Polycarbonate resin and molded product comprising the same

Abstract

To provide a polycarbonate resin having excellent scratch resistance, heat resistance, and flowability and a molded product comprising the same.SOLUTION: There is provided a polycarbonate resin comprising a repeating unit (A) represented by the following formula (1) and a repeating unit (B) having a specific bisphenol structure in the main chain and comprising a unit (C) represented by the following formula (4) at the end. (Ring Z is a condensed polycyclic arene ring, R1 and R2 are groups of specific structures.) (In the formula (4), m is an integer of 0 or 1 and R19 is an alkyl group having 5 to 20 carbon atoms.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin having excellent scratch resistance, heat resistance and flowability, and to a molded article made from the same. [Background technology]

[0002] Polycarbonate resin has excellent transparency, impact resistance, heat resistance, and dimensional stability, making it an engineering plastic that is used in a wide range of fields, including housings for electrical and electronic devices, interior and exterior parts for automobiles, building materials, furniture, musical instruments, and miscellaneous goods. Furthermore, compared to inorganic glass, its specific gravity is lower, allowing for weight reduction and excellent productivity, making it used for windows in automobiles, etc.

[0003] Furthermore, sheets and films using polycarbonate resins are widely used as various display devices and protective parts for automobile interiors by being subjected to additional secondary processing such as coating, lamination, and surface modification.

[0004] However, when uncoated polycarbonate resin is measured in accordance with JIS K5600-5-4, General Test Methods for Paints - Part 5: Mechanical Properties of Coatings - Section 4: Scratch Hardness (Pencil Method), the pencil hardness of polycarbonate resin is only about 2B, which presents an issue as a paint-less material, as it is prone to scratches on the surface.

[0005] Therefore, it is known to use copolymer polycarbonate resins with high surface hardness (Patent Document 1). Also, methods have been described in which polycarbonates or copolycarbonates are produced using 2,2-bis(4-hydroxy-3-methylphenyl)propane as a repeating unit (Patent Documents 2 to 6). Although such polycarbonate resins have higher surface hardness, they have the problem of being inferior in heat resistance compared to polycarbonate resins.

[0006] Furthermore, Patent Document 7 describes that a polycarbonate resin having 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine as a structural unit has excellent abrasion resistance as a binder resin for electrophotographic photoreceptors. However, when a structural unit having a rigid structure is introduced to improve scratch resistance, there is a problem that while heat resistance is improved, fluidity is reduced.

[0007] One method for improving the fluidity of polycarbonate resins is to increase the number of carbon atoms in the alkylphenol used as a terminal terminator to make it longer chain-like (for example, Patent Documents 8 and 9). However, when a long-chain alkylphenol is used as a terminal terminator for ordinary polycarbonate resins, although the fluidity is improved, the heat resistance is reduced, and it may not be possible to use the resin in applications requiring heat resistance, such as automobile interior parts. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 5173803 [Patent Document 2] Japanese Patent Application Publication No. 64-069625 [Patent Document 3] Japanese Patent Application Publication No. 08-183852 [Patent Document 4] Japanese Patent Application Publication No. 08-034846 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-117580 [Patent Document 6] Patent No. 3768903 [Patent Document 7] Patent No. 3297469 [Patent Document 8] Patent No. 3758874 [Patent Document 9] Japanese Patent Application Publication No. 60-215020 Summary of the Invention [Problem to be solved by the invention]

[0009] As mentioned above, there is no polycarbonate resin that combines high levels of scratch resistance, heat resistance, and fluidity. Therefore, an object of the present invention is to solve the above problems and to provide a polycarbonate resin having excellent scratch resistance, heat resistance and flowability, and a molded article made from the same. [Means for solving the problem]

[0010] As a result of extensive research aimed at achieving this object, the present inventors discovered that a polycarbonate resin having a specific structure can solve the above problems, and arrived at the present invention. That is, the present invention is as follows:

[0011] 1. A polycarbonate resin containing in its main chain a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), and containing a unit (C) represented by the following formula (4) at its terminal, wherein, when all repeating units in the main chain are taken as 100 mol %, the proportion of repeating units (A) represented by formula (1) is 5 to 95 mol %, and the proportion of units (C) represented by formula (4) is 0.01 mol % or more based on the number of moles of all constituent units. [ka] (In the above formula (1), ring Z is a fused polycyclic arene ring, R 1 and R 2 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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. [ka] (In the above formula (2), R 3 and R 4 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following formula (3): [ka] (In the above formula (3), R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 ,R 11 and R 12 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different; R 13 and R 14 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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; R 15 ,R 16 ,R 17and R 18 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl 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, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, h and i are integers of 1 to 3, and g is an integer of 1 to 100. [ka] (In formula (4), m represents an integer of 0 or 1, and R 19 represents an alkyl group having 5 to 20 carbon atoms.

