 is a general polycarbonate resin having a unit structure of Bis-A, but is inferior in scratch resistance and organic solvent resistance.

  Since the polycarbonate resin of the present invention is a polycarbonate resin having high scratch resistance and excellent heat resistance and organic solvent resistance, it includes transparent members such as lighting covers, signboards, water tanks, resin windows, and front plates. , Optical parts such as light guide plate, diffuser plate, ride guide, optical lens, optical film, electrical / electronic parts such as protective film, plastic substrate, display device member, automobile parts such as lamp lens, interior member, exterior member, Furthermore, it is also useful as an OPC binder, housing, tray, and the like. In particular, it is useful as an automobile member such as a lamp lens, an interior member, and an exterior material, or as a transparent member such as a lighting cover, a resin window, and a front plate.

Claims (11)

The repeating unit represented by the following formula (1) is contained in a proportion of 30 to 100 mol% in all repeating units, the weight average molecular weight measured by GPC method is 40,000 to 80,000, and JIS Polycarbonate resin whose pencil hardness measured according to K5600 is F or more.

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom having 1 to 6 carbon atoms. Represents an alkyl group.) 2. The polycarbonate resin according to claim 1, wherein the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (2).

(In the formula, R ³ and R ⁴ have the same meanings as the formula (1).)   The repeating unit represented by the formula (1) is a repeating unit derived from 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane. Item 5. The polycarbonate resin according to Item 1. The polycarbonate resin in any one of Claims 1-3 containing the repeating unit represented by following formula (3).

(In formula (3), W is (4)

Or at least one divalent organic residue selected from the group consisting of a single bond, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an aromatic having 1 to 9 carbon atoms. Represents an alkyl group which may contain a group, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to R ⁶ carbon atoms. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an aromatic group. Represent. n is an integer of 4-7. )   The repeating unit represented by the formula (3) is 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, α, α′-bis ( The polycarbonate resin according to claim 4, wherein the polycarbonate resin is a repeating unit derived from any of 4-hydroxyphenyl) -1,3-diisopropylbenzene.   The polycarbonate resin according to claim 4, wherein the repeating unit represented by the formula (3) is a repeating unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane.   The polycarbonate resin according to any one of claims 1 to 6, which has a glass transition temperature of 135 ° C to 200 ° C.   A molded product obtained by molding the polycarbonate resin according to claim 1.   An automobile lamp lens, an automobile interior member, or an automobile exterior member made of the polycarbonate resin according to claim 1.   An illumination cover, a resin window, or a front plate made of the polycarbonate resin according to claim 1.   A film or sheet obtained by molding the polycarbonate resin according to claim 1.