Polycarbonate resin and molded article comprising same

Abstract

A polycarbonate resin containing a repeating unit (A) represented by formula (1), the proportion of the repeating unit (A) represented by formula (1) being 1-99 mol% with respect to the total repeating units of the polycarbonate resin, the polycarbonate resin having excellent scratch resistance and heat resistance. (In formula (1), ring Z represents a fused polycyclic aromatic hydrocarbon ring; r1 and R2 each independently represent 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, and an aldehyde group; and at least one of a cyano group and a carboxyl group. > # imgabs0 #

Description

Technical Field

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

[0002] Polycarbonate resins are excellent in transparency, impact resistance, heat resistance, and dimensional stability, and are therefore used as engineering plastics in a wide range of fields such as casings for electrical and electronic devices, interior and exterior automotive trim parts, building materials, furniture, musical instruments, and sundries. In addition, compared with inorganic glass, they have a low specific gravity, can be lightweight, and have excellent productivity, so they are used in window applications for automobiles and the like.

[0003] In addition, sheets or films made of polycarbonate resin are widely used as various display devices and protective parts for automotive interiors through additional secondary processing such as coating treatment, laminate formation, and surface modification.

[0004] However, the pencil hardness of the polycarbonate resin without coating treatment is only about 2B as measured according to the general test method for coatings - Part 5: Mechanical properties of coating films - Section 4: Scratch hardness (pencil method) described in JIS K5600-5-4. As an uncoated material, it can be said that there is a problem that the surface is easily damaged.

[0005] Therefore, copolycarbonate resins having a high surface hardness are known. In addition, methods for producing polycarbonates and copolycarbonates having 2,2-bis(4-hydroxy-3-methylphenyl)propane as a repeating unit have been described. Although the surface hardness of this polycarbonate resin is improved, there is a problem that its heat resistance is poor compared with that of polycarbonate resins (Patent Documents 1 to 6).

[0006] In addition, Patent Document 7 describes a method for producing a polycarbonate and a copolycarbonate having 2,2-bis(4-hydroxy-3-methylphenyl)fluorene as a repeating unit, and it is proposed that this is effective for high pencil hardness and high heat resistance. However, there is a problem that the scratch resistance is insufficient.

[0007] Therefore, an object of the present invention is to solve the above problems and to provide a polycarbonate resin having excellent scratch resistance and heat resistance, and a molded article made of the same.

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: Japanese Patent No. 5173803 Gazette

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 64-069625

[0012] Patent Document 3: Japanese Unexamined Patent Application Publication No. 08-183852

[0013] Patent Document 4: Japanese Unexamined Patent Application Publication No. 08-034846

[0014] Patent Document 5: Japanese Unexamined Patent Application Publication No. 2002-117580

[0015] Patent Document 6: Japanese Patent No. 3768903

[0016] Patent Document 7: International Publication No. 2017 / 073508 SUMMARY OF THE INVENTION

[0017] The problem to be solved by the present invention is to provide a polycarbonate resin having excellent heat resistance and scratch resistance and a molded article made of the same.

[0018] The inventors of the present invention repeatedly conducted in-depth studies to achieve the above object, and as a result, found that a polycarbonate resin having a specific structure can solve the above problem, thereby completing the present invention. That is, the present invention is as described in the following items 1 to 13.

[0019] 1. A polycarbonate resin comprising a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), and the proportion of the repeating unit (A) represented by the formula (1) is 1 to 99 mol% based on the total repeating units of the polycarbonate resin.

[0020]

[0021] (In the above formula (1), ring Z represents a fused polycyclic aromatic ring, and R 1 and R 2 each independently represent at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.)

[0022]

[0023] (In the above formula (2), R 3 and R 4Each independently represents at least one group selected from 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 aralkoxy 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 them respectively, they may be the same or different. e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the groups represented by the following formula (3).)

[0024]

[0025] (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 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. When there are a plurality of them, they may be the same or different. R 13 and R 14 each independently represents at least one group selected from 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 aralkoxy 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 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. When there are a plurality of them, 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 each an integer of 1 to 3, and g is an integer of 1 to 100.)

[0026] 2. The polycarbonate resin according to item 1 above, wherein in the repeating unit (A) represented by the above formula (1), the ring Z is a naphthalene ring.

[0027] 3. The polycarbonate resin according to item 1 or 2 above, wherein the content ratio of the repeating unit (B) is in the range of 1 to 99 mol% based on the total repeating units.

[0028] 4. The polycarbonate resin according to any one of items 1 to 3 above, wherein W in the above formula (2) contains at least one group selected from the groups represented by the following formula (4).

[0029]

[0030] (In the above formula (4), R 29 , R 30 , R 31 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and when there are a plurality of them respectively, they may be the same or different, and k is an integer of 1 to 3.)

[0031] 5. The polycarbonate resin according to any one of items 1 to 4 above, wherein the repeating unit (B) represented by the above formula (2) contains a repeating unit derived from at least one compound selected from 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimide.

[0032] 6. The polycarbonate resin according to any one of items 1 to 5 above, wherein the glass transition temperature is 125 to 310 °C.

[0033] 7. The polycarbonate resin according to any one of items 1 to 6 above, wherein the indentation hardness measured according to ISO / TS 19278 is 235 to 450 (N / mm 2 ).

[0034] 8. The polycarbonate resin according to any one of items 1 to 7 above, wherein the pencil hardness measured according to JIS K5600 is 2H or more.

[0035] 9. The polycarbonate resin according to any one of items 1 to 8 above, wherein the 5% weight loss temperature is 400 °C or higher.

[0036] 10. The polycarbonate resin according to any one of items 1 to 9 above, wherein the saturated water absorption rate is 0.5% or less.

[0037] 11. The polycarbonate resin according to any one of items 1 to 10 above, wherein the linear expansion coefficient is 30 to 60 ppm / °C.

[0038] 12. A molded article made of the polycarbonate resin according to any one of Items 1 to 11 above.

[0039] 13. The molded article according to Item 12 above, wherein the molded article is an automotive interior trim part.

[0040] 14. The molded article according to Item 12 above, wherein the molded article is an optical molded article.

[0041] 15. The molded article according to Item 14 above, wherein the spectral transmittance is 85% or more at wavelengths of 850 nm, 1310 nm, and 1550 nm, 82% or more at a wavelength of 1610 nm, and 78% or more at a wavelength of 1625 nm.

[0042] 16. A polycarbonate resin composition containing 1 to 99 parts by weight of a copolymerized polycarbonate resin (Component A) and 99 to 1 part by weight of an aromatic polycarbonate resin (Component B). In the above copolymerized polycarbonate resin, the content ratio of the repeating unit (a) represented by the following formula (1) is 5 to 95 mol% based on the total repeating units, and the content ratio of the repeating unit (b) represented by the following formula (2) is 95 to 5 mol%.

[0043]

[0044] (In the above formula (1), ring Z represents a fused polycyclic aromatic ring, and R 1 and R 2 each independently represent at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.)

[0045]

[0046] (In the above formula (2), R 3 and R 4Each independently represents at least one group selected from 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 aralkoxy 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 them respectively, they may be the same or different. e and f are each an integer from 1 to 4, and W is a single bond or at least one group selected from the groups represented by the following formula (3).)

[0047]

[0048] (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 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. When there are a plurality of them, they may be the same or different. R 13 and R 14 each independently represents at least one group selected from 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 aralkoxy 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 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. When there are a plurality of them, they may be the same or different. c is an integer from 1 to 10, d is an integer from 4 to 7, h and i are integers from 1 to 3, and g is an integer from 1 to 100.)

[0049] 17. The polycarbonate resin composition according to the previous item 16, wherein the aromatic polycarbonate resin (component B) is an aromatic polycarbonate resin containing repeating units derived from bisphenol A.

[0050] 18. The polycarbonate resin composition according to item 16 or 17 above, wherein the glass transition temperature is single.

[0051] 19. A molded article composed of the polycarbonate resin according to any one of items 16 to 18 above.

[0052] The polycarbonate resin of the present invention and the molded article composed of the same are excellent in scratch resistance and heat resistance, and are therefore suitable for use in automotive interior trim parts. Therefore, the industrial effects exerted by them are remarkable. Detailed implementation mode

[0053] Hereinafter, the details of the present invention will be described.

[0054] (Mode 1)

[0055] <Polycarbonate resin>

[0056] The polycarbonate resin of 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).

[0057]

[0058] (In the above formula (1), ring Z represents a fused polycyclic aromatic ring, and R 1 and R 2 each independently represent at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.)

[0059]

[0060] (In the above formula (2), R 3 and R 4 each independently represent at least one group selected from 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 aralkoxy 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 them respectively, they may be the same or different, and e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the groups represented by the following formula (3).)

[0061]

[0062] (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 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. When there are a plurality of them, they may be the same or different. R 13 and R 14 each independently represents at least one group selected from 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 aralkoxy 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 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. When there are a plurality of them, 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.)

[0063] In the above formula (1), as the fused polycyclic aromatic hydrocarbon ring represented by ring Z, a fused bicyclic aromatic hydrocarbon ring (for example, a fused bicyclic aromatic hydrocarbon ring having 10 to 16 carbon atoms such as a naphthalene ring and an indene ring), a fused tricyclic aromatic hydrocarbon ring (for example, an anthracene ring and a phenanthrene ring), etc. can be mentioned. As ring Z, a naphthalene ring or an anthracene ring is preferred, and a naphthalene ring is more preferred. The two rings Z connected to the 9-position carbon atom of the fluorene ring may be of different types from each other, but usually they are the same in many cases.