[0012] 2. The polycarbonate resin according to item 1 above, wherein in the repeating unit (A) represented by formula (1), ring Z is a naphthalene ring. 3. The polycarbonate resin according to item 1 or 2 above, wherein W in formula (2) contains at least one group selected from the group consisting of groups represented by formula (5): [ka] (In the above formula (5), R 29 , R 30 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and when there are a plurality of each, they may be the same or different. 4. The polycarbonate resin according to any one of items 1 to 3 above, wherein the repeating unit (B) represented by formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 2,2-bis(4-hydroxyphenyl)propane. 5. The polycarbonate resin according to any one of items 1 to 4 above, wherein the content of the repeating unit (B) is in the range of 5 to 95 mol % based on all repeating units in the main chain. 6. The polycarbonate resin according to any one of items 1 to 5 above, wherein the proportion of the structural unit (C) represented by formula (4) is 0.01 to 10 mol % when all repeating units in the main chain are taken as 100 mol %. 7. The above R 19 7. The polycarbonate resin according to any one of items 1 to 6 above, wherein is an alkyl group having 8 to 20 carbon atoms. 8. The polycarbonate resin according to any one of items 1 to 7 above, which has a glass transition temperature of 100 to 220°C. 9. Indentation hardness measured in accordance with ISO / TS 19278 is 200 to 400 (N / mm 2 9. The polycarbonate resin according to any one of items 1 to 8 above, wherein 10. The polycarbonate resin according to any one of items 1 to 9 above, which has a pencil hardness of 2H or more as measured in accordance with JIS K5600. 10. The polycarbonate resin according to any one of items 1 to 9 above, which has an 11.5% weight loss temperature of 400°C or higher. 12. The melt viscosity measured with a capillary rheometer at 320°C is 608 sec. -1 12. The polycarbonate resin according to any one of items 1 to 11 above, wherein the viscosity is 1,500 Pa·s or less under the conditions. 13. A molded article obtained by injection molding the polycarbonate resin according to any one of items 1 to 12 above. 14. A sheet or film obtained by extrusion molding the polycarbonate resin according to any one of items 1 to 12 above. 15. Automobile interior parts using the molded products described in the preceding paragraph 13. 16. Automobile interior parts using the sheets or films described in the preceding paragraph 14. [Effects of the Invention]

[0013] The polycarbonate resin of the present invention and molded articles made thereof have excellent scratch resistance, heat resistance, and flowability, and are therefore suitable for use in automobile interior parts, and therefore have exceptional industrial effects. DETAILED DESCRIPTION OF THE INVENTION

[0014] <Polycarbonate resin> The polycarbonate resin in the present invention is a polycarbonate resin containing a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2) in the main chain, and containing a unit (C) represented by the following formula (4) at the terminal.

[0015] <Main chain of polycarbonate resin> [ka]

[0016] (In the above formula (1), ring Z is a fused polycyclic arene ring, R 1 and R 2 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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.

[0017] [ka]

[0018] (In the above formula (2), R 3 and R 4each independently represents at least one group selected from the group consisting of a hydrogen atom, 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; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following formula (3):

[0019] [ka]

[0020] (In the above formula (3), R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 ,R 11 and R 12 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different; R 13 and R 14 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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; R 15 ,R 16 ,R 17and R 18 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl 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, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, h and i are integers of 1 to 3, and g is an integer of 1 to 100.

[0021] In the formula (1), examples of the fused polycyclic arene ring represented by ring Z include fused bicyclic arene rings (for example, fused bicyclic arene rings having 10 to 16 carbon atoms, such as a naphthalene ring or an indene ring) and fused tricyclic arene rings (for example, an anthracene ring or a phenanthrene ring). Ring Z is preferably a naphthalene ring or an anthracene ring, more preferably a naphthalene ring. The two rings Z connected to the carbon atom at position 9 of the fluorene ring may be different from each other, but are usually the same in most cases.

[0022] The substitution position of ring Z relative to position 9 of the fluorene ring is not particularly limited. For example, when ring Z is a naphthalene ring, the substitution may be at either position 1 or 2 of the naphthalene ring relative to position 9 of the fluorene ring, and substitution at position 2 is preferred.

[0023] The substitution positions of the oxygen atom (—O—) and ester bond [—O—C(═O)—] that form a carbonate bond for linking the 9,9-bis-fused polycyclic arylfluorene skeleton are not particularly limited, as long as they are positions other than the bonding position between ring Z and the fluorene ring. For example, when ring Z is a naphthalene ring, they are usually substituted at any of positions 5 to 8 of a naphthyl group that is bonded to position 9 of the fluorene ring at the 1st or 2nd position. The 1st or 2nd position of the naphthalene ring is substituted with respect to position 9 of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and substitution in a 1,5-position or 2,6-position relationship with respect to this substitution position is preferred, and substitution in a 2,6-position relationship is more preferred.

[0024] In the formula (1), R 1 and R 2 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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.

[0025] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0026] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0027] Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0028] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0029] Preferred examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyloxy group, etc. A cycloalkoxy group having 6 to 12 carbon atoms is preferred.

[0030] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkenyl group having 2 to 6 carbon atoms is preferred.

[0031] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

[0032] Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group and a naphthyloxy group.

[0033] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0034] Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group and a phenylethyloxy group.

[0035] Among them, R 1 and R 2 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and particularly preferably a hydrogen atom.

