Aromatic polycarbonate resin, polycarbonate resin composition and molded article

Abstract

The present invention relates to an aromatic polycarbonate resin which comprises a repeating unit represented by formula (II). (In formula (II), R11, R12, R13, c, d and n are as defined above.)

Description

Aromatic polycarbonate resin, polycarbonate resin composition and molded article

[0001] The present invention relates to an aromatic polycarbonate resin, a polycarbonate resin composition, and a molded article.

[0002] Polycarbonate resins have excellent impact resistance, transparency, heat resistance, and self-extinguishing properties, and are widely used as engineering plastics in various fields, such as electrical and electronic equipment and automobiles. However, polycarbonate resins have low surface hardness and may have insufficient scratch resistance. Patent Document 1 discloses a polycarbonate copolymer having improved scratch resistance, which contains units derived from a hydroxy-terminated monocyclic, polycyclic, or fused cyclic compound having a (meth)acrylate group and carbonate units. Patent Document 2 discloses branched or crosslinked fire-resistant polycarbonate resins and intermediates thereof.

[0003] Korean Patent Publication No. 2016-0141268 JP 2-219818 A

[0004] A known method for improving surface hardness is to coat the top layer of a structure made of a polycarbonate-based resin, but this requires a coating process, which complicates the manufacturing process and increases the environmental impact. Another known method involves blending with an acrylic resin such as polymethyl methacrylate resin, which has excellent surface hardness and transparency, but this tends to result in insufficient transparency due to phase separation and differences in refractive index. Furthermore, the invention described in Patent Document 1 has insufficient surface hardness and transparency. Patent Document 2 does not describe any method for improving surface hardness. Thus, further investigation was needed to achieve both transparency and scratch resistance using a polycarbonate-based resin alone.

[0005] An object of the present invention is to provide an aromatic polycarbonate resin, a polycarbonate resin composition, and a molded article that have improved surface hardness without impairing the appearance and that combine transparency and scratch resistance.

[0006] The present inventors have found that the above problems can be solved by an aromatic polycarbonate resin containing a specific repeating unit. That is, the present invention encompasses the following 1 to 18. 1. An aromatic polycarbonate resin containing a repeating unit represented by the following formula (II):

[0007]

[0008] [In formula (II), R 11 and R 12 R each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 13 represents a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20. 2. The aromatic polycarbonate resin according to item 1 above, further comprising a repeating unit represented by the following formula (I), wherein the molar ratio of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) ((I):(II)) is 0:100 to 99.5:0.5:

[0009]

[0010] [In formula (I), R １ and R ２each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, -S-, -SO-, -SO ２ represents -, -O-, or -CO-. a and b each independently represent an integer of 0 to 4.] 3. The aromatic polycarbonate resin according to 2 above, wherein the molar ratio ((I):(II)) of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) is 0.5:99.5 to 99.5:0.5. 4. The aromatic polycarbonate resin according to 2 above, wherein the molar ratio ((I):(II)) of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) is 60:40 to 99.5:0.5. 5. R 14 5. The aromatic polycarbonate resin according to any one of items 1 to 4 above, wherein R represents a saturated or unsaturated alicyclic group having 3 to 12 carbon atoms or a saturated or unsaturated heterocyclic group having 3 to 12 members. 14 is a cyclopentyl group or a cyclohexyl group, and n is 2. 7. The aromatic polycarbonate resin according to any one of items 1 to 6 above, having a viscosity average molecular weight of 10,000 to 100,000. 8. The aromatic polycarbonate resin according to any one of items 1 to 7 above, having a scratch hardness of F or more as evaluated in accordance with JIS K5600-5-4. 9. The aromatic polycarbonate resin according to any one of items 1 to 8 above, having a total light transmittance of 87% or more at a thickness of 1.5 mm. 10. A dihydric phenol compound represented by the following formula (ii):

[0011]

[0012] [In formula (ii), R 11 and R 12 R each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 13 represents a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20.] 11. A method for producing an aromatic polycarbonate resin, comprising a step of interfacially polycondensing a dihydric phenol compound and a polycarbonate oligomer in the presence of a water-insoluble organic solvent and an aqueous alkaline compound solution, wherein the dihydric phenol compound comprises a dihydric phenol compound (a) represented by formula (ii) above.

[0013]

[0014] [In formula (ii), R 11 and R 12 R each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 13represents a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20. 12. A polycarbonate-based resin composition comprising the aromatic polycarbonate-based resin described in any one of items 1 to 9 above. 13. The polycarbonate-based resin composition described in item 12 above for use in scratch-resistant applications. 14. A molded article made from the polycarbonate-based resin composition described in item 12 or 13 above. 15. The molded article described in item 14 above, which is a plastic window, a touch panel, an interior product, an exterior product, an interior or exterior part of a vehicle, a housing, an electrical appliance, a building material, or office automation equipment. 16. A structure having an outer surface formed from the polycarbonate-based resin composition described in item 12 or 13 above. 17. 17. Use of the aromatic polycarbonate resin according to any one of items 1 to 9 above or the polycarbonate resin composition according to item 11 above for scratch-resistant applications. 18. Use of the aromatic polycarbonate resin according to any one of items 1 to 9 above or the polycarbonate resin composition according to item 12 above for producing a plastic window, a touch panel, an interior product, an exterior product, an interior or exterior part of a vehicle, a housing, an electrical appliance, a building material, or an office automation device. 19. Use of a dihydric phenol compound represented by the following formula (ii) for producing an aromatic polycarbonate resin.

[0015]

[0016] [In formula (ii), R 11 and R 12R each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 13 represents a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20.]

[0017] According to the present invention, it is possible to provide an aromatic polycarbonate resin, a polycarbonate resin composition, and a molded article that have both transparency and scratch resistance.

[0018] FIG. 1 shows the cyclohexyl diphenolate obtained in Synthesis Example 1. １ 2 is a H-NMR chart of cyclopentyl diphenolate obtained in Synthesis Example 2. １ 3 is a H-NMR chart of methyl diphenolate obtained in Synthesis Example 3. １ 4 is a H-NMR chart of the intermediate compound 2,2-bis(4-hydroxyphenyl)propanoic acid obtained in Synthesis Example 4. １ 5 is a H-NMR chart of cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate obtained in Synthesis Example 4. １ 6 is a H-NMR chart of the BPA-cyclohexyl diphenolate copolymer obtained in Production Example 1. １ 7 is a H-NMR chart of the BPA-cyclopentyl diphenolate copolymer obtained in Production Example 2. １8 is a H-NMR chart of the BPA-methyl diphenolate copolymer obtained in Production Example 3. １ 9 is a H-NMR chart of the BPA-cyclohexyl diphenolate copolymer obtained in Production Example 4. １ 10 is a H-NMR chart of the BPA-cyclohexyl diphenolate copolymer obtained in Production Example 5. １ 11 is a H-NMR chart of the BPA-cyclohexyl diphenolate copolymer obtained in Production Example 6. １ 12 is a H-NMR chart of the BPA-cyclohexyl diphenolate copolymer obtained in Production Example 7. １ 13 is a H-NMR chart of the BPA-cyclopentyl diphenolate copolymer obtained in Production Example 8. １ 14 is a H-NMR chart of the BPA-cyclopentyl diphenolate copolymer obtained in Production Example 9. １ 15 is a H-NMR chart of the BPA-cyclopentyl diphenolate copolymer obtained in Production Example 10. １ 16 is a H-NMR chart of the BPA-2,2-bis(4-hydroxyphenyl)cyclohexyl propanoate copolymer obtained in Production Example 11. １ 17 is a H-NMR chart of the BPA-2,2-bis(4-hydroxyphenyl)cyclohexyl propanoate copolymer obtained in Production Example 12. １ 18 is a H-NMR chart of the BPA-methyl diphenolate copolymer obtained in Production Example 13. １ 1H-NMR chart.

[0019] The aromatic polycarbonate resin, polycarbonate resin composition, and molded article of the present invention will be described in detail below. In this specification, any definition that is considered preferable can be adopted at will, and a combination of preferable definitions can be considered more preferable. In this specification, the expression "XX to YY" means "XX or more and YY or less."

[0020] 1. Aromatic Polycarbonate Resin The aromatic polycarbonate resin of the present invention contains a repeating unit represented by the following formula (II):

[0021]

[0022] [In formula (II), R 11 and R 12 R each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 13 represents a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20.]