[0064] In addition, there is no particular limitation on the substitution position of ring Z at the 9-position of the fluorene ring. For example, when ring Z is a naphthalene ring, for the 9-position of the fluorene ring, it can be substituted at any position of the 1-position or 2-position of the naphthalene ring, and substitution at the 2-position is preferred.

[0065] The substitution positions of the oxygen atom (-O-) forming the carbonate bond and the ester bond [-O-C(=O)-] for connecting the 9,9-bifused polycyclic arylfluorene skeleton are not particularly limited as long as they are positions other than the bonding position of the ring Z and the fluorene ring. For example, when the ring Z is a naphthalene ring, generally, substitution at any position of the 5th to 8th positions of the naphthyl group bonded to the 9th position of the fluorene ring at the 1st or 2nd position is more common. The 1st or 2nd position of the naphthalene ring substitutes the 9th position of the fluorene ring (substitution in the relationship of 1-naphthyl or 2-naphthyl). Relative to this substitution position, substitution in the relationship of 1,5 positions or 2,6 positions is preferred, and substitution in the relationship of 2,6 positions is more preferred.

[0066] In the above formula (1), R 1 and R 2 each independently represents at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0067] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc.

[0068] 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, a tetradecyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0069] 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 pentyloxy group, a hexyloxy group, an octyloxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0070] 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.

[0071] Examples of the cycloalkoxy group having 6 to 20 carbon atoms preferably include a cyclohexyloxy group, a cyclooctyloxy group, etc. A cycloalkoxy group having 6 to 12 carbon atoms is preferred.

[0072] Examples of the alkenyl group having 2 to 10 carbon atoms include a methylene group, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkenyl group having 2 to 6 carbon atoms is preferred.

[0073] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, etc.

[0074] Examples of the aryloxy group having 6 to 14 carbon atoms include a phenoxy group, a naphthyloxy group, etc.

[0075] Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl and phenylethyl.

[0076] Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy and phenylethoxy.

[0077] Among them, R 1 and R 2 are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and particularly preferably a hydrogen atom.

[0078] The content ratio of the repeating unit (A) is 1 to 99 mol%, preferably 5 to 95 mol%, more preferably 10 to 90 mol% with respect to the total repeating units of the polycarbonate resin. If it is within the above range, the pencil hardness and indentation hardness are increased, the scratch resistance is excellent, and the glass transition temperature and 5% weight loss temperature are excellent and the heat resistance is good, so it is preferred.

[0079] In the above formula (2), R 3 and R 4 each independently represent at least one group selected from 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 cycloalkyloxy 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 them respectively, they may be the same or different.

[0080] Here, as 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 cycloalkyloxy 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, the same groups as the above groups can be cited.

[0081] In the above formula (2), W is a single bond or at least one group selected from the groups represented by the above formula (3).

[0082] In the above formula (3), R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12Each independently represents at least one group selected from 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. When there are a plurality of them, they may be the same or different.

[0083] 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 described above.

[0084] In the above formula (3), R 13 and R 14 Each independently represents at least one group selected from 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.

[0085] 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.

[0086] In the above formula (3), R 15 , R 16 , R 17 and R 18 Each independently represents at least one group selected from 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. When there are a plurality of them, they may be the same or different.

[0087] 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.

[0088] In the above formula (3), c is an integer of 1 to 10, preferably an integer of 1 to 4, more preferably 1. d is an integer of 4 to 7, preferably 5. h and i are integers of 1 to 3, preferably 1. g is an integer of 1 to 100, preferably an integer of 10 to 90, more preferably an integer of 20 to 80.

[0089] In the above formula (2), preferably, W contains at least one group selected from the groups represented by the following formula (4).

[0090]

[0091] (In the above formula (4), R 29 , R 30 , R 31 each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. When there are a plurality of them respectively, they may be the same or different, and k is an integer of 1 to 3.)

[0092] In the above formula (4), R 29 , R 30 , R 31 each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

[0093] Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0094] As R 29 , R 30 , an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is preferred, and methyl is particularly preferred.

[0095] As R 31 , a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom or methyl is particularly preferred.

[0096] The repeating unit (B) represented by the above formula (2) particularly preferably contains a repeating unit derived from at least one compound selected from 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes simply referred to as BPC), 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes simply referred to as BPA), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes simply referred to as BisP-HTG), and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimididine (hereinafter sometimes simply referred to as PPPBP).

[0097] Relative to the total repeating units of the polycarbonate resin, the content ratio of the repeating unit (B) is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, and still more preferably 10 to 90 mol%. If it is within the above range, the pencil hardness and indentation hardness are increased and the scratch resistance is excellent, and the glass transition temperature and 5% weight loss temperature are excellent and the heat resistance is good, so it is preferred.

[0098] The polycarbonate resin of the present invention, to the extent that the properties of the polycarbonate resin are not impaired, may contain, in addition to the repeating unit (A) and the repeating unit (B), repeating units derived from other dihydroxy compounds and other diol compounds described below. With respect to the total repeating units, the repeating unit (C) other than the repeating unit (A) and the repeating unit (B) is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0099] <Raw materials of polycarbonate resin>

[0100] The repeating unit (A) represented by the above formula (1) is a repeating unit derived from a diol compound. 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.

[0101] The repeating unit (B) represented by the above formula (2) is a repeating unit 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-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-tetramethylphenyl)propane, 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 and other bis(hydroxyaryl)alkanes; dihydroxyaryl ethers such as 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; dihydroxy diaryl sulfoxides such as 4,4'-dihydroxy diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; dihydroxy diaryl sulfones such as 4,4'-dihydroxy diphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone; dihydroxy diphenyls such as 4,4'-dihydroxy diphenyl; dihydroxy diaryl fluorenes such as 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene; 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxy-3,3'-dimethylbenzophenone, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-biphenyldiol, 3,3'-dimethyl-4,4'-biphenyldiol, α,α'-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimididine, etc.

[0102] Among these, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidinedine are preferred, and 2,2-bis(4-hydroxyphenyl)propane (BPA), 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisP-HTG), and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidinedine (PPPBP) are more preferred. These diols can be used alone or in combination of two or more.

[0103] The polycarbonate resin of the present invention can copolymerize other dihydroxy compounds and diol compounds to the extent that the properties of the polycarbonate resin are not impaired, in addition to the repeating unit (A) and the repeating unit (B).

[0104] Examples of 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-dioxapentene, bisphenoxyethanol fluorene, and the like.

[0105] Examples of other diol compounds include isosorbide: 1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutane diol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, 1,4-cyclohexanedimethanol (シクロヘクス-1,4-イルエンジメタノール), 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'-di(cyclohexyl)-4,4'-diol, spirodiol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexane, and poly(ethylene glycol), etc.

[0106] <Manufacturing method of polycarbonate resin>

[0107] The polycarbonate resin of the present invention is a polycarbonate resin obtained by reacting the above-mentioned diol compound with a carbonate precursor. As the reaction method, an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, a ring-opening polymerization method of a cyclic carbonate compound, etc. can be cited. In the case of interfacial polycondensation, a monohydric phenol-based end-capping agent is usually used.

[0108] The polycarbonate resin contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. As the aliphatic difunctional carboxylic acid, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid and other linear saturated aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be preferably cited. These carboxylic acids can be copolymerized within the range that does not hinder the purpose. In addition, the polycarbonate resin can also copolymerize a structural unit containing a polyorganosiloxane unit as needed.

[0109] The polycarbonate resin can also copolymerize a structural unit containing a polyfunctional aromatic compound having three or more functional groups as needed to form a branched polycarbonate.

[0110] As the polyfunctional aromatic compound having three or more functional groups used for the branched polycarbonate, 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 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other triphenols can be preferably exemplified. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The structural unit derived from the above polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1 to 1.2 mol%, and particularly preferably 0.2 to 1.0 mol% in the total of 100 mol% of the structural units from other diol components.

[0111] In addition, the branched structural unit is not only derived from a polyfunctional aromatic compound, but can also be a structural unit derived without using a polyfunctional aromatic compound such as a side reaction generated during the polymerization reaction based on the melt transesterification method. It should be noted that regarding the ratio of the above-mentioned branched structure, it can be calculated by 1 1H-NMR measurement.

[0112] As a carbonate precursor, for example, in a reaction using phosgene, the reaction is usually carried out in the presence of an acid scavenger and a solvent. As the acid scavenger, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide or amine compounds such as pyridine can be used. As the solvent, for example, halogenated hydrocarbons such as dichloromethane and chlorobenzene can be used. In addition, in order to promote the reaction, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. At this time, the reaction temperature is usually 0 to 40 °C, and the reaction time is several minutes to 5 hours.

[0113] As a carbonate precursor, for example, the transesterification reaction using a dicarbonate is carried out by heating and stirring a specified proportion of an aromatic diol component and a dicarbonate in an inert gas atmosphere, and distilling out the generated alcohol or phenol. The reaction temperature varies depending on the boiling point of the generated alcohol or phenol, etc., but is usually in the range of 120 to 300 °C. The reaction is carried out under reduced pressure from its initial stage, and the reaction is completed while distilling out the generated alcohol or phenol. In addition, in order to promote the reaction, a catalyst commonly used for transesterification reactions can also be used. As the dicarbonate used for the transesterification reaction described above, for example, diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc. can be cited. Among these, diphenyl carbonate is particularly preferred.

[0114] As a capping agent, commonly used monofunctional phenols can be used. Especially in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a capping agent for molecular weight regulation. In addition, since the obtained polycarbonate resin has its terminals blocked by groups based on monofunctional phenols, its thermal stability is excellent compared to the case where it is not capped. Specific examples of the above monofunctional phenols include phenol, m-cresol, p-cresol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, p-long-chain alkylphenol, etc.