[0036] The content of the repeating unit (A) represented by the formula (1) is 5 to 95 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%, and even more preferably 20 to 35 mol%, assuming that all repeating units in the main chain are 100 mol%. Being within the above ranges is preferable because it results in high pencil hardness and indentation hardness, excellent scratch resistance, and excellent glass transition temperature and 5% weight loss temperature, resulting in good heat resistance. The main chain referred to here means all structural units excluding terminal structural units.

[0037] The proportion of the repeating unit (A) may be achieved by a polycarbonate copolymer or by mixing polycarbonate resins with different composition ratios (polycarbonate blend).

[0038] In the formula (2), R 3 and R 4each independently represents at least one group selected from the group consisting of a hydrogen atom, 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, and when there are a plurality of each, they may be the same or different.

[0039] Here, examples of the alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the cycloalkyl group having 6 to 20 carbon atoms, the cycloalkoxy group having 6 to 20 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the aryl group having 6 to 14 carbon atoms, the aryloxy group having 6 to 14 carbon atoms, the aralkyl group having 7 to 20 carbon atoms, and the aralkyloxy group having 7 to 20 carbon atoms include the same groups as those described above.

[0040] In the formula (2), W is a single bond or at least one group selected from the group consisting of groups represented by the formula (3).

[0041] In the formula (3), R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 ,R 11 and R 12 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different.

[0042] Examples of the alkyl group having 1 to 18 carbon atoms, the aryl group having 6 to 14 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms include the same groups as those mentioned above.

[0043] In the formula (3), R 13 and R 14 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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.

[0044] Examples of the alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the cycloalkyl group having 6 to 20 carbon atoms, the cycloalkoxy group having 6 to 20 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the aryl group having 6 to 14 carbon atoms, the aryloxy group having 6 to 14 carbon atoms, the aralkyl group having 7 to 20 carbon atoms, and the aralkyloxy group having 7 to 20 carbon atoms include the same groups as those described above.

[0045] In the formula (3), R 15 ,R 16 ,R 17 and R 18 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl 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, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different.

[0046] Examples of the alkyl group having 1 to 18 carbon atoms, the cycloalkyl group having 6 to 20 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the aryl group having 6 to 14 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms include the same groups as those described above.

[0047] In the formula (3), c is an integer of 1 to 10, preferably an integer of 1 to 4, and more preferably 1. d is an integer of 4 to 7, and preferably 5. h and i are integers of 1 to 3, and preferably 1. g is an integer of 1 to 100, preferably an integer of 10 to 90, and more preferably an integer of 20 to 80.

[0048] In the formula (2), it is preferable that W contains at least one group selected from the group consisting of groups represented by the following formula (5).

[0049] [ka]

[0050] (In the above formula (5), R 29 , R 30 each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and when there are a plurality of each, they may be the same or different, and k is an integer of 1 to 3. In the formula (5), R 29 , R 30 each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

[0051] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0052] R 29 , R 30 As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is particularly preferred.

[0053] R 31 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

[0054] It is particularly preferred that the repeating unit (B) represented by the formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 2,2-bis(4-hydroxyphenyl)propane.

[0055] The content of the repeating unit (B) is preferably 5 to 95 mol%, more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%, and particularly preferably 65 to 80 mol%, assuming that all repeating units in the main chain are 100 mol%. Being within the above ranges is preferable because it results in high pencil hardness and indentation hardness, excellent scratch resistance, and excellent glass transition temperature and 5% weight loss temperature, resulting in good heat resistance. The main chain referred to here means all structural units excluding terminal structural units.

[0056] The main chain of the polycarbonate resin in the present invention may contain, in addition to the repeating units (A) and (B), repeating units derived from other dihydroxy compounds or other diol compounds, as described below, to the extent that the properties of the polycarbonate resin are not impaired. The repeating units (D) other than the repeating units (A) and (B) are preferably 30 mol % or less, more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 5 mol % or less, when the total repeating units of the main chain are taken as 100 mol %.

[0057] <Polycarbonate resin end> The polycarbonate resin in the present invention has a terminal structural unit represented by the following formula (4).

[0058] [ka] (In formula (4), m represents an integer of 0 or 1, and R 19 represents an alkyl group having 5 to 20 carbon atoms. In the formula (4), R 19is an alkyl group having 5 to 20 carbon atoms, preferably an alkyl group having 8 to 20 carbon atoms, and more preferably an alkyl group having 10 to 18 carbon atoms.

[0059] The content of the unit (C) represented by the formula (4) is 0.01 mol % or more, preferably 0.01 to 10 mol %, more preferably 0.1 to 9 mol %, even more preferably 0.5 to 8 mol %, and particularly preferably 1 to 7 mol %, when all repeating units in the main chain are taken as 100 mol %. If it is less than the lower limit, the glass transition temperature will increase and the fluidity will decrease, and if it exceeds the upper limit, the molecular weight will decrease and the polymer will become brittle.

[0060] Examples of monohydroxy compounds that induce the terminal structure represented by the formula (4) include 4-tert-octylphenol, 4-isooctylphenol, 4-octylphenol, 4-nonylphenol, 4-dodecylphenol, and 3-pentadecylphenol, with 4-dodecylphenol and 3-pentadecylphenol being preferred.

[0061] The terminals of the polycarbonate resin in the present invention may contain, in addition to the unit (C) represented by the formula (4), units derived from other monofunctional phenol compounds described below, to the extent that the properties of the polycarbonate resin are not impaired.