[0023] In the above formula (II), R 11 and R 12 The halogen atoms independently represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 11 and R 12 Examples of alkyl groups that R each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups (the term "various" refers to both linear and branched groups, and the same applies hereinafter), various pentyl groups, and various hexyl groups. 11 and R 12 The alkoxy groups each independently represent include those in which the alkyl group moiety is the above-mentioned alkyl group. 11 and R 12Examples of the cycloalkyl group that each independently represents include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. 11 and R 12 The cycloalkyl group represented by each independently includes a case where the cycloalkyl group moiety is the above-mentioned cycloalkyl group. 11 and R 12 Examples of the alkenyl group that each independently represents include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. 11 and R 12 Examples of the aryl group that each independently represents include a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. 11 and R 12 The aryloxy groups each independently represent include those in which the aryl group moiety is the above-mentioned aryl group. 11 and R 12 Examples of the aralkyl group that each independently represents include a phenylmethyl group and a phenylethyl group. 11 and R 12 The aralkyloxy groups represented by each independently include those in which the aralkyl group moiety is the above-mentioned aralkyl group.

[0024] In the above formula (II), R 13 Examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups (the term "various" refers to both linear and branched groups, and the same applies hereinafter), various pentyl groups, and various hexyl groups. 13 Examples of the cycloalkyl group represented by R include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. 13 The cycloalkoxy group represented by R is a group in which the cycloalkyl group moiety is the above-mentioned cycloalkyl group. 13 Examples of the alkenyl group represented by R include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. 13Examples of the aryl group represented by the formula (I) include a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

[0025] In the above formula (II), R 14 The saturated or unsaturated alicyclic group represented by R has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples thereof include cycloalkyl groups, which are saturated alicyclic groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group, and nobornyl group, and cycloalkenyl groups, which are unsaturated alicyclic groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, and cycloheptenyl group. Note that unsaturated alicyclic groups do not include aromatic groups. R 14 The heterocyclic group represented by the formula (I) has 3 to 20 ring-membering atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. The heterocyclic group is a cyclic group containing at least one heteroatom, for example, 1, 2, or 3, among the ring-forming atoms. Specific examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom. Examples of the heterocyclic group include a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, an indolinyl group, a quinolinyl group, an acridinyl group, a pyrrolidinyl group, a dioxanyl group, a piperidinyl group, an oxiranyl group (an epoxy group), an oxetanyl group, a morpholidinyl group, a piperazinyl group, a carbazolyl group, a furanyl group, a thiophenyl group, an oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzimidazolyl group, and a puranyl group. 14 represents preferably a saturated or unsaturated alicyclic group having 3 to 12 carbon atoms or a saturated or unsaturated heterocyclic group having 3 to 12 members, more preferably a cycloalkyl group having 3 to 18 carbon atoms, and even more preferably a cyclopentyl group or a cyclohexyl group.

[0026] c and d each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0027] n represents an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably 0, 1, 2, 3, or 4, and still more preferably 2. In another embodiment, n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4.

[0028] In a preferred embodiment of the formula (II), from the viewpoint of achieving both transparency and scratch resistance, R 14 represents a cyclopentyl group or a cyclohexyl group, and n is 2. Furthermore, each of c and d is preferably 0, and R 13 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. In the aromatic polycarbonate resin, the repeating unit represented by the above formula (II) may be of one type alone or a combination of two or more types.

[0029] The aromatic polycarbonate resin may further contain a repeating unit represented by the following formula (I).

[0030]

[0031] [In formula (I), R １ and R ２ each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, -S-, -SO-, -SO ２ represents —, —O—, or —CO—; and a and b each independently represent an integer of 0 to 4.]

[0032] In the above formula (I), R 1 and R2 The halogen atoms independently represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 1 and R 2 Examples of alkyl groups that R each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups (the term "various" includes linear and branched groups, and the same applies hereinafter), various pentyl groups, and various hexyl groups. 1 and R 2 The alkoxy groups each independently represent include those in which the alkyl group moiety is the above-mentioned alkyl group. 1 and R 2 Examples of the cycloalkyl group that each independently represents include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. 1 and R 2 The cycloalkyl group represented by each independently includes a case where the cycloalkyl group moiety is the above-mentioned cycloalkyl group. 1 and R 2 Examples of the alkenyl group that each independently represents include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. 1 and R 2 Examples of the aryl group that each independently represents include a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. 1 and R 2 The aryloxy groups each independently represent include those in which the aryl group moiety is the above-mentioned aryl group. 1 and R 2 Examples of the aralkyl group that each of R independently represents include a phenylmethyl group and a phenylethyl group. 1 and R 2 The aralkyloxy groups represented by each independently include those in which the aralkyl group moiety is the above-mentioned aralkyl group.

[0033] The alkylene group represented by X has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. The cycloalkylene group represented by X has 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples thereof include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group. Examples of the arylene group represented by X include a phenylene group, a naphthylene group, a biphenylene group, and a tetraphenyl group. The cycloalkylidene group represented by X has 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples thereof include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group. Examples of the aryl moiety of the aralkyl group (aryl alkylene group) represented by X include aryl groups having 6 to 14 ring carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. Among the above, when X is an isopropylidene group, a cyclohexylidene group, or a 3,5,5-trimethylcyclohexylidene group, it is preferable because the molded article of the aromatic polycarbonate resin can satisfy both surface hardness and mechanical properties.

[0034] a and b each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among these, a case where a and b are 0 and X represents a single bond or an alkylene group having 1 to 8 carbon atoms, or a case where a and b are 0 and X represents an alkylidene group, particularly an isopropylidene group, is preferred. In another embodiment, a case where a and b are 1 and X represents a single bond or an alkylene group having 1 to 8 carbon atoms, or a and b are 1 and X represents an alkylidene group, particularly an isopropylidene group, is also preferred because molded articles of aromatic polycarbonate resins can achieve both surface hardness and mechanical properties.

[0035] Specific examples of the repeating unit represented by the above formula (I) include repeating units represented by the following general formulae (Ii) to (I-iv).

[0036]

[0037] In the aromatic polycarbonate resin, the repeating unit represented by formula (I) may be a single type or a combination of two or more types. Specific examples include an embodiment consisting solely of a repeating unit represented by general formula (Ii); and an embodiment consisting of a combination of a repeating unit represented by general formula (Ii) with one or more repeating units selected from the group consisting of repeating units represented by general formulas (I-ii) to (I-iv). Such aromatic polycarbonate resins can be easily produced by an interfacial polymerization method, described below, in which a polycarbonate oligomer is produced in advance.

[0038] When the aromatic polycarbonate-based resin contains a repeating unit represented by formula (I), the aromatic polycarbonate-based resin is an aromatic polycarbonate-based copolymer containing a repeating unit represented by formula (I) and a repeating unit represented by formula (II).

[0039] In the aromatic polycarbonate resin, the molar ratio ((I):(II)) of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) is preferably 0:100 to 99.5:0.5, more preferably 0.5:99.5 to 99.5:0.5, even more preferably 0.5:99.5 to 99:1, still more preferably 0.5:99.5 to 94:6, and most preferably 0.5:99.5 to 92:8. In particular, the molar ratio ((I):(II)) of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) is preferably 60:40 to 99.5:0.5, more preferably 70:30 to 99:1, and even more preferably 80:20 to 98:2. The molar ratio of the repeating unit represented by the formula (I) to the repeating unit represented by the formula (II) in the aromatic polycarbonate resin is calculated by nuclear magnetic resonance (NMR) measurement. １ H NMR measurement is carried out, and the value is calculated from the integrated values ​​of the peak derived from the repeating unit represented by formula (I) above and the peak derived from the repeating unit represented by formula (II) above.

[0040] The aromatic polycarbonate resin of the present invention may contain structural units other than the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II), such as a terminal structure derived from a terminal terminator described below, and a structural unit containing a silicon atom.

[0041] From the viewpoints of mechanical properties and moldability, the viscosity average molecular weight of the aromatic polycarbonate resin is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 15,000 to 30,000, and even more preferably 17,000 to 25,000. In the present invention, the viscosity average molecular weight (Mv) is calculated by measuring the viscosity of a methylene chloride solution (concentration: g / L) at 20°C using an Ubbelohde viscometer, determining the intrinsic viscosity [η] from this, and then calculating the viscosity average molecular weight (Mv) using the following Schnell formula: [η]=1.23×10 －５ Mv ０．８３

[0042] The aromatic polycarbonate resin of the present invention can provide a molded product thereof with both excellent transparency and scratch resistance. The scratch resistance can be evaluated by scratch hardness (pencil method). The scratch hardness (pencil method) of the molded product of the aromatic polycarbonate resin is preferably F or higher, as evaluated in accordance with JIS K5600-5-4:1999.