[0115] (Other components)

[0116] In the polycarbonate resin of the present invention, in order to impart various properties within the range not impairing the object of the present invention, it can be made into a resin composition containing various additives. As the additives, a mold release agent, a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a heat ray shielding agent, a fluorescent dye (including a fluorescent brightening agent), a pigment, a light diffusing agent, a reinforcing filler, other resins, an elastomer, etc. can be compounded.

[0117] As a mold release agent, preferably more than 90% by weight thereof is composed of an ester of an alcohol and a fatty acid. As the ester of an alcohol and a fatty acid, specifically, an ester of a monohydric alcohol and a fatty acid, a partial ester or a full ester of a polyhydric alcohol and a fatty acid can be cited. Specifically, as the ester of a monohydric alcohol and a saturated fatty acid, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. can be cited. Stearyl stearate is preferred. As the partial ester or full ester of a polyhydric alcohol and a saturated fatty acid, monoglyceryl stearate, diglyceryl stearate, triglycerin stearate, sorbitan monostearate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraisononanoate, propylene glycol monostearate, biphenylphenol biphenyl ester, sorbitan monostearate, 2-ethylhexyl stearate, and full esters or partial esters of dipentaerythritol such as dipentaerythritol hexastearate can be cited. Among these esters, monoglyceryl stearate, triglycerin stearate, pentaerythritol tetrastearate, and a mixture of triglycerin stearate and stearyl stearate are preferred, and monoglyceryl stearate and pentaerythritol tetrastearate are more preferred.

[0118] Regarding the compounding amount of the mold release agent, relative to 100 parts by weight of the polycarbonate resin, a range of 0.05 to 0.5 parts by weight is preferred, a range of 0.1 to 0.4 parts by weight is more preferred, and a range of 0.12 to 0.3 parts by weight is further preferred.

[0119] As heat stabilizers, phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers can be cited. As phosphorus-based heat stabilizers, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, etc. can be cited. Specifically, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, [1,1-biphenyl]-4,4-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are preferred, and tris(2,4-di-tert-butylphenyl) phosphite, stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are more preferred.

[0120] Regarding the compounding amount of the heat stabilizer, relative to 100 parts by weight of the polycarbonate resin, a range of 0.001 to 0.5 parts by weight is preferred, a range of 0.005 to 0.4 parts by weight is more preferred, and a range of 0.01 to 0.3 parts by weight is further preferred.

[0121] (Viscosity-average molecular weight)

[0122] The viscosity-average molecular weight of the polycarbonate resin of 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, further preferably in the range of 8,000 to 28,000, particularly preferably in the range of 9,000 to 25,000, and most preferably in the range of 10,000 to 22,000. If it is within the above range, the scratch resistance, heat resistance, and moldability are excellent, so it is preferred.

[0123] The viscosity-average molecular weight of the polycarbonate resin of the present invention is calculated as follows. First, using an Ubbelohde viscometer, the specific viscosity (η SP ) calculated by the following formula is obtained from a solution formed by dissolving 0.7 g of the resin in 100 ml of dichloromethane at 20°C.

[0124] Specific viscosity (η SP ) = (t - t 0 ) / t 0

[0125] [t 0 is the dropping time in seconds of dichloromethane, and t is the dropping time in seconds of the sample solution]

[0126] The viscosity-average molecular weight Mv is calculated from the obtained specific viscosity (η SP ) according to the following mathematical formula.

[0127] η SP / c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity)

[0128] [η] = 1.23 × 10 －4 Mv 0.83

[0129] c = 0.7

[0130] (Glass transition temperature: Tg)

[0131] The glass transition temperature (Tg) of the polycarbonate resin of the present invention is preferably in the range of 125 to 310°C, more preferably in the range of 125 to 300°C, further preferably in the range of 130 to 290°C, particularly preferably in the range of 135 to 280°C, and most preferably in the range of 140 to 270°C. If Tg is within the above range, the heat resistance and moldability are good, so it is preferred. The glass transition temperature (Tg) is measured using a DSC 2910 type manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20°C / min.

[0132] (5% weight loss temperature: Td5%)

[0133] The lower limit of the 5% weight loss temperature (Td5%) of the polycarbonate resin of the present invention is preferably 400 °C or higher, more preferably 410 °C or higher, and further preferably 420 °C or higher. If the 5% weight loss temperature is above the lower limit, the heat resistance, thermal stability, and moldability are good, so it is preferred. The upper limit is not particularly limited, but it is preferably 700 °C or lower, more preferably 600 °C or lower, and further preferably 500 °C or lower, which is sufficient. The 5% weight loss temperature is measured by TGA (model TGA2950) manufactured by TA Instruments.

[0134] (Pencil hardness)

[0135] The pencil hardness of the polycarbonate resin of the present invention is preferably 2H or higher, more preferably 3H or higher. The pencil hardness refers to the hardness at which no scratch marks are left even when a pencil with a specific pencil hardness is rubbed on the polycarbonate resin. It is preferred to use the pencil hardness for the surface hardness test of the coating film that can be measured according to JIS K-5600 as an index. The pencil hardness becomes softer in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B. The hardest pencil is 9H, and the softest pencil is 6B. If the pencil hardness is above the above, the scratch resistance of the molded product is excellent.

[0136] (Indentation hardness)

[0137] The polycarbonate resin of the present invention preferably has an indentation hardness of 235 - 450 (N / mm 2 ) measured according to ISO / TS19278, more preferably 240 - 430 (N / mm 2 ), further preferably 245 - 420 (N / mm 2 ), particularly preferably 250 - 410 (N / mm 2 ), and most preferably 260 - 400 (N / mm 2 ). If the indentation hardness is within the above range, the scratch resistance of the molded product is excellent.

[0138] It should be noted that the pencil hardness, which is a frequently used index for the scratch resistance of materials, is an index with a width discreteness. Therefore, for example, it is difficult to compare the hardness between materials with the same "2H" pencil hardness. Therefore, by using the indentation hardness that can be quantitatively evaluated as an index, even for materials with the same pencil hardness, the degree of hardness can be evaluated.

[0139] The indentation hardness is measured according to ISO / TS19278 and using a dynamic ultra-micro hardness tester (Shimadzu Corporation, model DUH-210S) to measure the relationship between the load on the surface of the resin plate and the indentation depth in real time.

[0140] (Molding method and molded article)

[0141] As a molding method of the polycarbonate resin of the present invention, common molding methods for polycarbonate resins such as injection molding, extrusion molding, compression molding, and solution casting can be adopted. A method of molding into a molded article by injection molding and a method of molding into a sheet or film by extrusion molding are particularly preferably adopted.

[0142] The polycarbonate resin of the present invention is excellent in scratch resistance, heat resistance, and transparency, and thus can be used as various molded articles. In particular, due to its excellent scratch resistance, a coating treatment is not required, and it is suitable for various interior automotive decoration parts such as lamp lenses for interior lighting, instrument covers for displays, instrument nameplates, various switch covers, display covers, heat control panels, instrument panels, central instrument clusters, central panels, interior lamp lenses for vehicles, and heads-up displays, as well as various display devices, protective parts, and light-transmitting parts.

[0143] (Optical molded article)

[0144] In addition, the polycarbonate resin of the present invention is excellent in heat resistance, dimensional stability, low water absorption, and light transmittance, and thus is useful as an optical molded article. In particular, it is suitable for use as an optical molded article for optical components such as optical connectors or transceivers that require reflow soldering resistance.

[0145] Examples of the optical molded article include various lenses such as sensor lenses, condenser lenses, collimating lenses, and lens arrays, mirrors, optical waveguides, and wide-angle diffusion elements.

[0146] When used for an optical molded article, the repeating unit (B) represented by the above formula (2) particularly preferably contains a repeating unit derived from at least one compound selected from 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes simply referred to as BPA), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes simply referred to as BisP-HTG), and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimididine (hereinafter sometimes simply referred to as PPPBP). Moreover, the (glass transition temperature: Tg), (linear expansion coefficient), (saturated water absorption rate), (spectral transmittance), and (reflow soldering resistance) characteristics are preferably in the following ranges.

[0147] (Glass transition temperature: Tg)

[0148] The glass transition temperature (Tg) of the polycarbonate resin of the present invention is preferably in the range of 220 to 310 °C, more preferably in the range of 230 to 307 °C, further preferably in the range of 240 to 305 °C, and most preferably in the range of 250 °C to 300 °C. If the Tg is within the above range, the heat resistance, dimensional stability, and moldability are good, so it is preferred. The glass transition temperature (Tg) is measured using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20 °C / min.

[0149] (Coefficient of linear expansion)

[0150] The coefficient of linear expansion of the polycarbonate resin of the present invention is preferably in the range of 30 to 60 ppm / °C, more preferably in the range of 32 to 58 ppm / °C, further preferably in the range of 34 to 56 ppm / °C, and most preferably in the range of 35 to 55 ppm / °C. If the coefficient of linear expansion is within the above range, the dimensional change caused by heat is small, so it is preferred. The coefficient of linear expansion is obtained as follows: Using a thermomechanical analysis device (SS6100 manufactured by SII Nano Technology Inc.), a sample with a length of 4 mm and a width of 20 mm is measured 3 times at a heating rate of 10 °C / min and a cooling rate of 50 °C / min, and the coefficient of linear expansion in the temperature range of 50 to 90 °C is calculated, and the average value is obtained.

[0151] (Saturated water absorption rate)

[0152] The saturated water absorption rate of the polycarbonate resin of the present invention is measured according to JIS K7209:2000, and is preferably 0.50% or less, more preferably 0.49% or less, and further preferably 0.48% or less. If the saturated water absorption rate is within the above range, the dimensional change caused by water absorption is small, so it is preferred. The lower limit of the saturated water absorption rate is not particularly limited, and it is sufficient if it is 0.1% or more.