[0062] <Raw material for polycarbonate resin> The repeating unit (A) represented by the formula (1) is derived from a diol compound, and specifically, 9,9-bis(6-hydroxy-2-naphthyl)fluorene or 9,9-bis(6-hydroxy-1-naphthyl)fluorene is preferred, and 9,9-bis(6-hydroxy-2-naphthyl)fluorene is more preferred. These diol compounds may be used alone or in combination of two or more.

[0063] The repeating unit (B) represented by the formula (2) is derived from a diol compound, and examples thereof include 2,2-bis(4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 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;2,2-bis(4-hydroxy-3-bromophenyl)propane;2,2-bis(4-hydroxy-3,5-tetramethylphenyl)propane Bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxy-3-chlorophenyl)propane; 2,2-bis(4-hydroxy-3,5-tetrachlorophenyl)propane; 2,2-bis(4-hydroxy-3,5-tetrabromophenyl)propane, 4,4'-dihydroxyphenyl ether; 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxy-3,3'- Dihydroxydiaryl sulfides such as dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone; dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, dihydroxydiphenyls such as 4,4'-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)- (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-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, etc.;

[0064] Among these, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane or α,α'-bis(4-hydroxyphenyl)propane 2,2-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene is preferred, and 2,2-bis(4-hydroxyphenyl)propane (BPA) or 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) is more preferred. These diols may be used alone or in combination of two or more.

[0065] The polycarbonate resin of the present invention may be copolymerized with other dihydroxy compounds or diol compounds in addition to the repeating units (A) and (B) to the extent that the properties of the polycarbonate resin are not impaired.

[0066] Other dihydroxy compounds 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-dioxapentaenebisphenoxyethanolfluorene, and the like.

[0067] Other diol compounds include isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, and cyclohex-1,4-ylenedimethanol. Examples of suitable cyclohexanedimethanol include cyclohexane, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).

[0068] The unit (C) represented by the formula (4) is derived from a monofunctional phenol and is introduced into the polymer as a terminal terminator in the production method described below. Specific examples of the monofunctional phenol include 4-octylphenol, 4-isooctylphenol, 4-tert-octylphenol, nonylphenol, 4-dodecylphenol, and 3-pentadecylphenol, as described above. Among these, 4-dodecylphenol or 3-pentadecylphenol is preferred. These monofunctional phenols may be used alone or in combination of two or more.

[0069] In addition to the unit (C) represented by formula (4), commonly used monofunctional phenols can be used in combination as the end terminator. In particular, in reactions using phosgene as a carbonate precursor, monofunctional phenols are commonly used as end terminators to adjust molecular weight, and the resulting polycarbonate resin has superior thermal stability compared to those without the end terminator, since the end is blocked with a group based on the monofunctional phenol. Specific examples of the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, and p-cumylphenol. These monofunctional phenols may be used alone or in combination of two or more.

[0070] <Manufacturing method of polycarbonate resin> The polycarbonate resin in the present invention is obtained by reacting the diol compound with a carbonate precursor. Reaction methods include interfacial polycondensation, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. In the case of interfacial polycondensation, a monofunctional phenolic end-capping agent is usually used.

[0071] Polycarbonate resins include polyester carbonates copolymerized with aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids. The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of preferred aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane dicarboxylic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that the objective is not impaired. Furthermore, the polycarbonate resin may also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.

[0072] The polycarbonate resin can also be made into a branched polycarbonate by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary.

[0073] Suitable examples of trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Of these, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The structural units derived from such polyfunctional aromatic compounds preferably account for 0.03 to 1.5 mol %, more preferably 0.1 to 1.2 mol %, and particularly preferably 0.2 to 1.0 mol %, of a total of 100 mol % including structural units derived from other diol components.

[0074] The branched structural units may be derived not only from polyfunctional aromatic compounds but also from side reactions occurring during polymerization by melt transesterification without using polyfunctional aromatic compounds. 1 It can be calculated by H-NMR measurement.

[0075] In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Examples of solvents include halogenated hydrocarbons such as methylene chloride and chlorobenzene. To promote the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. The reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.

[0076] Transesterification using, for example, a carbonate diester as a carbonate precursor is carried out by stirring a predetermined ratio of aromatic diol components with the carbonate diester under heating in an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is typically in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning of the reaction to distill off the resulting alcohol or phenol. A catalyst typically used in transesterification can also be used to promote the reaction. Examples of carbonate diesters used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

[0077] (Other ingredients) The polycarbonate resin of the present invention may contain various additives to impart various properties to the resin composition, provided that the object of the present invention is not impaired. Additives that can be used include mold release agents, heat stabilizers, ultraviolet absorbers, bluing agents, antistatic agents, flame retardants, heat-shielding agents, fluorescent dyes (including fluorescent brighteners), pigments, light diffusing agents, reinforcing fillers, other resins, elastomers, etc.

[0078] Preferably, the release agent is one that is composed of 90% by weight or more of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include ester of monohydric alcohol and fatty acid, and partial or complete ester of polyhydric alcohol and fatty acid. Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Stearyl stearate is preferred. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and mixtures of stearic acid triglyceride and stearyl stearate are preferred, with stearic acid monoglyceride and pentaerythritol tetrastearate being more preferred.