[0043] The transparency can be evaluated by the total light transmittance. The total light transmittance of the aromatic polycarbonate resin at a thickness of 1.5 mm, measured in accordance with ASTM D1003, is preferably 87% or more, more preferably 88% or more, and even more preferably 89% or more.

[0044] 2. Method for Producing Aromatic Polycarbonate Resin (Dihydric Phenol Compound) The aromatic polycarbonate resin can be preferably produced using a dihydric phenol compound (a) represented by the following formula (ii). The repeating unit represented by the above formula (II) of the aromatic polycarbonate resin is derived from the dihydric phenol compound (a). Therefore, the present invention also provides use of the dihydric phenol compound (a) represented by the following formula (ii) for producing an aromatic polycarbonate resin.

[0045]

[0046] [In formula (ii), R 11 , R 12 , R 13 , R 14 , c, d and n are as defined above, and the preferred values ​​are also the same.]

[0047] Preferred specific examples of the dihydric phenol compound (a) include cyclohexyl diphenolate represented by the following formula (ii-1) and cyclopentyl diphenolate represented by the following formula (ii-2).

[0048]

[0049] The dihydric phenol compound (a) can be produced, for example, by reacting a carboxylic acid compound (ax) represented by the following formula (ii-x) with an alcohol compound (ay) represented by the following formula (ii-y) in the presence of an acid catalyst, if necessary.

[0050]

[0051] [In formula (ii-x), R 11 , R 12 , R 13 , c, d and n are as defined above, and the preferred values ​​are also the same.]

[0052]

[0053] [In formula (ii-y), R 14 are as defined above, and the preferred definitions are also the same.]

[0054] (Method for producing aromatic polycarbonate resin) The aromatic polycarbonate resin can be produced by a known method for producing polycarbonate resins, as long as the dihydric phenol compound (a) is represented by the formula (ii) above. Examples of methods for producing polycarbonate resins include: (i) an interfacial polymerization method (phosgene method) in which a dihydric phenol compound and phosgene are reacted in the presence of an organic solvent inert to the reaction or an aqueous alkali solution, followed by polymerization by adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt; (ii) a melt polymerization method (ester exchange method) in which a dihydric phenol compound and a carbonate diester are subjected to an ester exchange reaction in a molten state without using a solvent, by adding a basic catalyst; and (iii) a pyridine method in which a dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is introduced to directly produce the polycarbonate resin. During the above reaction, a molecular weight modifier (terminal capping agent), a branching agent, etc. may be used as needed.

[0055] Among these, the following production method is preferred: a production method for an aromatic polycarbonate resin, comprising a step of interfacially polycondensing a dihydric phenol compound and a polycarbonate oligomer in the presence of a water-insoluble organic solvent and an aqueous alkaline compound solution, wherein the dihydric phenol compound comprises a dihydric phenol compound (a) represented by the above formula (ii).

[0056] Specifically, in the case of the interfacial polymerization method, the aromatic polycarbonate resin can be produced by dissolving a pre-produced polycarbonate oligomer (described below) in a water-insoluble organic solvent (e.g., methylene chloride), adding an alkaline compound aqueous solution of a dihydric phenol compound (e.g., sodium hydroxide aqueous solution), and using a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., trimethylbenzylammonium chloride) as a polymerization catalyst, and optionally in the presence of a terminal terminator (a monohydric phenol such as p-tert-butylphenol). In addition, in the case of the interfacial polymerization method, the aromatic polycarbonate resin can be produced by copolymerizing a dihydric phenol with phosgene, a carbonate ester, or a chloroformate.

[0057] Polycarbonate oligomers can be produced by reacting a dihydric phenol compound with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene, chloroform, etc. When producing a polycarbonate oligomer using the transesterification method, it can also be produced by reacting a dihydric phenol compound with a carbonate precursor such as diphenyl carbonate.

[0058] The dihydric phenol includes a dihydric phenol compound (a) represented by the following formula (ii) from which the repeating unit represented by the above formula (II) is derived. The dihydric phenol preferably further includes a dihydric phenol compound (b) represented by the following formula (i) from which the repeating unit represented by the above formula (I) is derived.

[0059]

[0060] [In formula (ii), R 11 , R 12 , R 13 , R 14 , c, d and n are as defined above, and the preferred values ​​are also the same.]

[0061]

[0062] [In formula (i), R １ , R ２ , X, a, and b are as defined above, and the preferred values ​​are also the same.]

[0063] Examples of the dihydric phenol compound (b) include bis(hydroxyphenyl)alkane compounds such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A (BPA)], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane; 4,4'-dihydroxydiphenyl; bis(4-hydroxyphenyl)cycloalkane; bis(4-hydroxyphenyl)oxide; bis(4-hydroxyphenyl)sulfide; bis(4-hydroxyphenyl)sulfone; bis(4-hydroxyphenyl)sulfoxide; and bis(4-hydroxyphenyl)ketone. These dihydric phenol compounds may be used alone or in combination of two or more. Among these, bis(hydroxyphenyl)alkane dihydric phenols are preferred, and bisphenol A is more preferred.

[0064] In a preferred production method, the dihydric phenol compound (b) alone can be used as the dihydric phenol compound for producing the polycarbonate oligomer. In this case, the dihydric phenol compound (a) and the dihydric phenol compound (b) are used in combination, or the dihydric phenol compound (a) alone is used in the interfacial polycondensation reaction step.

[0065] A terminal terminator (molecular weight regulator) can be used to adjust the molecular weight of the resulting aromatic polycarbonate resin. Examples of terminal terminators include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0066] The aromatic polycarbonate resin of the present invention can provide a molded article having both excellent transparency and scratch resistance, and therefore can be suitably used in scratch-resistant applications.

[0067] 3. Polycarbonate Resin Composition The polycarbonate resin composition of the present invention contains the above-mentioned aromatic polycarbonate resin and, if necessary, other components, such as hydrolysis stabilizers, antioxidants, ultraviolet absorbers, flame retardants, flame retardant auxiliaries, reinforcing materials, fillers, and additives such as impact-improving elastomers, pigments, and dyes.

[0068] For example, the polycarbonate resin composition may contain an antioxidant from the viewpoint of preventing oxidative degradation during melting and preventing coloration due to oxidative degradation. The content of the antioxidant is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.3 parts by mass, and even more preferably 0.02 to 0.2 parts by mass, per 100 parts by mass of the aromatic polycarbonate resin. When the content of the antioxidant is within the above range, a sufficient antioxidant effect can be obtained and mold contamination during molding can be suppressed.

[0069] The method for producing the polycarbonate resin composition of the present invention is not particularly limited as long as it includes a step of mixing the aromatic polycarbonate resin with any other components. For example, the polycarbonate resin composition can be produced by mixing the aromatic polycarbonate resin with any other components using a mixer or the like, followed by melt-kneading. The melt-kneading can be carried out by a commonly used method, such as a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder. The heating temperature during melt-kneading is appropriately selected, for example, from the range of 150°C to 300°C, preferably from about 220°C to 300°C.

[0070] The polycarbonate resin composition of the present invention can provide molded articles having both excellent transparency and scratch resistance, and therefore can be suitably used in scratch-resistant applications. Examples of scratch-resistant applications include structures whose outer surfaces are formed from the polycarbonate resin composition, and more specifically, plastic windows, touch panels, interior goods, exterior goods, interior or exterior parts of vehicles, housings, electrical appliances, building materials, office automation equipment, etc. The polycarbonate resin composition of the present invention can be suitably used to produce the above-mentioned articles.

[0071] 4. Molded Article The molded article of the present invention comprises the polycarbonate resin composition described above. The molded article can be produced by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, or the like, using a melt-kneaded product of the polycarbonate resin composition or pellets obtained through melt-kneading as a raw material. It is particularly preferable to produce a molded article by injection molding or injection compression molding using pellets obtained through melt-kneading. The thickness of the molded article can be set as desired depending on the application. When transparency is particularly required, the thickness is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and even more preferably 0.3 to 2.0 mm. A molded article having a thickness of 0.2 mm or more does not warp and has good mechanical strength. Furthermore, a molded article having a thickness of 4.0 mm or less achieves high transparency.

[0072] Molded articles made from the polycarbonate resin composition of the present invention can be suitably used, for example, as plastic windows, touch panels, interior and exterior products, interior and exterior vehicle parts, housings, electrical appliances, or building materials.