[0153] (Spectral transmittance)

[0154] The spectral transmittance of a 1-mm-thick portion of the optical molded article using the polycarbonate resin of the present invention is preferably 85% or more at a measurement wavelength of 850 nm, a measurement wavelength of 1310 nm, and a measurement wavelength of 1550 nm, 82% or more at a measurement wavelength of 1610 nm, and 78% or more at a measurement wavelength of 1625 nm. If the spectral transmittance is within the above range, the attenuation of the optical communication signal is small, so it is preferred.

[0155] (Reflow soldering resistance)

[0156] According to the "Moisture / Reflow Sensitivity Classification of Non-Sealed Solid State Surface Mount Devices" of IPC / JEDEC J - STD - 020C, a reflow test temperature profile was performed on the optical molded article. The molded article was placed in a humidity chamber at 60°C / 60% RH (relative humidity), exposed for 120 hours for humidity conditioning, and then placed in an oven and heated according to the temperature profile of IPC / JEDEC J - STD - 020C (peak temperature is 240°C or 260°C). It is preferred that no change in the transparency and shape of the molded article is observed at a peak temperature of 240°C, and more preferably no change in the transparency and shape of the molded article is observed at a peak temperature of 260°C.

[0157] (Method 2)

[0158] <Copolycarbonate resin (Component A)>

[0159] The polycarbonate resin composition of the present invention is a polycarbonate resin composition containing 1 to 99 parts by weight of a copolycarbonate resin (Component A) and 99 to 1 part by weight of an aromatic polycarbonate resin (Component B). In the above copolycarbonate resin (Component A), the content ratio of the repeating unit (a) represented by the following formula (1) is 5 to 95 mol% based on the total repeating units, and the content ratio of the repeating unit (b) represented by the following formula (2) is 95 to 5 mol%.

[0160]

[0161] (In the above formula (1), ring Z represents a fused polycyclic aromatic ring, and R 1 and R 2 each independently represents at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.)

[0162]

[0163] (In the above formula (2), R 3 and R 4Each independently represents at least one group selected from 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 aralkoxy 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 them respectively, they may be the same or different. e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the groups represented by the following formula (3).)

[0164]

[0165] (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 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. When there are a plurality of them, they may be the same or different. R 13 and R 14 each independently represents at least one group selected from 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 aralkoxy 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 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. When there are a plurality of them, 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 each an integer of 1 to 3, and g is an integer of 1 to 100.)

[0166] The ring Z, R 1 and R 2 in the above formula (1) are the same as those described in the item of (Mode 1).

[0167] In addition, R in the above formula (2) 3 and R 4 、W are the same as those described in the items of (Mode 1).

[0168] And, R in the above formula (3) 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、c, d, h, i, g are the same as those described in the items of (Mode 1).

[0169] The repeating unit (b) represented by the above formula (2) particularly preferably contains a repeating unit derived from at least one compound selected from 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter, sometimes simply referred to as BPC), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (hereinafter, sometimes simply referred to as OCZ).

[0170] With respect to the total repeating units of the copolycarbonate resin (Component A), the content ratio of the repeating unit (b) is 5 to 95 mol%, preferably 10 to 90 mol%, more preferably 20 to 90 mol%, and further preferably 30 to 90 mol%. If within the above range, in the resin composition with the polycarbonate resin (Component B), phase separation does not occur during extrusion or molding and the resin composition does not become cloudy, so it is preferred.

[0171] The copolycarbonate resin (Component A) of the present invention may, to the extent that it does not impair the properties of the polycarbonate resin composition, in addition to containing the repeating unit (a) and the repeating unit (b), further contain repeating units derived from other dihydroxy compounds and other diol compounds described later. With respect to the total repeating units, the repeating unit (c) other than the repeating unit (a) and the repeating unit (b) is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0172] <Raw materials of the copolycarbonate resin (Component A)>

[0173] The repeating unit (a) represented by the above formula (1) is a repeating unit derived from a diol compound. Specifically, it is preferably 9,9-bis(6-hydroxy-2-naphthyl)fluorene or 9,9-bis(6-hydroxy-1-naphthyl)fluorene, and more preferably 9,9-bis(6-hydroxy-2-naphthyl)fluorene. These diol compounds can be used alone or in combination of two or more.

[0174] The repeating unit (b) represented by the above formula (2) is a repeating unit derived from a diol compound, and examples thereof include bis(hydroxyaryl)alkanes such as 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-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-tetramethylphenyl)propane, 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; dihydroxyaryl ethers such as 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; dihydroxy diaryl sulfoxides such as 4,4'-dihydroxy diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; dihydroxy diaryl sulfones such as 4,4'-dihydroxy diphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone; dihydroxy diphenyls such as 4,4'-dihydroxy diphenyl; dihydroxy diaryl fluorenes such as 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene; 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxy-3,3'-dimethylbenzophenone, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-biphenyldiol, 3,3'-dimethyl-4,4'-biphenyldiol, α,α'-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimididine, etc.

[0175] Among these, 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (OCZ) are preferred. These diols can be used individually or in combination of two or more.

[0176] The copolycarbonate resin (component A) of the present invention can copolymerize other dihydroxy compounds and diol compounds to the extent that the properties of the polycarbonate resin composition are not impaired, in addition to the repeating unit (a) and the repeating unit (b).

[0177] As other dihydroxy compounds, it is the same as the description in the item of (Mode 1).

[0178] <Manufacturing method of copolycarbonate resin (component A)>

[0179] The copolycarbonate resin (component A) of the present invention is obtained by reacting the above diol compound with a carbonate precursor. As the reaction method, an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, a ring-opening polymerization method of a cyclic carbonate compound, etc. can be cited. In the case of interfacial polycondensation, a capping agent of monohydric phenols is usually used.

[0180] The copolycarbonate resin (component A) contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. As the aliphatic difunctional carboxylic acid, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid and other linear saturated aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be preferably cited. These carboxylic acids can be copolymerized within the range that does not hinder the purpose. In addition, the copolycarbonate resin (component A) can also copolymerize a structural unit containing a polyorganosiloxane unit as needed.

[0181] The copolycarbonate resin (component A) can also copolymerize a structural unit containing a polyfunctional aromatic compound having three or more functional groups as needed to form a branched polycarbonate.

[0182] Examples of the polyfunctional aromatic compound having three or more functional groups used as the branched-chain polycarbonate 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 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl}-α,α-dimethylbenzylphenol. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The structural unit derived from the above polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1 to 1.2 mol%, and particularly preferably 0.2 to 1.0 mol% in the total of 100 mol% with the structural unit derived from other diol components.

[0183] In addition, the branched-chain structural unit may be derived not only from the polyfunctional aromatic compound but also from a side reaction that occurs during the polymerization reaction by the melt transesterification method without using a polyfunctional aromatic compound. It should be noted that the ratio of the above branched-chain structure can be calculated by 1 1H-NMR measurement.

[0184] As the carbonate precursor, for example, in the reaction using phosgene, the reaction is usually carried out in the presence of an acid-binding agent and a solvent. As the acid-binding agent, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide or amine compounds such as pyridine are used. As the solvent, for example, halogenated hydrocarbons such as dichloromethane and chlorobenzene are used. In addition, in order to promote the reaction, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. At this time, the reaction temperature is usually 0 to 40 °C, and the reaction time is several minutes to 5 hours.

[0185] As the carbonate precursor, for example, the transesterification reaction using a carbonate diester is carried out by heating and stirring a specified ratio of an aromatic diol component and a carbonate diester in an inert gas atmosphere to distill out the generated alcohol or phenol. The reaction temperature varies depending on the boiling point of the generated alcohol or phenol, etc., but is usually in the range of 120 to 300 °C. The reaction is carried out under reduced pressure from the initial stage, and the reaction is completed while distilling out the generated alcohol or phenol. In addition, in order to promote the reaction, a catalyst usually used for transesterification can also be used. Examples of the carbonate diester used for the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc. Among these, diphenyl carbonate is particularly preferred.

[0186] As the end-capping agent, monofunctional phenols that are commonly used can be used. Especially in the case of a reaction using phosgene as the carbonate precursor substance, monofunctional phenols are generally used as the end-capping agent for molecular weight regulation. In addition, the resulting polycarbonate resin has excellent thermal stability because its terminals are blocked by groups based on monofunctional phenols as compared with the case where it is not end-capped. Specific examples of the above monofunctional phenols include, for example, phenol, m-cresol, p-cresol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, p-long-chain alkylphenol, and the like.

[0187] (Viscosity-average molecular weight)

[0188] The viscosity-average molecular weight of the copolycarbonate resin (component A) of the present invention is preferably in the range of 6,000 to 35,000, more preferably in the range of 7,000 to 30,000, still more preferably in the range of 8,000 to 28,000, particularly preferably in the range of 9,000 to 25,000, and most preferably in the range of 10,000 to 22,000. If it is within the above range, in the resin composition with the polycarbonate resin (component B), phase separation does not occur during extrusion or molding, and the resin composition does not become cloudy, and it has excellent heat resistance, scratch resistance, and impact resistance, so it is preferred.

[0189] The viscosity-average molecular weight of the polycarbonate resin of the present invention is calculated as follows: First, using an Ostwald viscometer, the specific viscosity (η SP ) calculated by the following formula is obtained from a solution formed by dissolving 0.7 g of the resin in 100 ml of dichloromethane at 20°C.

[0190] Specific viscosity (η SP ) = (t - t 0 ) / t 0

[0191] [t 0 is the dropping seconds of dichloromethane, and t is the dropping seconds of the sample solution]

[0192] From the obtained specific viscosity (η SP ), the viscosity-average molecular weight Mv is calculated using the following mathematical formula.