[0079] The amount of the release agent to be added is preferably in the range of 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.4 parts by weight, and even more preferably 0.12 to 0.3 parts by weight, relative to 100 parts by weight of the polycarbonate resin.

[0080] Examples of heat stabilizers include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Examples of phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include 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-butylphenyl)phosphine, 3,9-bis(2,6-di-tert-butylphenyl)phosphine, 3,9-bis(2,6-di-tert-butylphenyl)phosphite, 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis(2,6-di-tert-butylphenyl)phosphine, 3,9-bis(2,6-di-tert-butylphenyl)phosphine, 3,9-bis(2,6-di-tert-butylphenyl)phosphite ... butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is preferred, and tris(2,4-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are more preferred.

[0081] The amount of the heat stabilizer to be added is preferably in the range of 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.4 parts by weight, and even more preferably 0.01 to 0.3 parts by weight, relative to 100 parts by weight of the polycarbonate resin.

[0082] (viscosity average molecular weight) The viscosity average molecular weight of the polycarbonate resin in the present invention is preferably in the range of 6,000 to 350,000, more preferably in the range of 7,000 to 30,000, even more preferably in the range of 8,000 to 28,000, particularly preferably in the range of 9,000 to 27,000, and most preferably in the range of 10,000 to 25,000. A viscosity average molecular weight within the above range is preferred because it provides excellent scratch resistance, heat resistance, and fluidity.

[0083] The viscosity average molecular weight of the polycarbonate resin in the present invention is determined by first calculating the specific viscosity (η SP ) was determined using an Ostwald viscometer from a solution of 0.7 g of resin dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0084] (glass transition temperature: Tg) The glass transition temperature (Tg) of the polycarbonate resin in the present invention is preferably in the range of 100 to 220°C, more preferably in the range of 120 to 200°C, even more preferably in the range of 130 to 190°C, and particularly preferably in the range of 140 to 180°C. A Tg within the above range is preferred because it provides good heat resistance and flowability. The glass transition temperature (Tg) is measured using a Model 2910 DSC manufactured by TA Instruments Japan, Inc., at a heating rate of 20°C / min.

[0085] (5% weight loss temperature: Td5%) The lower limit of the 5% weight loss temperature (Td5%) of the polycarbonate resin in the present invention is preferably 400°C or higher, more preferably 410°C or higher, and even more preferably 420°C or higher. When the 5% weight loss temperature is at or above the lower limit, the heat resistance, thermal stability, and fluidity are good, which is preferable. There is no particular upper limit, but a temperature of 700°C or lower, more preferably 600°C or lower, and even more preferably 500°C or lower is sufficient. The 5% weight loss temperature is measured using a TGA (model TGA2950) manufactured by TA Instruments.

[0086] (Pencil hardness) The pencil hardness of the polycarbonate resin in the present invention is preferably 2H or higher, more preferably 3H or higher, and even more preferably 4H or higher. Pencil hardness refers to the hardness at which no scratch marks remain when the polycarbonate resin is rubbed with a pencil having a specific pencil hardness. It is preferable to use the pencil hardness used in the surface hardness test of a coating film, which can be measured according to JIS K-5600, as an index. Pencil hardness decreases in the following order: 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B. Pencil hardnesses above the above range result in excellent scratch resistance of molded products.

[0087] (indentation hardness) The polycarbonate resin of the present invention has an indentation hardness of 200 to 400 (N / mm) as measured in accordance with ISO / TS 19278. 2 ), and 220 to 380 (N / mm 2 ), and more preferably 240 to 360 (N / mm 2 ), and particularly preferably 260 to 300 (N / mm 2 When the indentation hardness is within the above range, the molded product has excellent scratch resistance.

[0088] Pencil hardness, which is a commonly used index for measuring the scratch resistance of materials, is a discrete index with a range, making it difficult to compare the hardness of materials with the same pencil hardness of 2H, for example. Therefore, by using indentation hardness, which allows for quantitative evaluation, as an index, it is possible to evaluate the degree of hardness even for materials with the same pencil hardness.

[0089] Indentation hardness is measured based on ISO / TS 19278, using a dynamic ultra-micro hardness tester (Shimadzu Corporation, model DUH-210S) to measure the relationship between the load and indentation depth on the surface of the resin plate in real time.

[0090] (melt viscosity) The polycarbonate resin of the present invention has a melt viscosity measured by a capillary rheometer at 320°C and a shear rate of 608 sec -1 Under these conditions, the melt viscosity is preferably 1,500 Pa s or less, more preferably 1,200 Pa s or less, even more preferably 1,000 Pa s or less, and particularly preferably 950 Pa s or less. A melt viscosity of not more than the above upper limit is preferred because good fluidity can be achieved.

[0091] (Molding method and molded product) As a method for molding the polycarbonate resin in the present invention, general methods for molding polycarbonate resins can be used, such as injection molding, extrusion molding, compression molding, solution casting, etc. In particular, a method for molding a molded product by injection molding or a method for molding a sheet or film by extrusion molding are preferably used.