[0073] The present invention will be further described with reference to examples. However, the present invention is not limited to these examples. Measurements and evaluations in each example were carried out by the methods shown below.

[0074] 1. Measurement of Viscosity Average Molecular Weight (Mv) The viscosity average molecular weight (Mv) was determined by measuring the viscosity of a methylene chloride solution (concentration: g / L) at 20°C using an Ubbelohde viscometer, determining the intrinsic viscosity [η] from the viscosity, and calculating the viscosity average molecular weight (Mv) using the following formula (Schnell's formula): [η] = 1.23 × 10 －５ Mv ０．８３

[0075] 2. １ H-NMR measurement conditions Nuclear magnetic resonance (NMR) apparatus: "Asend 500" manufactured by Bruker Japan Co., Ltd. Probe: 5 mm diameter TCI cryoprobe Observation width: 20 ppm Observation center: 6.175 ppm Pulse repetition time: 10 seconds Flip angle: 30° NMR sample tube: 5 mm diameter Sample amount: 50 mg Solvent: deuterated chloroform containing tetramethylsilane (TMS) Measurement temperature: 25°C Number of accumulations: 256 Chemical shift correction: TMS peak set as the reference at 0 ppm

[0076] 3. Quantitative determination of the composition ratio of aromatic polycarbonate resins. Using the "Asend 500" manufactured by Bruker Japan Co., Ltd., the sample dissolved in deuterated chloroform containing TMS was １ H-NMR was measured under the same conditions as above, and the structure of the aromatic polycarbonate resin was assigned. Specifically, the integral values ​​of the following peaks (i) to (iii) were determined. - In the case of BPA-cyclohexyl diphenolate copolymer: (i) The integral value obtained by summing the phenyl groups of the bisphenol A (BPA) moiety, the phenyl groups of the cyclohexyl diphenolate moiety, and the phenyl groups of the p-tert-butylphenol (PTBP) moiety observed at around δ 6.8 to 7.5; (ii) The integral value of the methine group of the cyclohexyl diphenolate moiety observed at around δ 4.6 to 4.8; (iii) The integral value of the methyl group of the PTBP moiety observed at around δ 1.30 to 1.33.

[0077] In the case of BPA-cyclopentyl diphenolate copolymer: (i) The total integral of the phenyl group of the BPA part, the phenyl group of the cyclopentyl diphenolate part, and the phenyl group of the PTBP part observed in the vicinity of δ 6.8 to 7.5. (ii) The integral of the methine group of the cyclopentyl diphenolate part observed in the vicinity of δ 5.05 to 5.15. (iii) The integral of the methyl group of the PTBP part observed in the vicinity of δ 1.30 to 1.33.

[0078] In the case of BPA-2,2-bis(4-hydroxyphenyl)propanoic acid cyclohexyl copolymer (i) The integral value of the sum of the phenyl groups of the bisphenol A (BPA) part, the phenyl groups of the 2,2-bis(4-hydroxyphenyl)propanoic acid cyclohexyl part, and the phenyl groups of the p-tert-butylphenol (PTBP) part observed in the vicinity of δ 6.8 to 7.5 (ii) The integral value of the methine group of the 2,2-bis(4-hydroxyphenyl)propanoic acid cyclohexyl part observed in the vicinity of δ 4.75 to 4.95 (iii) The integral value of the methyl group of the PTBP part observed in the vicinity of δ 1.30 to 1.33

[0079] In the case of BPA-methyl diphenolate copolymer: (i) The total integral of the phenyl group of the BPA part, the phenyl group of the methyl diphenolate part, and the phenyl group of the PTBP part observed in the vicinity of δ 6.8 to 7.5. (ii) The integral of the methyl group of the methyl diphenolate part observed in the vicinity of δ 3.4 to 3.8. (iii) The integral of the methyl group of the PTBP part observed in the vicinity of δ 1.25 to 1.35.

[0080] Based on the above integral value and taking into consideration the number of protons, the content of each repeating unit in the aromatic polycarbonate resin was calculated using the following formula: - For cyclohexyl diphenolate, cyclopentyl diphenolate, and cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate: a = ((i) - (ii) x 8 - (iii) x 4 / 9) / 8 b = (ii) c = (iii) / 9 T = a + b + c BPA copolymerization composition ratio (mol%) A = (a / T x 100) x (100 / (100 - c)) Diphenolate ester copolymerization composition ratio (mol%) B = (b / T x 100) x (100 / (100 - c))

[0081] In the case of methyl diphenolate, a = ((i) - (ii) x 8 - (iii) x 4 / 9) / 8 b = (ii) / 3 c = (iii) / 9 T = a + b + c BPA copolymer composition ratio (mol%) A = (a / T x 100) x (100 / (100 - c)) Diphenolate ester copolymer composition ratio (mol%) B = (b / T x 100) x (100 / (100 - c))

[0082] Synthesis Example 1 (Synthesis of Cyclohexyl Diphenolate) 620 mL of cyclohexanol, 111 g (388 mmol) of diphenolic acid, and 5.69 g (58.0 mmol) of sulfuric acid were charged into a 1 L flask to obtain a reaction solution, and a stirrer tip, thermometer, and reflux condenser were attached. The reaction solution was heated to 80°C using an oil bath and stirred for 19 hours using a magnetic stirrer. After confirming the disappearance of diphenolic acid by thin layer chromatography (TLC), the reaction solution was returned to room temperature. 600 mL of toluene was added to the reaction solution, and the solution was washed twice with 800 mL of aqueous sodium bicarbonate (saturated aqueous sodium bicarbonate solution) and once with 800 mL of brine (saturated saline solution). The organic phase was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 316 g of a pale brown liquid as a crude product. The obtained crude product was purified using a silica gel column (1.05 kg of neutral silica gel, solvent: heptane / ethyl acetate = 4 / 1) to obtain 263 g of a pale yellow liquid. The resulting pale yellow liquid was azeotropically distilled eight times with a mixed solvent of acetonitrile / water = 2 / 1 (300 g). The precipitated solid was collected by vacuum filtration and washed twice by suspension in 500 mL of hexane. The resulting solid was dried under reduced pressure at 40 °C for 12 hours to obtain 113 g of a white solid of cyclohexyl diphenolate. Figure 1 shows the obtained compound. １ The H-NMR chart is shown below.

[0083] Synthesis Example 2 (Synthesis of Cyclopentyl Diphenolate) A 1-L flask was charged with 694 mL of cyclopentanol, 124 g (434 mmol) of diphenolic acid, and 6.37 g (65.0 mmol) of sulfuric acid to obtain a reaction solution. A stirrer tip, thermometer, and reflux condenser were then installed. The reaction solution was heated to 80°C using an oil bath and stirred for 22 hours using a magnetic stirrer. After confirming the disappearance of diphenolic acid by thin-layer chromatography (TLC), the reaction solution was returned to room temperature. 600 mL of ethyl acetate was added to the reaction solution, which was then washed twice with 600 mL of aqueous sodium bicarbonate (saturated aqueous sodium bicarbonate solution) and once with 600 mL of brine (saturated saline solution). The organic phase was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 172 g of a light brown liquid as a crude product. The resulting crude product was dissolved in 350 mL of a 9 / 1 hexane / ethyl acetate mixed solvent and allowed to stand overnight at room temperature. 108.2 g of the target cyclopentyl diphenolate was obtained by recrystallization. The compound obtained in FIG. １ The H-NMR chart is shown below.

[0084] Synthesis Example 3 (Synthesis of Methyl Diphenolate) 500 mL of methanol was added to a 1 L flask, and 50.0 g of diphenolic acid was dissolved therein. Next, 2.5 mL of sulfuric acid was added and refluxed for 5 hours. After that, the reaction solution was allowed to cool to room temperature and concentrated using a rotary evaporator. 200 mL of ethyl acetate was added thereto, and the mixture was washed three times with 100 mL of sodium bicarbonate water (saturated aqueous sodium bicarbonate solution) and twice with 100 mL of pure water. The recovered organic phase was concentrated using a rotary evaporator and then dried under reduced pressure to obtain 57.14 g of a pale yellow solid of methyl diphenolate. The resulting compound is shown in Figure 3. １ The H-NMR chart is shown below.