[0193] η SP / c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity)

[0194] [η] = 1.23 × 10 －4 Mv 0.83

[0195] c = 0.7

[0196] (Glass transition temperature: Tg)

[0197] The glass transition temperature (Tg) of the copolycarbonate resin (Component A) of the present invention is preferably in the range of 100 to 300 °C, more preferably in the range of 120 to 280 °C, and still more preferably in the range of 130 to 270 °C. If the Tg is within the above range, in the resin composition with the polycarbonate resin (Component B), phase separation does not occur during extrusion or molding, and the resin composition does not become cloudy, and the heat resistance and moldability are good, so it is preferred. The glass transition temperature (Tg) is measured using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20 °C / min. <Aromatic polycarbonate resin (Component B)>

[0198] The aromatic polycarbonate resin (Component B) of the present invention can be either a homopolymer or a copolymer. In addition, the aromatic polycarbonate resin (B) can have a branched structure, a linear structure, or a mixture of a branched structure and a linear structure.

[0199] As a method for manufacturing the aromatic polycarbonate resin (B) using bisphenol as a raw material, any known method such as the phosgene method, the transesterification method, or the pyridine method can be used.

[0200] As representative examples of bisphenol, bisphenols can be cited, and 2,2-bis(4-hydroxyphenyl)propane, that is, bisphenol A, is particularly preferably used. In addition, a part or all of bisphenol A can be replaced with other bisphenols. As other bisphenols, bis(4-hydroxyphenyl)alkanes such as hydroquinone, 4,4-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, and 1,1-bis(4-hydroxyphenyl)ethane can be cited; bis(4-hydroxyphenyl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane; compounds such as bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)ether; alkylated bisphenols such as 2,2-bis(3-methyl-4-hydroxyphenyl)propane and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; and halogenated bisphenols such as 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane. Among bisphenols, an aromatic polycarbonate resin obtained by preferably using 50 mol% or more of bisphenol A, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol% is desired.

[0201] (Viscosity-average molecular weight)

[0202] The viscosity-average molecular weight of the aromatic polycarbonate resin (Component B) used in the present invention is not particularly limited, but from the balance of heat resistance, impact resistance, and moldability of the resin composition, it is preferably in the range of 15,000 to 35,000, more preferably 18,000 to 32,000. Here, using an Ostwald viscometer, the specific viscosity (η SP ) calculated by the following formula is obtained from a solution formed by dissolving 0.7 g of the sample in 100 ml of dichloromethane at 20 °C.

[0203] Specific viscosity (η SP ) = (t - t 0 ) / t 0

[0204] [t 0 is the dropping time of dichloromethane, and t is the dropping time of the sample solution]

[0205] From the obtained specific viscosity (η SP ), the viscosity-average molecular weight Mv is calculated using the following mathematical formula.

[0206] η SP / c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity)

[0207] [η] = 1.23 × 10 －4 Mv 0.83

[0208] c = 0.7

[0209] (Glass transition temperature: Tg)

[0210] The glass transition temperature (Tg) of the aromatic polycarbonate resin (B) is preferably 120 to 180 °C, more preferably 140 to 160 °C. If Tg is within the above range, when forming the polycarbonate resin composition, the heat resistance and impact resistance are good, so it is preferred.

[0211] The glass transition temperature (Tg) is measured using a DSC 2910 type manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20 °C / min.

[0212] <Manufacturing method of polycarbonate resin composition and molded article>

[0213] When manufacturing the resin composition of the present invention, its manufacturing method is not particularly limited, and known manufacturing methods can be used. Generally, the copolymerized polycarbonate resin (A), the aromatic polycarbonate resin (B), and the additive are pre-mixed and then put into an extruder for melt-kneading. Then, the extruded filament bundle is cooled and cut by a granulator to manufacture a granular molding material. As the extruder, either a single-screw extruder or a twin-screw extruder can be used, but from the viewpoints of productivity and kneading property, a twin-screw extruder is preferred. As a representative example of the above twin-screw extruder, KZW15-25MG (manufactured by TECHNOVEL Co., Ltd.) and ZSK (manufactured by Werner & Pfleiderer) can be cited. As specific examples of the same type, TEX (manufactured by Nippon Steel & Sumitomo Metal Corporation), TEM (manufactured by Toshiba Machine Co., Ltd.), KTX (manufactured by Kobe Steel, Ltd.), etc. can be cited. As the extruder, an extruder having an exhaust port capable of degassing the moisture in the raw materials and the volatile gases generated by the melt-kneaded resin is preferably used. A vacuum pump for efficiently discharging the generated moisture and volatile gases from the exhaust port to the outside of the extruder is preferably provided. In addition, a screen for removing foreign substances and the like mixed in the extrusion raw materials can be provided in the area in front of the extruder die part, so as to remove the foreign substances from the resin composition. As the above screen, a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), etc. can be cited.

[0214] Furthermore, the additive can be independently supplied to the extruder, but as described above, pre-mixing with the resin raw materials is preferred. In the above pre-mixing methods, a Nauta mixer, a V-type mixer, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc. can be exemplified. A more preferred method is, for example, a method in which a part of the raw materials and the additive are mixed by a high-speed mixer such as a Henschel mixer to prepare a masterbatch, and then the masterbatch and the remaining full amount of the resin raw materials are mixed by a non-high-speed mixer such as a Nauta mixer.

[0215] The resin extruded by an extruder can be directly cut and granulated, or after forming a tow, the tow can be cut by a granulator to form granules. When it is necessary to reduce the influence of external dust, etc., it is preferable to clean the environment around the extruder. Also, in the production of the above-mentioned granules, various methods that have been proposed are used, and it is preferable to narrow the shape distribution of the granules, further reduce the uncut materials, further reduce the fine powder generated during transportation, and reduce the air bubbles (true air bubbles) generated inside the tow and the granules. In reducing uncut materials, methods such as temperature management of the screw during cutting by a granulator, blowing of ionic wind during cutting, rationalization of the inclination angle of the granulator, and appropriate combination of mold release agents, and methods such as filtering a mixture of the cut granules and water to separate the granules from water and uncut materials can be cited. An example of this measurement method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. Through these treatment methods, high cycle molding can be achieved, and the occurrence ratio of defects such as silver streaks can be reduced.

[0216] The resin composition of the present invention can also obtain a target molded product by methods such as injection molding, injection compression molding, injection blow molding, extrusion molding, or blow molding. Also, various surface treatments can be performed on the molded product of the present invention. The surface treatment mentioned here refers to vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dip plating, etc.), painting, coating, printing, etc., which form a new layer on the surface layer of the resin molded product, and methods applicable to ordinary thermoplastic resins can be used. As surface treatments, specifically, various surface treatments such as hard coating, waterproof and oil-proof coating, ultraviolet absorption coating, infrared absorption coating, and metal spraying (vapor deposition, etc.) can be exemplified.

[0217] In the polycarbonate resin composition of the present invention, various additives can be contained within the scope of not impairing the object of the present invention to impart various properties. As additives, a mold release agent, a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a heat ray shielding agent, a fluorescent dye (including a fluorescent brightening agent), a pigment, a light diffusing agent, a reinforcing filler, other resins, an elastomer, etc. can be compounded.

[0218] Specific examples and compounding ratios of the mold release agent and the heat stabilizer are the same as those described in the item of (Mode 1).

[0219] (by weight)

[0220] The weight ratio of the copolycarbonate resin (Component A) to the aromatic polycarbonate resin (Component B) can be arbitrarily mixed in the range of 1:99 to 99:1. It is preferably in the range of 5:95 to 95:5, and more preferably in the range of 10:90 to 90:10. By being in the above range, a polycarbonate resin composition excellent in heat resistance, scratch resistance, and impact resistance can be obtained.

[0221] (Viscosity-average molecular weight)

[0222] The viscosity-average molecular weight of the polycarbonate resin composition of the present invention is preferably in the range of 6,000 to 35,000, more preferably in the range of 8,000 to 32,000, further preferably in the range of 10,000 to 30,000, particularly preferably in the range of 13,000 to 28,000, and most preferably in the range of 15,000 to 25,000. It is preferred because it is excellent in heat resistance, scratch resistance, and impact resistance.

[0223] The viscosity-average molecular weight of the polycarbonate resin composition of the present invention is calculated as follows. First, using an Ostwald viscometer, the specific viscosity (η SP )

[0224] Specific viscosity (η SP ) = (t - t 0 ) / t 0

[0225] [t 0 is the dropping seconds of dichloromethane, and t is the dropping seconds of the sample solution]

[0226] From the obtained specific viscosity (η SP ), the viscosity-average molecular weight Mv is calculated using the following mathematical formula.

[0227] η SP / c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity)

[0228] [η] = 1.23 × 10 －4 Mv 0.83

[0229] c = 0.7

[0230] (Glass transition temperature: Tg)

[0231] Preferably, the polycarbonate resin composition of the present invention has a single glass transition temperature (Tg), and the temperature range is preferably in the range of 100 to 300 °C, more preferably in the range of 120 to 250 °C, further preferably in the range of 130 to 220 °C, and particularly preferably in the range of 140 to 200 °C. If the Tg is within the above range, in the resin composition with the polycarbonate resin (Component B), phase separation does not occur during extrusion or molding, and the resin composition does not become cloudy, and the heat resistance and moldability are good, so it is preferred. The glass transition temperature (Tg) is measured using a 2910-type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20 °C / min. In the present invention, if the glass transition temperature (Tg) is single, when measuring the glass transition temperature using DSC, only one inflection point representing the glass transition temperature appears.

[0232] Generally speaking, the single glass transition temperature of a blended polymer composition means that the mixed resins are in a compatible state at the nanoscale (molecular level), and it can be confirmed as a compatible system.