[0092] The polycarbonate resin of the present invention has excellent scratch resistance, heat resistance, and transparency and can be used for various molded articles. In particular, because of its excellent scratch resistance, it does not require a coating treatment and can be suitably used for automobile interior parts such as interior lamp lenses for interior lighting, display meter covers, meter dial plates, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts. [Example]

[0093] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Evaluation was performed according to the following methods.

[0094] (1) Composition ratio Each repeating unit was measured by proton NMR using JNM-AL400 manufactured by JEOL Ltd., and the composition ratio (molar ratio) of the copolymer was calculated. (2) Viscosity average molecular weight The specific viscosity (η SP) was measured using an Ostwald viscometer from a solution of 0.7 g of sample dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7 (3) Glass transition temperature (Tg) Using a TA Instruments DSC (model DSC2910), approximately 10 mg of the sample was heated at a temperature increase rate of 20°C / min and measured. (4) 5% weight loss temperature (Td5%) Using a TA Instruments TGA (Model TGA2950), approximately 10 mg of the sample was heated at a temperature increase rate of 20°C / min and measured. (5) Pencil hardness Polycarbonate resin was press-molded using a heat press molding machine (Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to form a circle with a thickness of approximately 3 mm. A disk-shaped resin plate was obtained. The press molding conditions were a mold temperature of 150 to 350°C, a primary pressure of 1 MPa (30 seconds), and a secondary pressure of 1.5 MPa (12 minutes). Using this resin plate, a line was drawn on the surface of the resin plate in accordance with JIS K5600 in a thermostatic chamber at an ambient temperature of 23°C, with a pencil held at a 45° angle and a load of 750 g applied, and the surface condition was evaluated visually. Load: 750g Measurement speed: 50mm / min Measurement distance: 7mm Pencil: Mitsubishi Pencil Hi-uni (6) Indentation hardness (Hit) Polycarbonate resin was press-molded using a heat press molding machine (Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to form a circle with a thickness of approximately 3 mm. A disk-shaped resin plate was obtained. The press molding conditions were a mold temperature of 150 to 350°C, a primary pressure of 1 MPa (30 seconds), and a secondary pressure of 1.5 MPa (12 minutes). Using this resin plate, a dynamic ultra-microhardness tester (Shimadzu Corporation, model DUH-210S) was used to measure the relationship between the load and the indentation depth on the surface of the resin plate in real time in accordance with ISO / TS 19278, and the indentation hardness (N / mm 2 ) was measured. (Measurement conditions) Measurement indenter: Berkovich indenter (made of diamond) Test force: 500mN Minimum test force: 4.9 mN Loading / unloading time: 30sec Load holding time: 40sec Unloading holding time: 0sec Number of tests: 5 (Method for calculating indentation hardness) Indentation hardness (Hit) is a measure of resistance to semi-permanent deformation or damage. Indentation hardness is calculated using the following formula: Hit=F max / Ap F max : Maximum test force A p : Projected area where the indenter and test piece are in contact A p =23.96×h c 2 (In the case of a triangular pyramidal indenter (115°)) h c =h max -ε(h max -h r ) ε=3 / 4 (in the case of a triangular pyramid) h r : F of the test force-depth curve max The intercept where the tangent to the unloading curve intersects with the depth axis at (7) Melt viscosity Using a capillary rheometer (Capillograph Model 1D) manufactured by Toyo Seiki Co., Ltd., the shear rate / viscosity curve obtained by measuring at a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, a measurement temperature of 320°C, and by arbitrarily changing the measurement speed was 608 sec -1 The melt viscosity was read at 100°C.

[0095] [Example 1] A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of a 25% aqueous sodium hydroxide solution, and 38.23 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as diol compounds, 40.34 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.157 parts by mass of hydrosulfite were dissolved therein. Then, 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24°C with stirring. Next, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide and 2.032 parts by mass of 4-dodecylphenol (4-DDP; Sigma-Aldrich) dissolved in 20.32 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26-31°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. This was followed by repeated washing with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was dried at 120° C. for 24 hours to obtain a white flake-like polycarbonate resin. The obtained polycarbonate resin was subjected to various evaluations using the above-mentioned methods, and the results are shown in Table 1.

[0096] [Example 2] A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of a 25% aqueous sodium hydroxide solution, and 38.23 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as diol compounds, 40.34 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.157 parts by mass of hydrosulfite were dissolved therein. Then, 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24°C with stirring. Next, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide and 2.362 parts by mass of 3-pentadecylphenol (3-PDP; manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 20.32 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added at a temperature of 26 to 31°C while the reaction solution was at 28°C, and the reaction was terminated by continuing stirring for 1 hour at a temperature of 26 to 31°C. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washing solution became neutral, hydrochloric acid was added. This was followed by repeated washing with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50 to 80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was dried at 120° C. for 24 hours to obtain a white flake-like polycarbonate resin. The obtained polycarbonate resin was subjected to various evaluations using the above-mentioned methods, and the results are shown in Table 1.