[0085] Synthesis Example 4 (Synthesis of cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate) 131 g of phenol, 60.3 g of pyruvic acid, and 45.6 mL of ion-exchanged water were placed in a 1 L four-neck flask equipped with a stirrer and a thermometer, and the mixture was cooled with ice. 112 g of 95% sulfuric acid was added dropwise to the mixture over 50 minutes, and the mixture was then warmed to room temperature and stirred for 14 hours. 1 L of diethyl ether was added to the reaction mixture, and the mixture was washed once with 1 L of ion-exchanged water. The organic phase was extracted twice with 1 L of 0.1 mol / L aqueous sodium hydroxide solution. The extracted organic phase was adjusted to pH 2 with 1 mol / L aqueous hydrochloric acid solution, and extracted twice with 1 L of diethyl ether. The organic phase was dried over sodium sulfate and then dried under reduced pressure to obtain 139 g of a light brown solid of 2,2-bis(4-hydroxyphenyl)propanoic acid as an intermediate compound. The obtained intermediate compound is shown in FIG. 4. １ The H-NMR chart is shown below. Subsequently, 2.01 L of cyclohexanol, 130 g of 2,2-bis(4-hydroxyphenyl)propanoic acid, and 27.7 g of 95% sulfuric acid were added to a 5 L four-neck flask equipped with a stirring blade, thermometer, and reflux condenser. The reaction solution was heated to 100°C and stirred for 15 days. After cooling to room temperature, the reaction solution was diluted two-fold with diethyl ether and washed twice with aqueous sodium bicarbonate, once with ion-exchanged water, and once with saturated saline. The organic phase was isolated, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 815 g of crude product. The crude product was purified three times by silica gel chromatography (neutral silica gel 5.0 kg, solvent: chloroform / ethyl acetate = 1 / 0 to 0 / 1 vol%). It was then purified by recrystallization (chloroform / ethyl acetate = 1 / 1 vol%) to obtain 52.9 g of a white solid, cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate. The compound obtained in FIG. １ The H-NMR chart is shown below.

[0086] Synthesis Example 5 (Synthesis of Polycarbonate Oligomer (1)) Sodium dithionite was added to a 5.6% by mass aqueous solution of sodium hydroxide to a concentration of 2000 ppm relative to the bisphenol A (BPA) to be dissolved later. BPA was dissolved in this solution to a BPA concentration of 13.5% by mass, preparing an aqueous sodium hydroxide solution of BPA. This aqueous sodium hydroxide solution of BPA was continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 L / hr, methylene chloride at 15 L / hr, and phosgene at 4.0 kg / hr. The tubular reactor had a jacket, and cooling water was passed through the jacket to maintain the temperature of the reaction solution below 40°C. The reaction solution leaving the tubular reactor was continuously introduced into a 40 L baffled tank reactor equipped with swept-back blades. A sodium hydroxide solution of BPA was added at a rate of 2.8 L / hr, a 25% by weight sodium hydroxide solution at a rate of 0.07 L / hr, water at a rate of 17 L / hr, and a 1% by weight triethylamine solution at a rate of 0.64 L / hr. The reaction was carried out by continuously withdrawing the reaction solution overflowing from the tank reactor and allowing it to stand, thereby separating and removing the aqueous phase, and collecting the methylene chloride phase. The methylene chloride solution of polycarbonate oligomer (PCO) thus obtained (PCO solution (a)) had a concentration of 341 g / L and a chloroformate group concentration of 0.71 mol / L.

[0087] Synthesis Example 6 (Synthesis of Polycarbonate Oligomer (2)) Sodium dithionite was added to a 5.6% by mass aqueous solution of sodium hydroxide to a concentration of 2000 ppm relative to the bisphenol A (BPA) to be dissolved later. BPA was dissolved in this solution to a BPA concentration of 13.5% by mass, to prepare an aqueous sodium hydroxide solution of BPA. This aqueous sodium hydroxide solution of BPA was continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 L / hr, methylene chloride at 18 L / hr, and phosgene at 4.5 kg / hr. The tubular reactor had a jacket, and cooling water was passed through the jacket to maintain the temperature of the reaction solution below 40 ° C. The reaction solution exiting the tubular reactor was continuously withdrawn and allowed to stand, allowing the aqueous phase to be separated and removed, and the methylene chloride phase to be collected. The methylene chloride solution of polycarbonate oligomer (PCO) thus obtained (PCO solution (b)) had a concentration of 308 g / L and a chloroformate group concentration of 0.94 mol / L.

[0088] Production Example 1 (Synthesis of aromatic polycarbonate resin (PC-1) [BPA-cyclohexyl diphenolate copolymer]) 82.70 mL of methylene chloride was added to a 200 mL separable flask equipped with a baffle, and 2.26 g of cyclohexyl diphenolate obtained in Synthesis Example 1 above was dissolved therein. Subsequently, 111.3 mL of the PCO solution (a) obtained in Synthesis Example 5 above was added, followed by dissolving 0.612 g of p-tert-butylphenol (PTBP). Next, 13.93 μL of triethylamine (TEA) and 23.42 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution obtained by dissolving 1.50 g of sodium hydroxide in 21.92 mL of pure water) were added, and the reaction was carried out for 20 minutes to obtain a polymerization solution (1). Separately, 3.50 g of sodium hydroxide and 20.35 mg of sodium dithionite were dissolved in 51.16 mL of purified water to obtain an aqueous solution. 7.92 g of BPA was then dissolved in this aqueous solution to obtain a sodium hydroxide solution of BPA (1). The sodium hydroxide solution of BPA (1) was added to the polymerization solution, and the polymerization reaction was carried out for 40 minutes. 220 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. After this, the mixture was separated into an organic phase containing the BPA-cyclohexyl diphenolate copolymer and an aqueous phase containing excess BPA and sodium hydroxide, and the organic phase was isolated. The methylene chloride solution of BPA-cyclohexyl diphenolate copolymer thus obtained was washed successively with a 15% by volume solution of 0.03 mol / L sodium hydroxide and 0.2 mol / L hydrochloric acid, and then repeatedly washed with purified water until the electrical conductivity of the aqueous phase after washing was 5 μS / cm or less. The washed organic phase was flaked by distilling off the solvent using an evaporator, yielding a white product. The viscosity average molecular weight Mv was 19,600. １ The H-NMR chart is shown below.

[0089] Production Example 2 (Synthesis of aromatic polycarbonate resin (PC-2) [BPA-cyclopentyl diphenolate copolymer]) Synthesis was performed using the cyclopentyl diphenolate obtained in Synthesis Example 2 above instead of the cyclohexyl diphenolate in Production Example 1, to synthesize an aromatic polycarbonate resin (PC-2) [cyclopentyl diphenolate copolymer]. Specifically, 62.02 mL of methylene chloride was added to a 200 mL separable flask equipped with a baffle, and 5.09 g of cyclopentyl diphenolate obtained in Synthesis Example 2 above was dissolved therein. Subsequently, 87.98 mL of the PCO solution (a) obtained in Synthesis Example 5 above was added, and then 0.459 g of p-tert-butylphenol (PTBP) was dissolved therein. Next, 4.35 μL of triethylamine (TEA) and 29.28 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution prepared by dissolving 1.87 g of sodium hydroxide in 27.41 mL of pure water) were added, and the reaction was carried out for 20 minutes to obtain a polymerization solution (2). Separately, 1.87 g of sodium hydroxide and 16.74 mg of sodium dithionite were dissolved in 27.41 mL of pure water to obtain an aqueous solution. 3.28 g of BPA was then dissolved in this aqueous solution to obtain an aqueous sodium hydroxide solution of BPA (2). The aqueous sodium hydroxide solution of BPA (2) was added to the polymerization solution (2), and the polymerization reaction was carried out for 40 minutes. 100 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Thereafter, the methylene chloride solution of BPA-cyclopentyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, and further washed in the same manner as in Production Example 1. The solvent was then distilled off and the mixture was flaked to obtain a white product. The viscosity average molecular weight Mv was 15,900. １ The H-NMR chart is shown below.