[0233] (Transparency: Total light transmittance)

[0234] The polycarbonate resin composition of the present invention preferably has a total light transmittance of 85% or more for a 2-mm-thick molded sheet. If the total light transmittance is within the above range, there is no limitation on the range of use as an optical component, so it is preferred.

[0235] (Indentation hardness)

[0236] The polycarbonate resin composition of the present invention preferably has an indentation hardness measured according to ISO / TS19278 of 150 to 400 (N / mm 2 ), more preferably 170 to 350 (N / mm 2 ), further preferably 200 to 300 (N / mm 2 ), particularly preferably 215 to 290 (N / mm 2 ), and most preferably 225 to 280 (N / mm 2 ). If the indentation hardness is within the above range, the scratch resistance of the molded product is excellent.

[0237] It should be noted that since the pencil hardness, which is an index often used for the scratch resistance of materials, is an index with a discrete width, it is difficult to compare the hardness between materials with the same pencil hardness of "2H", for example. Therefore, the indentation hardness that can be quantitatively evaluated is used as an index, so that even for materials with the same pencil hardness, the degree of hardness can be evaluated.

[0238] The indentation hardness is measured in accordance with ISO / TS 19278 using a dynamic ultra-micro hardness tester (Shimadzu Corporation, model DUH-210S), and measuring in real time the relationship between the load on the surface of the resin plate and the indentation depth.

[0239] (Pencil hardness)

[0240] The pencil hardness of the polycarbonate resin composition of the present invention is preferably H or more, more preferably 2H or more, and still more preferably 3H or more. Pencil hardness refers to the hardness such that no rubbing marks are left even when rubbing with a pencil having a specific pencil hardness on the polycarbonate resin. Preferably, the pencil hardness used in the surface hardness test of the coating film that can be measured according to JIS K-5600 is used as an index. The pencil hardness becomes softer in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B. The hardest pencil is 9H and the softest pencil is 6B. If the pencil hardness is above the above, the scratch resistance of the molded product is excellent.

[0241] (Notched Charpy impact value)

[0242] The notched Charpy impact strength of the polycarbonate resin composition of the present invention measured according to ISO 179 is preferably 1.5 kJ / m 2 or more, more preferably 2.0 kJ / m 2 or more, and still more preferably 3.0 kJ / m 2 or more. It should be noted that the notched Charpy impact strength has sufficient function at 100 kJ / m 2 or less. (Weight drop resistance test: DuPont impact test)

[0243] The polycarbonate resin composition of the present invention uses a DuPont type impact deformation tester, uses an impact die (radius 6.35 mm), a receiving die (inner diameter 15.2 mm, outer diameter 25.0 mm), and a parallel flat plate with a length and width of 50 mm and a thickness of 2 mm is provided between the receiving die and the impact die. Preferably, it is not damaged when a 1 kg drop hammer is dropped from a height of 1 m.

[0244] Examples

[0245] Hereinafter, the present invention will be described in more detail based on examples, which do not limit the present invention. It should be noted that the evaluation is carried out according to the following method.

[0246] (Method 1-A)

[0247] (1) Composition ratio

[0248] The proton NMR of JNM-AL400 manufactured by JEOL Ltd. is used to measure each repeating unit, and the composition ratio (molar ratio) of the copolymer is calculated.

[0249] (2) Viscosity-average molecular weight

[0250] Using an Ostwald viscometer, the specific viscosity (η SP ) is determined from a solution formed by dissolving 0.7 g of the sample in 100 ml of dichloromethane at 20 °C,

[0251] Specific viscosity (η SP ) = (t - t 0 ) / t 0

[0252] [t 0 is the dropping time in seconds of dichloromethane, and t is the dropping time in seconds of the sample solution]

[0253] The viscosity-average molecular weight Mv is calculated from the determined specific viscosity (η SP ) using the following mathematical formula.

[0254] η SP / c = [η] + 0.45 × [η] 2 c (where [η] is the intrinsic viscosity)

[0255] [η] = 1.23 × 10 －4 Mv 0.83

[0256] c = 0.7

[0257] (3) Glass transition temperature (Tg)

[0258] Using a DSC (model DSC 2910) manufactured by TA Instruments, about 10 mg of the sample is heated at a heating rate of 20 °C / min for measurement.

[0259] (4) 5% weight loss temperature (Td5%)

[0260] Using a TGA (model TGA2950) manufactured by TA Instruments, about 10 mg of the sample is heated at a heating rate of 20 °C / min for measurement.

[0261] (5) Pencil hardness

[0262] The obtained polycarbonate resin was compression-molded using a hot press machine (compression molding machine manufactured by Shindo Metal Industry Co., Ltd.: SFV-10, vacuum pump unit: GXD-360) to obtain a disc-shaped resin plate with a thickness of approximately 3 mm. The compression molding conditions were a mold temperature of 150 to 350 °C, first press: 1 MPa (30 seconds), second press: 1.5 MPa (12 minutes). Using this resin plate, according to JIS K5600, in a constant temperature chamber at an ambient temperature of 23 °C, while holding a pencil at an angle of 45 degrees and applying a load of 750 g to the surface of the resin plate, draw a line and evaluate the surface condition by visual observation.

[0263] Load: 750 g

[0264] Measurement speed: 50 mm / min

[0265] Measurement distance: 7 mm

[0266] Pencil: Hi-uni manufactured by Mitsubishi Pencil Co., Ltd.

[0267] (6) Indentation hardness (Hit)

[0268] The obtained polycarbonate resin was compression-molded using a hot press machine (compression molding machine manufactured by Shindo Metal Industry Co., Ltd.: SFV-10, vacuum pump unit: GXD-360) to obtain a disc-shaped resin plate with a thickness of approximately 3 mm. The compression molding conditions were a mold temperature of 150 to 350 °C, first press: 1 MPa (30 seconds), second press: 1.5 MPa (12 minutes). Using this resin plate, according to ISO / TS 19278, using a dynamic ultra-micro hardness tester (manufactured by Shimadzu Corporation, model DUH-210S), the relationship between the surface load on the resin plate and the indentation depth was measured in real time to determine the indentation hardness (N / mm 2 ).

[0269] (Measurement conditions)

[0270] Indentation indenter: Berkovich indenter (made of diamond)

[0271] Test force: 500 mN

[0272] Minimum test force: 4.9 mN

[0273] Load / unload time: 30 sec

[0274] Load holding time: 40 sec

[0275] Unload holding time: 0 sec

[0276] Number of tests: 5

[0277] (Indentation hardness calculation method)

[0278] Indentation hardness (Hit) measures the resistance to semi-permanent deformation or damage. Indentation hardness is calculated by the following formula.

[0279] Hit = F max / A p

[0280] F max : Maximum test force

[0281] A p : Projected area where the indenter contacts the test piece

[0282] A p = 23.96 × h c 2 (For a triangular pyramid indenter (115°))

[0283] h c = h max - ε(h max - h r )

[0284] ε = 3 / 4 (for a triangular pyramid)

[0285] h r : Intercept of the tangent of the unloading curve of the F of the test force - depth curve with the depth axis [Example A - 1] max

[0286] To a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 131.56 parts by mass of ion-exchanged water and 40.28 parts by mass of a 25% aqueous sodium hydroxide solution were added. After dissolving 29.27 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 4.16 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC, manufactured by Honshu Chemical Co., Ltd.), and 0.067 parts by mass of sodium dithionite, 103.55 parts by mass of dichloromethane was added. While stirring, 10.05 parts by mass of phosgene was blown in at 16 - 24°C over 80 minutes. Then, a solution formed by dissolving 6.50 parts by mass of a 25% aqueous sodium hydroxide solution and 0.365 parts by mass of p-tert-butylphenol in 3.65 parts by mass of dichloromethane was added and stirred to form an emulsified state. While stirring, 0.021 parts by mass of triethylamine was added when the reaction solution was at 28°C, and stirring was continued at 26 - 31°C for 1 hour to complete the reaction. After the reaction was completed, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into 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 flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 1.

[0287] [Example A-2]

[0288] 114.80 parts by mass of ion-exchanged water, 35.15 parts by mass of 25% aqueous sodium hydroxide solution were added to a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 15.96 parts by mass of BNF, 9.07 parts by mass of BPC, which are diol compounds, and 0.050 parts by mass of sodium dithionite, 90.35 parts by mass of dichloromethane were added. While stirring, 9.19 parts by mass of phosgene was blown in at 16 - 24°C over 80 minutes. Then, a solution formed by dissolving 5.67 parts by mass of 25% aqueous sodium hydroxide solution and 0.319 parts by mass of p-tert-butylphenol in 3.19 parts by mass of dichloromethane was added and stirred to form an emulsified state. While stirring, 0.018 parts by mass of triethylamine was added in a state where the reaction solution was at 28°C, and stirring was continued at 26 - 31°C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into 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 flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 1.

[0289] [Example A - 3]

[0290] To a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 120.29 parts by mass of ion-exchanged water and 36.83 parts by mass of a 25% aqueous sodium hydroxide solution were added. After dissolving 16.73 parts by mass of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 8.46 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (BPA, manufactured by Nippon Steel Chemical & Material Co., Ltd.), and 0.050 parts by mass of sodium dithionite, 94.67 parts by mass of dichloromethane was added, and 9.63 parts by mass of phosgene was blown in at 16 to 24°C for 80 minutes with stirring. Then, a solution formed by dissolving 5.94 parts by mass of a 25% aqueous sodium hydroxide solution and 0.334 parts by mass of p-tert-butylphenol in 3.34 parts by mass of dichloromethane was added and stirred to form an emulsified state. Under the above stirring, 0.019 parts by mass of triethylamine was added in a state where the reaction solution was at 28°C, and stirring was continued at a temperature of 26 to 31°C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into 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 flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 1.