[0097] [Reference example 1] A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of 25% aqueous sodium hydroxide solution, and 38.23 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as a diol compound, 40.34 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.157 parts by mass of hydrosulfite were dissolved therein. 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24 ° C. with stirring. Then, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide solution and 1.164 parts by mass of p-tert-butylphenol (PTBP; manufactured by DIC Corporation) dissolved in 11.64 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added while the reaction solution was at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. The solution was then repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50 to 80°C, and the solvent was evaporated to obtain a flaky solid. The resulting solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. The resulting polycarbonate resin was subjected to various evaluations using the methods described above, and the results are shown in Table 1.

[0098] [Table 1]

[0099] [Example 3] A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of a 25% aqueous sodium hydroxide solution, and 38.23 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as diol compounds, 40.34 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.157 parts by mass of hydrosulfite were dissolved therein. Then, 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24°C with stirring. Next, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide and 4.446 parts by mass of 4-dodecylphenol (4-DDP; Sigma-Aldrich) dissolved in 20.32 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added at a temperature of 26-31°C while the reaction solution was at 28°C, and the reaction was terminated by continuing stirring for 1 hour at a temperature of 26-31°C. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washing solution became neutral, hydrochloric acid was added. This was followed by repeated washing with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was dried at 120° C. for 24 hours to obtain a white flake-like polycarbonate resin. The obtained polycarbonate resin was subjected to various evaluations using the above-mentioned methods, and the results are shown in Table 2.

[0100] [Example 4] A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of 25% aqueous sodium hydroxide solution, and 31.67 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.), 42.20 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), 1.66 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (BPA; manufactured by Nippon Steel Chemical & Material Co., Ltd.), and 0.148 parts by mass of hydrosulfite were dissolved therein. Then, 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24°C with stirring. Next, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide and 2.032 parts by mass of 4-dodecylphenol (4-DDP; Sigma-Aldrich) dissolved in 20.32 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26-31°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. This was followed by repeated washing with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was dried at 120° C. for 24 hours to obtain a white flake-like polycarbonate resin. The obtained polycarbonate resin was subjected to various evaluations using the above-mentioned methods, and the results are shown in Table 2.

[0101] [Reference example 2] A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of 25% aqueous sodium hydroxide solution, and 38.23 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as a diol compound, 40.34 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.157 parts by mass of hydrosulfite were dissolved therein. 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24 ° C. with stirring. Then, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide solution and 2.255 parts by mass of p-tert-butylphenol (PTBP; manufactured by DIC Corporation) dissolved in 22.55 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added while the reaction solution was at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. The solution was then repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50 to 80°C, and the solvent was evaporated to obtain a flaky solid. The resulting solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. The resulting polycarbonate resin was subjected to various evaluations using the methods described above, and the results are shown in Table 2.

[0102] [Table 2]

[0103] [Example 5] A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of a 25% aqueous sodium hydroxide solution, and 26.21 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as diol compounds, 47.17 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.147 parts by mass of hydrosulfite were dissolved therein. Then, 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24°C with stirring. Next, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide and 2.032 parts by mass of 4-dodecylphenol (4-DDP; Sigma-Aldrich) dissolved in 20.32 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26-31°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. This was followed by repeated washing with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was dried at 120°C for 24 hours to obtain a white flake-like polycarbonate resin. The obtained polycarbonate resin was subjected to various evaluations using the above-mentioned methods, and the results are shown in Table 3.

[0104] [Reference example 3] A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of 25% aqueous sodium hydroxide solution, and 26.21 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as a diol compound, 47.17 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.147 parts by mass of hydrosulfite were dissolved therein. 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24 ° C. with stirring. Then, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide solution and 1.164 parts by mass of p-tert-butylphenol (PTBP; manufactured by DIC Corporation) dissolved in 11.64 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added while the reaction solution was at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. The solution was then repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50 to 80°C, and the solvent was evaporated to obtain a flaky solid. The resulting solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. The resulting polycarbonate resin was subjected to various evaluations using the methods described above, and the results are shown in Table 3.

[0105] [Table 3]

[0106] [Example 6] A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of a 25% aqueous sodium hydroxide solution, and 21.84 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as diol compounds, 49.65 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.143 parts by mass of hydrosulfite were dissolved therein. Then, 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24°C with stirring. Next, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide and 2.032 parts by mass of 4-dodecylphenol (4-DDP; Sigma-Aldrich) dissolved in 20.32 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26-31°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. This was followed by repeated washing with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was dried at 120°C for 24 hours to obtain a white flake-like polycarbonate resin. The obtained polycarbonate resin was subjected to various evaluations using the above-mentioned methods, and the results are shown in Table 4.

[0107] [Reference example 4] A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of 25% aqueous sodium hydroxide solution, and 21.84 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as a diol compound, 49.65 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.143 parts by mass of hydrosulfite were dissolved therein. 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24 ° C. with stirring. Then, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide solution and 1.164 parts by mass of p-tert-butylphenol (PTBP; manufactured by DIC Corporation) dissolved in 11.64 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added while the reaction solution was at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. The solution was then repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50 to 80°C, and the solvent was evaporated to obtain a flaky solid. The resulting solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. The resulting polycarbonate resin was subjected to various evaluations using the methods described above, and the results are shown in Table 4.