[0090] Production Example 3 (Synthesis of aromatic polycarbonate resin (PC-3) [BPA-methyl diphenolate copolymer]) Synthesis was performed using the methyl diphenolate obtained in Synthesis Example 3 above instead of cyclohexyl diphenolate in Production Example 1, to synthesize aromatic polycarbonate resin (PC-3) [BPA-methyl diphenolate copolymer]. Specifically, 62.0 mL of methylene chloride was added to a 1 L separable flask equipped with a baffle, and 4.50 g of methyl diphenolate obtained in Synthesis Example 3 above was dissolved therein. Subsequently, 88.0 mL of the PCO solution (a) obtained in Synthesis Example 5 above was added, and then 0.34 g of p-tert-butylphenol (PTBP) was dissolved therein. Next, 17.0 μL of triethylamine (TEA) and 24.3 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution prepared by dissolving 1.55 g of sodium hydroxide in 22.7 mL of pure water) were added, and the reaction was carried out for 10 minutes to obtain a polymerization solution (3). Separately, 2.70 g of sodium hydroxide and 5.98 mg of sodium dithionite were dissolved in 39.5 mL of pure water to obtain an aqueous solution. 2.99 g of BPA was then dissolved in this aqueous solution to obtain an aqueous sodium hydroxide solution of BPA (3). The aqueous sodium hydroxide solution of BPA (3) was added to the polymerization solution (3), and the polymerization reaction was carried out for 50 minutes. 100 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Thereafter, the methylene chloride solution of the BPA-methyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 20,900. FIG. 8 shows the obtained aromatic polycarbonate resin. １ The H-NMR chart is shown below.

[0091] Production Example 4 (Synthesis of aromatic polycarbonate resin (PC-5) [BPA-cyclohexyl diphenolate copolymer]) Synthesis was performed in Production Example 1 so that the monomer charging ratio was BPA:cyclohexyl diphenolate = 94:6, to obtain aromatic polycarbonate resin (PC-5) [BPA-cyclohexyl diphenolate copolymer]. Specifically, 490 mL of methylene chloride, 6.35 g of cyclohexyl diphenolate obtained in Synthesis Example 1 above, and 176 mL of the PCO solution (a) obtained in Synthesis Example 5 above were added to a 1 L separable flask equipped with a baffle, and then 0.673 g of p-tert-butylphenol (PTBP) was added and dissolved. Next, 20.9 μL of triethylamine (TEA) and 35.2 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution prepared by dissolving 2.25 g of sodium hydroxide in 32.9 mL of pure water) were added, and the reaction was carried out for 20 minutes to obtain a polymerization solution (4). Separately, 5.25 g of sodium hydroxide and 31.1 mg of sodium dithionite were dissolved in 76.7 mL of pure water to obtain an aqueous solution. 9.18 g of BPA was then dissolved in this aqueous solution to obtain an aqueous sodium hydroxide solution of BPA (4). 48.8 μL of triethylamine (TEA) and the aqueous sodium hydroxide solution of BPA (4) were added to the polymerization solution (4), and the polymerization reaction was carried out for 40 minutes. Thereafter, a methylene chloride solution of BPA-cyclohexyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 20,500. FIG. 9 shows the obtained aromatic polycarbonate resin. １ The H-NMR chart is shown below.

[0092] Production Example 5 (Synthesis of aromatic polycarbonate resin (PC-6) [BPA-cyclohexyl diphenolate copolymer]) Synthesis was performed in Production Example 1, except that the monomer charging ratio was BPA:cyclohexyl diphenolate = 83:17, to obtain aromatic polycarbonate resin (PC-6) [BPA-cyclohexyl diphenolate copolymer]. Specifically, 82.7 mL of methylene chloride, 13.7 g of the cyclohexyl diphenolate obtained in Synthesis Example 1 above, and 117 mL of the PCO solution (a) obtained in Synthesis Example 5 above were added to a 1 L separable flask equipped with a baffle, and then 0.612 g of p-tert-butylphenol (PTBP) was added and dissolved. Next, 27.9 μL of triethylamine (TEA) and 46.9 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution prepared by dissolving 3.00 g of sodium hydroxide in 43.9 mL of pure water) were added, and the reaction was carried out for 20 minutes to obtain a polymerization solution (5). Separately, 2.00 g of sodium hydroxide and 29.1 mg of sodium dithionite were dissolved in 29.2 mL of pure water to obtain an aqueous solution. 0.82 g of BPA was then dissolved in this aqueous solution to obtain a sodium hydroxide aqueous solution of BPA (5). 18.6 μL of triethylamine (TEA) and the above sodium hydroxide aqueous solution of BPA (5) were added to the polymerization solution (5), and the polymerization reaction was carried out for 40 minutes. Thereafter, a methylene chloride solution of BPA-cyclohexyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 18,000. FIG. 10 shows the obtained aromatic polycarbonate resin. １ The H-NMR chart is shown below.

[0093] Production Example 6 (Synthesis of aromatic polycarbonate resin (PC-7) [BPA-cyclohexyl diphenolate copolymer]) Synthesis was performed in Production Example 1, except that the monomer charging ratio was BPA:cyclohexyl diphenolate = 85:15, to obtain aromatic polycarbonate resin (PC-7) [cyclohexyl diphenolate copolymer]. Specifically, to a 1 L separable flask equipped with a baffle, 237 mL of methylene chloride, 9.68 g of cyclohexyl diphenolate obtained in Synthesis Example 1 above, 113 mL of the PCO solution (b) obtained in Synthesis Example 6 above, 92.0 μL of triethylamine (TEA), and 36.4 g of an 8.1 mass % aqueous sodium hydroxide solution (aqueous solution obtained by dissolving 2.96 g of sodium hydroxide in 33.4 mL of pure water) were added and dissolved, and the reaction was carried out for 20 minutes to obtain polymerization solution (6). Separately, 5.10 g of sodium hydroxide and 17.0 mg of sodium dithionite were dissolved in 75.1 mL of purified water to obtain an aqueous solution. Then, 8.30 g of BPA was dissolved in this aqueous solution to obtain a sodium hydroxide aqueous solution of BPA (6). To the above polymerization solution (6), 6.00 mL of a methylene chloride solution containing 0.80 g of p-tert-butylphenol (PTBP) and the above sodium hydroxide aqueous solution of BPA (6) were added, and a polymerization reaction was carried out for 40 minutes. 373 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Thereafter, the methylene chloride solution of BPA-cyclohexyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 23,300. Figure 11 shows the aromatic polycarbonate resin obtained. １ The H-NMR chart is shown below.

[0094] Production Example 7 (Synthesis of aromatic polycarbonate resin (PC-8) [BPA-cyclohexyl diphenolate copolymer]) Synthesis was performed in Production Example 1, except that the monomer charging ratio was BPA:cyclohexyl diphenolate = 89:11, to obtain aromatic polycarbonate resin (PC-8) [cyclohexyl diphenolate copolymer]. Specifically, 237 mL of methylene chloride, 6.83 g of cyclohexyl diphenolate obtained in Synthesis Example 1 above, 113 mL of the PCO solution (b) obtained in Synthesis Example 6 above, 92.0 μL of triethylamine (TEA), and 36.4 g of an 8.1 mass % aqueous sodium hydroxide solution (aqueous solution obtained by dissolving 2.95 g of sodium hydroxide in 33.4 mL of pure water) were added to a 1 L separable flask equipped with a baffle plate and dissolved, and the reaction was carried out for 20 minutes to obtain a polymerization solution (7). Separately, 5.10 g of sodium hydroxide and 17.0 mg of sodium dithionite were dissolved in 75.0 mL of pure water to obtain an aqueous solution. Then, 8.31 g of BPA was dissolved in this aqueous solution to obtain a sodium hydroxide aqueous solution of BPA (7). To the above polymerization solution (7), 6.00 mL of a methylene chloride solution containing 0.81 g of p-tert-butylphenol (PTBP) and the above sodium hydroxide aqueous solution of BPA (7) were added, and a polymerization reaction was carried out for 40 minutes. 331 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Thereafter, the methylene chloride solution of BPA-cyclohexyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 22,000. Figure 12 shows the aromatic polycarbonate resin obtained. １ The H-NMR chart is shown below.

[0095] Production Example 8 (Synthesis of aromatic polycarbonate resin (PC-9) [BPA-cyclopentyl diphenolate copolymer]) Synthesis was performed in Production Example 2, except that the monomer charging ratio was BPA:cyclopentyl diphenolate = 94:6, to obtain aromatic polycarbonate resin (PC-9) [BPA-cyclopentyl diphenolate copolymer]. Specifically, 491 mL of methylene chloride, 6.11 g of the cyclopentyl diphenolate obtained in Synthesis Example 2 above, and 176 mL of the PCO solution (a) obtained in Synthesis Example 5 above were added to a 1 L separable flask equipped with a baffle, and then 0.673 g of p-tert-butylphenol (PTBP) was added and dissolved. Next, 20.9 μL of triethylamine (TEA) and 35.2 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution prepared by dissolving 2.25 g of sodium hydroxide in 32.9 mL of pure water) were added, and the reaction was carried out for 20 minutes to obtain a polymerization solution (8). Separately, 5.25 g of sodium hydroxide and 31.1 mg of sodium dithionite were dissolved in 76.7 mL of pure water to obtain an aqueous solution. 9.18 g of BPA was then dissolved in this aqueous solution to obtain an aqueous sodium hydroxide solution of BPA (8). 48.8 μL of triethylamine (TEA) and the aqueous sodium hydroxide solution of BPA (8) were added to the polymerization solution (8), and the polymerization reaction was carried out for 40 minutes. Thereafter, a methylene chloride solution of BPA-cyclopentyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 21,200. FIG. 13 shows the obtained aromatic polycarbonate resin. １ The H-NMR chart is shown below.