[0291] [Example A-4]

[0292] 122.91 parts by mass of ion-exchanged water, 37.63 parts by mass of 25% aqueous sodium hydroxide solution were added to a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 6.84 parts by mass of BNF, 15.54 parts by mass of BPC, which are diol compounds, and 0.045 parts by mass of sodium dithionite, 96.74 parts by mass of dichloromethane were added. While stirring, 9.84 parts by mass of phosgene was blown in at 16 - 24 °C over 70 minutes. Then, a solution formed by dissolving 6.07 parts by mass of 25% aqueous sodium hydroxide solution and 0.341 parts by mass of p-tert-butylphenol in 3.41 parts by mass of dichloromethane was added and stirred to form an emulsified state. While stirring as described above, 0.019 parts by mass of triethylamine was added when the reaction solution was at 28 °C, and stirring was continued at 26 - 31 °C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into 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 flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 1.

[0293] [Example A - 5]

[0294] 110.92 parts by mass of ion-exchanged water, 33.96 parts by mass of 25% aqueous sodium hydroxide solution were added to a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 6.17 parts by mass of BNF, 7.01 parts by mass of BPC, 6.24 parts by mass of BPA, which are diol compounds, and 0.039 parts by mass of sodium dithionite, 87.30 parts by mass of dichloromethane was added, and 8.88 parts by mass of phosgene was blown in with stirring at 16 - 24 °C for 70 minutes. Then, a solution formed by dissolving 5.48 parts by mass of 25% aqueous sodium hydroxide solution and 0.308 parts by mass of p-tert-butylphenol in 3.08 parts by mass of dichloromethane was added and stirred to form an emulsified state. Under the above stirring, 0.017 parts by mass of triethylamine was added in a state where the reaction solution was at 28 °C, and stirring was continued at a temperature of 26 - 31 °C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into 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 flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 1.

[0295] [Example A - 6]

[0296] 120.67 parts by mass of ion-exchanged water, 36.94 parts by mass of 25% aqueous sodium hydroxide solution were added to a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 3.36 parts by mass of BNF, 17.16 parts by mass of BPC, which are diol compounds, and 0.041 parts by mass of sodium dithionite, 94.67 parts by mass of dichloromethane were added. While stirring, 9.66 parts by mass of phosgene was blown in at 16 - 24 °C over 70 minutes. Then, a solution formed by dissolving 36.94 parts by mass of 25% aqueous sodium hydroxide solution and 0.335 parts by mass of p-tert-butylphenol in 3.35 parts by mass of dichloromethane was added and stirred to form an emulsified state. While stirring, 0.019 parts by mass of triethylamine was added when the reaction solution was at 28 °C, and stirring was continued at 26 - 31 °C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into 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 flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 1.

[0297] [Comparative Example A - 1]

[0298] To a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 304.13 parts by mass of ion-exchanged water and 149.65 parts by mass of a 25% aqueous sodium hydroxide solution were added. After dissolving 3.36 parts by mass of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 69.61 parts by mass of BPC, and 0.162 parts by mass of sodium dithionite, 384.69 parts by mass of dichloromethane were added. While stirring, 39.13 parts by mass of phosgene were blown in at 16 - 24°C over 70 minutes. Then, a solution formed by dissolving 42.23 parts by mass of a 25% aqueous sodium hydroxide solution and 1.358 parts by mass of p-tert-butylphenol in 13.58 parts by mass of dichloromethane was added and stirred to form an emulsified state. While stirring, 0.076 parts by mass of triethylamine were added in a state where the reaction solution was at 28°C, and stirring was continued at a temperature of 26 - 31°C for 1 hour to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, to obtain a dichloromethane solution of polycarbonate. Next, the obtained dichloromethane solution was dropped into 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 flaky polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 2.

[0299] [Reference Example A-1] Synthesis of 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene (BCHP-FL)

[0300] Into a flask equipped with a stirrer, a cooler, a Dean-Stark tube, and a thermometer, 15.00 g of fluorenone, 30.81 g of 2-cyclohexylphenol, 1.42 g of phosphotungstic acid, 0.49 g of octanethiol, and 100 ml of toluene were charged, and the reaction was carried out at 100°C and 50 kPa for 11 hours. After the reaction, it was diluted with 300 ml of toluene, and then subjected to liquid-liquid separation washing with distilled water 5 times. The washed organic layer was concentrated, and when 400 ml of acetone was added to the concentrated residue, white crystals of 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene (BCHP-FL) precipitated. The crystals were recovered by filtration and dried under reduced pressure at 70°C for 4 hours to obtain 29.9 g of BCHP-FL (yield 70%).

[0301] [Comparative Example A-2]

[0302] 80.81 parts by mass of ion-exchanged water, 35.91 parts by mass of 25% aqueous sodium hydroxide solution were added to a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 12.95 parts by mass of BPC as a diol compound, 2.91 parts by mass of BCHP-FL, and 0.032 parts by mass of sodium dithionite, 71.55 parts by mass of dichloromethane were added. While stirring, 7.50 parts by mass of phosgene were blown in at 16 - 24°C over 70 minutes. Then, a solution formed by dissolving 4.49 parts by mass of 25% aqueous sodium hydroxide solution and 0.253 parts by mass of p-tert-butylphenol in 2.53 parts by mass of dichloromethane, and 0.003 parts by mass of triethylamine were added and stirred to form an emulsified state. Under the above stirring, 0.014 parts by mass of triethylamine were added when the reaction solution was at 28°C, and stirring was continued at 26 - 31°C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into 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 white flaky polycarbonate. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 2.

[0303] [Comparative Example A-3]

[0304] 9.0 parts by mass of BNF, 35.08 parts by mass of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF, manufactured by Honshu Chemical Co., Ltd.), 21.64 parts by mass of diphenyl carbonate (DPC), and 0.167 parts by mass of an aqueous sodium hydrogen carbonate solution with a concentration of 60 mmol / L as a catalyst were added, and it was heated to 180°C in a nitrogen atmosphere to melt it. Then, the degree of vacuum was adjusted to 20 kPa over 5 minutes. The temperature was raised to 265°C at a heating rate of 60°C / hr, and after 70% of phenol had flowed out, the pressure was reduced at 40 kPa / hr, and the polymerization reaction was carried out until the specified power was reached. After the reaction ended, the resin was taken out from the flask. The properties of the obtained polycarbonate resin are shown in Table 2.

[0305] [Comparative Example A-4]

[0306] Add 43.85 parts by mass of BPEF, 16.23 parts by mass of DPC, and 0.083 parts by mass of an aqueous sodium bicarbonate solution with a concentration of 60 mmol / L as a catalyst, and heat it to 180 °C in a nitrogen atmosphere to melt it. Then, adjust the degree of vacuum to 20 kPa over 5 minutes. Raise the temperature to 240 °C at a heating rate of 60 °C / hr, and reduce the pressure at a rate of 40 kPa / hr after 70% of the phenol has flowed out, and carry out the polymerization reaction until the specified power is reached. After the reaction is completed, take out the resin from the flask. The properties of the obtained polycarbonate resin are shown in Table 2.

[0307] [Comparative Example A-5]

[0308] Add 10663 parts of ion-exchanged water and 6015 parts of a 25% aqueous sodium hydroxide solution to a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 2921 parts of BPC as a diol compound and 5.84 parts of sodium dithionite, add 12588 parts of dichloromethane, and blow 1500 parts of phosgene while stirring at 16 - 24 °C for 70 minutes. Then, add 911 parts of a 25% aqueous sodium hydroxide solution and 0.58 part of triethylamine, and add a solution formed by dissolving 51.26 parts of p-tert-butylphenol in 277 parts of dichloromethane, and stir to form an emulsified state. While stirring as described above, after adding 2.30 parts of triethylamine when the reaction solution is at 28 °C, continue stirring at a temperature of 26 - 31 °C for 1 hour to end the reaction. After the reaction is completed, separate the organic phase, dilute it with dichloromethane, and wash it repeatedly with ion-exchanged water. When the washing solution becomes neutral, wash it with hydrochloric acid acidic water. Then, wash it repeatedly with ion-exchanged water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, put it into a kneader filled with warm water, and evaporate the solvent while stirring to obtain a resin powder. After dehydration, dry it at 100 °C for 12 hours using a hot air circulation dryer to obtain a white powdery polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 2.

[0309] [Comparative Example A-6]

[0310] Add 14,876 parts of ion-exchanged water and 6,612 parts of 25% aqueous sodium hydroxide solution to a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 3,140 parts of BPA as a diol compound and 6.28 parts of sodium dithionite, add 14,050 parts of dichloromethane. While stirring, blow 1,500 parts of phosgene at 16 - 24 °C for 70 minutes. Then, add 1,102 parts of 25% aqueous sodium hydroxide solution, further add a solution formed by dissolving 88.84 parts of p-tert-butylphenol in 251 parts of dichloromethane, and stir to form an emulsified state. While stirring, add 2.78 parts of triethylamine when the reaction solution is at 28 °C, and continue stirring at 26 - 31 °C for 1 hour to end the reaction. After the reaction ends, separate the organic phase, dilute it with dichloromethane, wash it repeatedly with ion-exchanged water, and wash it with acidic hydrochloric acid water when the washing solution becomes neutral. Then, wash it repeatedly with ion-exchanged water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, put it into a kneader filled with warm water, and evaporate the solvent while stirring to obtain a powder of polycarbonate resin. After dehydration, dry it at 100 °C for 12 hours using a hot air circulation dryer to obtain a white powdery polycarbonate resin. Using the obtained polycarbonate resin, various evaluations were carried out by the above method, and the results are shown in Table 2.