[0108] [Table 4]

[0109] [Example 7] A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of a 25% aqueous sodium hydroxide solution, and 10.92 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as diol compounds, 55.86 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.143 parts by mass of hydrosulfite were dissolved therein. Then, 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24°C with stirring. Next, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide and 2.032 parts by mass of 4-dodecylphenol (4-DDP; Sigma-Aldrich) dissolved in 20.32 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26-31°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. This was followed by repeated washing with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was dried at 120° C. for 24 hours to obtain a white flake-like polycarbonate resin. The obtained polycarbonate resin was subjected to various evaluations using the above-mentioned methods, and the results are shown in Table 5.

[0110] [Reference example 5] A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 327.27 parts by mass of ion-exchanged water and 128.00 parts by mass of 25% aqueous sodium hydroxide solution, and 10.92 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemicals Co., Ltd.) as a diol compound, 55.86 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC; manufactured by Honshu Chemical Co., Ltd.), and 0.143 parts by mass of hydrosulfite were dissolved therein. 309.09 parts by mass of methylene chloride was added, and 30.00 parts by mass of phosgene was blown in over 80 minutes at 16 to 24 ° C. with stirring. Then, a solution of 19.39 parts by mass of 25% aqueous sodium hydroxide solution and 1.164 parts by mass of p-tert-butylphenol (PTBP; manufactured by DIC Corporation) dissolved in 11.64 parts by mass of methylene chloride was added and stirred to form an emulsion. While stirring, 0.0612 parts by mass of triethylamine was added while the reaction solution was at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, hydrochloric acid was added. The solution was then repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The resulting methylene chloride solution was then added dropwise to warm water maintained at 50 to 80°C, and the solvent was evaporated to obtain a flaky solid. The resulting solid was dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. The resulting polycarbonate resin was subjected to various evaluations using the methods described above, and the results are shown in Table 5.

[0111] [Table 5] [Industrial Applicability]

[0112] The polycarbonate resin of the present invention has excellent scratch resistance, heat resistance, and fluidity, and therefore does not require a coating treatment and can be used for automobile interior parts such as lamp lenses for interior lighting, display meter covers, meter dial plates, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts.

Claims

1. A polycarbonate resin containing a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2) in its main chain and a unit (C) represented by the following formula (4) at its terminal, wherein, when all repeating units in the main chain are taken as 100 mol %, the proportion of repeating units (A) represented by formula (1) is 5 to 95 mol %, and when all repeating units in the main chain are taken as 100 mol %, the proportion of units (C) represented by formula (4) is 0.01 mol % or more. 【Chemical 1】 (In the above formula (1), ring Z is a fused polycyclic arene ring, R 1 and R 2 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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. 【Chemistry 2】 (In the above formula (2), R 3 and R 4 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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; when there are a plurality of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following formula (3): 【Chemistry 3】 (In the above formula (3), R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different; R 13 and R 14 each independently represents at least one group selected from the group consisting of a hydrogen atom, 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; R 15 , R 16 , R 17 and R 18 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl 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, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, h and i are integers of 1 to 3, and g is an integer of 1 to 100. 【Chemistry 4】 (In formula (4), m represents an integer of 0 or 1, and R 19 represents an alkyl group having 5 to 20 carbon atoms.

2. 2. The polycarbonate resin according to claim 1, wherein in the repeating unit (A) represented by formula (1), ring Z is a naphthalene ring.

3. 2. The polycarbonate resin according to claim 1, wherein W in the formula (2) contains at least one group selected from the group consisting of groups represented by the following formula (5): 【Chemistry 5】 (In the above formula (5), R 29 , R 30 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and when there are a plurality of each, they may be the same or different.

4. The polycarbonate resin according to claim 1, wherein the repeating unit (B) represented by formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 2,2-bis(4-hydroxyphenyl)propane.

5. 2. The polycarbonate resin according to claim 1, wherein the content of the repeating unit (B) is in the range of 5 to 95 mol % based on all repeating units in the main chain.

6. 2. The polycarbonate resin according to claim 1, wherein the proportion of the structural unit (C) represented by formula (4) is 0.01 to 10 mol %, when all repeating units in the main chain are taken as 100 mol %.

7. The R 19 The polycarbonate resin according to claim 1, wherein is an alkyl group having 8 to 20 carbon atoms.

8. 2. The polycarbonate resin according to claim 1, which has a glass transition temperature of 100 to 220°C.

9. Indentation hardness measured in accordance with ISO / TS 19278 is 200 to 400 (N / mm 2 2. The polycarbonate resin according to claim 1, wherein

10. 2. The polycarbonate resin according to claim 1, which has a pencil hardness of 2H or more as measured in accordance with JIS K5600.

11. 2. The polycarbonate resin according to claim 1, wherein the 5% weight loss temperature is 400°C or higher.

12. The melt viscosity measured by a capillary rheometer at 320°C is 608 sec. -1 2. The polycarbonate resin according to claim 1, which has a viscosity of 1,500 Pa·s or less under the conditions of

13. A molded article obtained by injection molding the polycarbonate resin according to any one of claims 1 to 12.

14. A sheet or film obtained by extrusion molding the polycarbonate resin according to any one of claims 1 to 12.

15. 14. An automobile interior part using the molded product according to the preceding paragraph 13.

16. 15. An automobile interior part using the sheet or film according to the preceding paragraph 14.

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