[0096] Production Example 9 (Synthesis of aromatic polycarbonate resin (PC-10) [BPA-cyclopentyl diphenolate copolymer]) Synthesis was performed in Production Example 2, except that the monomer charging ratio was BPA:cyclopentyl diphenolate = 96:4, to obtain aromatic polycarbonate resin (PC-10) [BPA-cyclopentyl diphenolate copolymer]. Specifically, 41.4 mL of methylene chloride, 1.51 g of the cyclopentyl diphenolate obtained in Synthesis Example 2 above, and 58.6 mL of the PCO solution (a) obtained in Synthesis Example 5 above were added to a 200 mL separable flask equipped with a baffle, and then 0.100 g of p-tert-butylphenol (PTBP) was added and dissolved. Next, 1.16 μL of triethylamine (TEA) and 5.2 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution prepared by dissolving 0.33 g of sodium hydroxide in 4.87 mL of pure water) were added, and the reaction was carried out for 20 minutes to obtain a polymerization solution (9). Separately, 2.50 g of sodium hydroxide and 7.76 mg of sodium dithionite were dissolved in 36.5 mL of pure water to obtain an aqueous solution. 3.88 g of BPA was then dissolved in this aqueous solution to obtain an aqueous sodium hydroxide solution of BPA (9). 4.64 μL of triethylamine (TEA) and the above aqueous sodium hydroxide solution of BPA (9) were added to the above polymerization solution (9), and the polymerization reaction was carried out for 40 minutes. 100 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Thereafter, the methylene chloride solution of BPA-cyclopentyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, and further washed in the same manner as in Production Example 1. The solvent was then distilled off and the mixture was flaked to obtain a white product. The viscosity average molecular weight Mv was 25,300. １ The H-NMR chart is shown below.

[0097] Production Example 10 (Synthesis of aromatic polycarbonate resin (PC-11) [BPA-cyclopentyl diphenolate copolymer]) Synthesis was performed in Production Example 2, except that the monomer charging ratio was BPA:cyclopentyl diphenolate = 89:11, to obtain aromatic polycarbonate resin (PC-11) [cyclopentyl diphenolate copolymer]. Specifically, to a 1 L separable flask equipped with a baffle, 154 mL of methylene chloride, 8.84 g of the cyclopentyl diphenolate obtained in Synthesis Example 2 above, 146 mL of the PCO solution (b) obtained in Synthesis Example 6 above, 118 μL of triethylamine (TEA), and 27.4 g of an 8.0 mass % aqueous sodium hydroxide solution (an aqueous solution obtained by dissolving 2.20 g of sodium hydroxide in 25.2 mL of pure water) were added and dissolved, and the reaction was carried out for 20 minutes to obtain polymerization solution (10). Separately, 6.60 g of sodium hydroxide and 21.0 mg of sodium dithionite were dissolved in 96.0 mL of purified water to obtain an aqueous solution. Then, 10.6 g of BPA was dissolved in this aqueous solution to obtain a sodium hydroxide aqueous solution of BPA (10). To the above polymerization solution (10), 8.00 mL of a methylene chloride solution containing 1.10 g of p-tert-butylphenol (PTBP) and the above sodium hydroxide aqueous solution of BPA (10) were added, and a polymerization reaction was carried out for 40 minutes. 322 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Thereafter, the methylene chloride solution of BPA-cyclopentyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 25,100. Figure 15 shows the aromatic polycarbonate resin obtained. １ The H-NMR chart is shown below.

[0098] Production Example 11 (Synthesis of aromatic polycarbonate resin (PC-12) [BPA-cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate copolymer]) In Production Example 1, cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate obtained in Synthesis Example 4 was used in place of cyclohexyl diphenolate, and synthesis was performed such that the monomer charging ratio was BPA:cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate = 92:8, thereby synthesizing aromatic polycarbonate resin (PC-12) [cyclohexyl BPA-cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate copolymer]. Specifically, an aqueous solution of cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate was obtained by dissolving 6.18 g of the cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate obtained in Synthesis Example 4 above in 27.4 g of an 8.0 mass % aqueous sodium hydroxide solution (an aqueous solution prepared by dissolving 2.20 g of sodium hydroxide in 25.2 mL of pure water). This aqueous solution of cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate, 146 ml of the PCO solution (b) obtained in Synthesis Example 6 above, 154 mL of methylene chloride, and 118 μL of triethylamine (TEA) were added to a 1 L separable flask equipped with a baffle plate, and the mixture was reacted for 20 minutes to obtain a polymerized solution (11). Separately, 6.60 g of sodium hydroxide and 21.0 mg of sodium dithionite were dissolved in 96.1 mL of purified water to obtain an aqueous solution. Then, 10.6 g of BPA was dissolved in this aqueous solution to obtain a sodium hydroxide aqueous solution of BPA (11). To the above polymerization solution (11), 8.00 mL of a methylene chloride solution containing 1.10 g of p-tert-butylphenol (PTBP) and the above sodium hydroxide aqueous solution of BPA (11) were added, and a polymerization reaction was carried out for 40 minutes. 373 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Subsequently, a methylene chloride solution of BPA-2,2-bis(4-hydroxyphenyl)cyclohexyl propanoate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 21,900. Figure 16 shows the aromatic polycarbonate resin obtained. １ The H-NMR chart is shown below.

[0099] Production Example 12 (Synthesis of aromatic polycarbonate resin (PC-13) [BPA-2,2-bis(4-hydroxyphenyl)cyclohexyl propanoate copolymer]) Synthesis was performed in Production Example 2, except that the monomer charging ratio was BPA:2,2-bis(4-hydroxyphenyl)cyclohexyl propanoate = 84:16, to obtain aromatic polycarbonate resin (PC-13) [BPA-2,2-bis(4-hydroxyphenyl)cyclohexyl propanoate copolymer]. Specifically, first, 11.1 g of the 2,2-bis(4-hydroxyphenyl)cyclohexyl propanoate obtained in Synthesis Example 4 above was dissolved in 41.4 g of an 8.0 mass % aqueous sodium hydroxide solution (an aqueous solution obtained by dissolving 3.30 g of sodium hydroxide in 38.1 mL of pure water), to obtain an aqueous solution of cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate. This aqueous solution of cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate, 137 ml of the PCO solution (b) obtained in Synthesis Example 6, and 105 μL of triethylamine (TEA) were added to a 1 L separable flask equipped with a baffle plate and reacted for 20 minutes to obtain polymerization solution (12). Separately, 5.90 g of sodium hydroxide and 19.0 mg of sodium dithionite were dissolved in 86.0 mL of pure water to obtain an aqueous solution. 9.40 g of BPA was then dissolved in this aqueous solution to obtain aqueous sodium hydroxide solution of BPA (12). To the polymerization solution (12), 6.00 mL of a methylene chloride solution containing 0.86 g of p-tert-butylphenol (PTBP) and the aqueous sodium hydroxide solution of BPA (12) were added, and the polymerization reaction was carried out for 40 minutes. 36.0 mL of methylene chloride was added for dilution, and the mixture was stirred for 5 minutes. Thereafter, the methylene chloride solution of BPA-2,2-bis(4-hydroxyphenyl)propanoic acid cyclohexyl copolymer was isolated as an organic phase in the same manner as in Production Example 1, and then washed in the same manner as in Production Example 1. The solvent was then distilled off and the product was flaked to obtain a white product. The viscosity average molecular weight Mv was 23,500. Figure 17 shows the aromatic polycarbonate resin obtained. １ The H-NMR chart is shown below.

[0100] Production Example 13 (Synthesis of aromatic polycarbonate resin (PC-14) [BPA-methyl diphenolate copolymer]) Synthesis was performed in Production Example 3, except that the monomer charging ratio was BPA:methyl diphenolate = 96:4, to obtain aromatic polycarbonate resin (PC-14) [BPA-methyl diphenolate copolymer]. 491 mL of methylene chloride, 5.18 g of methyl diphenolate obtained in Synthesis Example 3 above, and 176 mL of the PCO(a) solution obtained in Synthesis Example 5 above were added to a 1 L separable flask equipped with a baffle, followed by the addition of 0.673 g of p-tert-butylphenol (PTBP) for dissolution. Next, 20.9 μL of triethylamine (TEA) and 35.2 g of a 6.4 mass% aqueous sodium hydroxide solution (aqueous solution prepared by dissolving 2.25 g of sodium hydroxide in 32.9 mL of pure water) were added, and the mixture was allowed to react for 20 minutes to obtain a polymerization solution (13). Separately, 5.25 g of sodium hydroxide and 31.1 mg of sodium dithionite were dissolved in 76.7 mL of pure water to obtain an aqueous solution. 9.18 g of BPA was then dissolved in this aqueous solution to obtain a sodium hydroxide aqueous solution of BPA (13). 48.8 μL of triethylamine (TEA) and the sodium hydroxide aqueous solution of BPA (13) were added to the above polymerization solution (13), and a polymerization reaction was carried out for 40 minutes. Thereafter, a methylene chloride solution of BPA-methyl diphenolate copolymer was isolated as an organic phase in the same manner as in Production Example 1, washed, and then the solvent was distilled off to form flakes, yielding a white product. The viscosity average molecular weight Mv was 22,100. Figure 18 shows the aromatic polycarbonate resin obtained. １ The H-NMR chart is shown below.

[0101] Examples 1 to 11, Comparative Examples 1 to 3 (1) Evaluation of scratch hardness (pencil method) The aromatic polycarbonate resins (PC-1) to (PC-3), (PC-5) to (PC-14) obtained in Production Examples 1 to 13 and the aromatic polycarbonate resin (PC-4) in Comparative Example 2 were "Taflon FN1900" (trade name, manufactured by Idemitsu Kosan Co., Ltd., an aromatic polycarbonate resin composed of BPA, viscosity average molecular weight Mv19,100) were injection molded using an injection molding machine ("Mini Jet Pro" manufactured by Thermo Fisher Scientific) under conditions of a cylinder temperature of 290 ° C. and a mold temperature of 90 ° C. to produce a disk-shaped molded body (diameter 30 mm, thickness 1.5 mm). According to JIS K 5600-5-4:1999, a line was drawn with a pencil at a 45-degree angle while applying a load of 750 g, and the presence or absence of scratches on the surface was inspected with the naked eye to evaluate the scratch hardness (pencil method). The pencil hardness determined by the scratch hardness (pencil method) is one of 14 levels: 6B to B, HB, F, and H to 6H. The results are shown in Table 1.

[0102] (2) Measurement of total light transmittance The molded article prepared in (1) above was measured for total light transmittance [%] at a thickness of 1.5 mm in accordance with ASTM D1003-21 using a haze meter NDH 5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) The results are shown in Tables 1 and 2.

[0103] (3) Notched Izod Impact Strength The aromatic polycarbonate resins (PC-5, PC-9, PC-10, PC-14) obtained in Production Examples 4, 8, 9, and 13 and the aromatic polycarbonate resin (PC-4) "Taflon FN1900" were used to measure the notched Izod impact strength [kJ / m ２] was measured. Specifically, using an injection molding machine ("Mini Jet Pro" manufactured by Thermo Fisher Scientific), injection molding was performed under conditions of a cylinder temperature of 270 to 290°C and a mold temperature of 80 to 100°C, and a rectangular molded body (length 60 mm, width 40 mm, thickness 4 mm) was produced. A notch (r = 0.25 mm ± 0.05 mm) was added to this molded body at a position 30 mm in length by post-processing to obtain a notched test specimen. The notched Izod impact strength at 23°C was measured so that the pendulum hammer hit the test specimen 22 mm above the notch portion. In Tables 1 and 2, the notched Izod impact strength was 9 kJ / m ２ The above cases are indicated as A.

[0104] (4) Indentation Hardness For the molded bodies of Examples 2, 3, 7, 8, Comparative Examples 2, and 3 prepared in (1) above, the indentation hardness [MPa] at 28 ° C was measured by a nanoindentation test in accordance with ISO 14577-1:2015 using an ultra-microindentation hardness tester ENT-1100a (manufactured by Elionix Co., Ltd.). A Vickers (square pyramid) indenter was used, and the test load was 96 mN. The results are shown in Tables 1 and 2.

[0105]

[0106]

[0107] The abbreviations in the table are as follows: BPA: Bisphenol A CyHex (1): Cyclohexyl diphenolate CyPen: Cyclopentyl diphenolate Me: Methyl diphenolate CyHex (2): Cyclohexyl 2,2-bis(4-hydroxyphenyl)propanoate In addition, "-" in the table means that no measurement was performed.

Claims

1. An aromatic polycarbonate resin containing a repeating unit represented by the following formula (II). 【Chemical 1】 [In formula (II), R 11 and R 12 each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. R 13 represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. R 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20.]

2. The aromatic polycarbonate resin according to claim 1, further containing a repeating unit represented by the following formula (I), and the molar ratio ((I):(II)) of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) being 0:100 to 99.5:0.

5. 【Chemical 2】 [In formula (I), R １ and R ２ each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, -S-, -SO-, -SO ２ -, -O- or -CO-. a and b each independently represent an integer of 0 to 4.]

3. The aromatic polycarbonate resin according to claim 2, wherein the molar ratio ((I):(II)) of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) is 0.5:99.5 to 99.5:0.

5.

4. The aromatic polycarbonate resin according to claim 2, wherein the molar ratio ((I):(II)) of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) is 60:40 to 99.5:0.

5.

5. R 14 is a saturated or unsaturated alicyclic group having 3 to 12 carbon atoms, or The aromatic polycarbonate resin according to any one of claims 1 to 4, which represents a saturated or unsaturated heterocyclic group having 3 to 12 members.

6. R 14 The aromatic polycarbonate resin according to any one of claims 1 to 4, wherein R is a cyclopentyl group or a cyclohexyl group, and n is 2.

7. The aromatic polycarbonate resin according to any one of claims 1 to 4, having a viscosity average molecular weight of 10,000 to 100,000.

8. The aromatic polycarbonate resin according to any one of claims 1 to 4, having a scratch hardness of F or more evaluated in accordance with JIS K5600-5-4.

9. The aromatic polycarbonate resin according to any one of claims 1 to 4, having a total light transmittance of 87% or more at a thickness of 1.5 mm.

10. A diphenolic compound represented by the following formula (ii). [Chemical Formula 3] [In formula (ii), R 11 and R 12 each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. R 13 represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. R 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20.]

11. A method for producing an aromatic polycarbonate resin, comprising a step of interfacial polycondensation of a diphenolic compound and a polycarbonate oligomer in the presence of a water-insoluble organic solvent and an aqueous solution of an alkaline compound, wherein the diphenolic compound contains the diphenolic compound (a) represented by the above formula (ii). 【Chemical Formula 4】 [In formula (ii), R 11 and R 12 each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. R 13 represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. R 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20.]

12. A polycarbonate resin composition comprising the aromatic polycarbonate resin according to any one of claims 1 to 4.

13. The polycarbonate resin composition according to claim 12, for use in scratch-resistant applications.

14. A molded article of the polycarbonate resin composition according to claim 12.

15. The molded article according to claim 14, which is a resin window, a touch panel, an interior article, an exterior article, an interior or exterior part of a vehicle, a housing, an electrical appliance, a building material, or an OA device.

16. A structure having an outer surface formed of the polycarbonate resin composition according to claim 12.

17. Use of the aromatic polycarbonate resin according to any one of claims 1 to 4 for scratch-resistant applications.

18. Use of the aromatic polycarbonate resin according to any one of claims 1 to 4 for manufacturing a resin window, a touch panel, an interior article, an exterior article, an interior or exterior part of a vehicle, a housing, an electrical appliance, a building material, or an OA device.

19. Use of a dihydric phenol compound represented by the following formula (ii) for producing an aromatic polycarbonate resin. [Chemical Formula 5] [In formula (ii), R 11 and R 12 each independently represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. R 13 represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. R 14 represents a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or a saturated or unsaturated heterocyclic group having 3 to 20 members. c and d each independently represent an integer of 0 to 4. n represents an integer of 0 to 20. ]

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