[0311]

[0312]

[0313] (Method 1 - B)

[0314] (1) Composition ratio

[0315] Use proton NMR of JNM-AL400 manufactured by JEOL Ltd. to measure each repeating unit and calculate the composition ratio (mol%) of the polycarbonate resin.

[0316] (2) Viscosity-average molecular weight

[0317] Use an Ostwald viscometer to obtain the specific viscosity (η SP ) calculated by the following formula from a solution formed by dissolving 0.7 g of the sample in 100 ml of dichloromethane at 20 °C,

[0318] Specific viscosity (η SP ) = (t - t 0 ) / t 0

[0319] [t 0 is the falling second number of dichloromethane, and t is the falling second number of the sample solution]

[0320] From the obtained specific viscosity (η SP) Calculate the viscosity-average molecular weight Mv according to the following mathematical formula.

[0321] η SP / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0322] [η] = 1.23×10 -4 Mv 0.83

[0323] c = 0.7

[0324] (3) Glass transition temperature (Tg)

[0325] Use a DSC 2910 type manufactured by TA Instruments Japan Co., Ltd. to heat approximately 10 mg of the sample at a heating rate of 20 °C / min for measurement.

[0326] (4) Saturated water absorption

[0327] According to JIS K7209:2000, after dissolving 3 g of the sample in dichloromethane, use the cast film obtained by evaporating dichloromethane. After drying at 50 °C for 24 hours, measure the weight after immersion in water at 25 °C, and calculate the water absorption using the following formula.

[0328] Water absorption (%) = {(weight of the resin after water absorption - weight of the resin before water absorption) / weight of the resin before water absorption} × 100

[0329] Measure the water absorption over time, and take the water absorption at the equilibrium value as the saturated water absorption.

[0330] (5) Coefficient of linear expansion

[0331] After dissolving 3 g of the sample in dichloromethane, use the cast film obtained by evaporating dichloromethane. Use a thermomechanical analyzer (SS6100 manufactured by SII Nano Technology Co., Ltd.) to measure the sample with a length of 4 mm and a width of 20 mm three times at a heating rate of 10 °C / min and a cooling rate of 50 °C / min, calculate the coefficient of linear expansion in the temperature range of 50 - 90 °C, and find the average value.

[0332] (6) Spectral transmittance

[0333] The powder of polycarbonate resin was melt-kneaded at a temperature of 350 to 450 °C using a twin-screw extruder (OMEGA30H manufactured by STEER Co., Ltd.) to obtain pellets. After drying the pellets at 140 °C for 5 to 10 hours, they were molded at 350 to 450 °C using an injection molding machine (FNX140 manufactured by Nissei Plastic Industrial Co., Ltd.) to obtain a molded product (thickness 1 mm). Using a UV-visible-infrared spectrophotometer (V-770DS manufactured by JASCO Corporation), the spectral transmittance in the wavelength range of 250 to 2500 nm was measured at the 1-mm-thick portion of the molded product.

[0334] (7) Reflow soldering resistance

[0335] The obtained molded product (thickness 1 mm) was placed in a humidity chamber at 60 °C / 60% RH (relative humidity), exposed for 120 hours for humidity conditioning, and then placed in an oven. After heating according to the temperature profile of IPC / JEDEC J-STD-020C (peak temperature 240 °C or 260 °C), the appearance was observed and the reflow soldering resistance was judged based on the following criteria.

[0336] No change was observed in the transparency and shape of the molded product: "〇"

[0337] A change was observed in the transparency or shape of the molded product: "×"

[0338] [Example B-1]

[0339] Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 19,176 parts by weight of ion-exchanged water and 7,575 parts by weight of a 25% aqueous sodium hydroxide solution were added. After dissolving 4,533 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 2,017 parts by weight of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisP-HTG, manufactured by Honshu Chemical Co., Ltd.), and 10.16 parts by weight of sodium dithionite, 30,184 parts by weight of dichloromethane were added. While stirring, 1,500 parts by weight of phosgene was blown in at 16 - 24°C over 80 minutes. Then, a solution formed by dissolving 947 parts by weight of a 25% aqueous sodium hydroxide solution and 53.27 parts by weight of p-tert-butylphenol in 530 parts by weight of dichloromethane was added and stirred to form an emulsified state. While stirring as described above, 2.99 parts by weight of triethylamine was added in a state where the reaction solution was at 28°C, and stirring was continued at 26 - 31°C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, obtaining a dichloromethane solution of polycarbonate. Next, the obtained dichloromethane solution was dropped into warm water maintained at 80°C, and the solvent was evaporated to obtain a powdery solid. The obtained solid was dried at 120°C for 24 hours to obtain a white powdery polycarbonate resin. The obtained powder was used to evaluate the composition ratio, viscosity-average molecular weight, glass transition temperature, saturated water absorption, and linear expansion coefficient. The evaluation results are shown in Table 3.

[0340] The powder of the polycarbonate resin was melt-kneaded with a cylinder and a mold at a temperature of 350 - 420°C using a twin-screw extruder (OMEGA30H manufactured by STEER Co., Ltd.) to obtain pellets. After drying the pellets at 140°C for 10 hours, molding was performed at a cylinder temperature of 350 - 450°C using an injection molding machine (FNX140 manufactured by Nissei Plastic Industrial Co., Ltd.) to obtain a molded product (thickness 1 mm). The obtained molded product was used to evaluate the spectral transmittance and reflow soldering resistance. The evaluation results are shown in Table 3.

[0341] [Example B-2]

[0342] Except that BNF as a diol compound was 3,466 parts by weight and BisP-HTG was 1,286 parts by weight, exactly the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0343] [Example B-3]

[0344] Except that the amounts of BNF as a diol compound were 2666 parts by weight, BisP-HTG was 1837 parts by weight, and p-tert-butylphenol was 79.90 parts by weight, the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0345] [Example B-4]

[0346] Except that the amount of BNF as a diol compound was 4533 parts by weight and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimide (PPPBP, manufactured by Sakai Kogyo Co., Ltd.) was 697 parts by weight, the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0347] [Example B-5]

[0348] Except that the amount of BNF as a diol compound was 2666 parts by weight, PPPBP was 697 parts by weight, and Bis P-HTG was 1284 parts by weight, the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0349] [Example B-6]

[0350] Except that the amount of BNF as a diol compound was 4266 parts by weight and 2,2-bis(4-hydroxyphenyl)propane (BPA, manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) was 535 parts by weight, the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0351] [Example B-7]

[0352] Except that the amount of BNF as a diol compound was 3733 parts by weight and BPA was 802 parts by weight, the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0353] [Example B-8]

[0354] Except that the amount of BNF as a diol compound was 266 parts by weight and BisP-HTG was 3490 parts by weight, the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0355] [Comparative Example B-1]

[0356] Except that the amount of BisP-HTG as a diol compound was 3674 parts by weight, the same operations as in Example B-1 were carried out. The evaluation results are shown in Table 3.

[0357] [Comparative Example B-2]

[0358] Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 12,784 parts by weight of ion-exchanged water and 6,628 parts by weight of a 25% aqueous sodium hydroxide solution were added. After dissolving 1,738 parts by weight of BPA, 1,286 parts by weight of BisP-HTG, and 6.05 parts by weight of sodium dithionite as diol compounds, 15,092 parts by weight of dichloromethane were added. While stirring, 1,500 parts by weight of phosgene were blown in at 16 - 24°C over 80 minutes. Then, a solution formed by dissolving 947 parts by weight of a 25% aqueous sodium hydroxide solution and 53.27 parts by weight of p-tert-butylphenol in 530 parts by weight of dichloromethane was added and stirred to form an emulsified state. While stirring as described above, 2.99 parts by weight of triethylamine were added in a state where the reaction solution was at 28°C, and stirring was continued at 26 - 31°C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into warm water maintained at 80°C, and the solvent was evaporated to obtain a powdery solid. The obtained solid was dried at 120°C for 24 hours to obtain a white powdery polycarbonate resin. The obtained powder was used to evaluate the composition ratio, viscosity-average molecular weight, glass transition temperature, saturated water absorption rate, and linear expansion coefficient. The evaluation results are shown in Table 3.

[0359] Using an exhaust-type twin-screw extruder [KZW15 - 25MG manufactured by Technovel Corporation], the powder of the polycarbonate resin was melt-kneaded together with a cylinder and a mold at 320°C to obtain pellets. A part of the obtained pellets was dried at 120°C for 12 hours or more, and then, using an injection molding machine (J - 75E3 manufactured by Japan Steel Works, Ltd.), a molded product (thickness 1 mm) was obtained under the conditions of a cylinder temperature of 320°C and a mold temperature of 100°C. The obtained molded product was used to evaluate the spectral transmittance and reflow soldering resistance. The evaluation results are shown in Table 3.

[0360] [Comparative Example B - 3]

[0361] Except that 2,140 parts by weight of BPA and 939 parts by weight of PPPBP were used as diol compounds, the same operations as in Comparative Example B - 2 were performed to obtain a powder of polycarbonate resin. The obtained powder was used to evaluate the composition ratio, viscosity-average molecular weight, glass transition temperature, saturated water absorption rate, and linear expansion coefficient. The evaluation results are shown in Table 3.

[0362] Using an exhaust-type twin-screw extruder [KZW15-25MG manufactured by Technovel Corporation], the powder of polycarbonate resin was melt-kneaded together with a cylinder and a mold at 320 °C to obtain pellets. A part of the obtained pellets was dried at 120 °C for 12 hours or more, and then a molded product (thickness 1 mm) was obtained using an injection molding machine (J-75E3 manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 320 °C and a mold temperature of 100 °C. The spectral transmittance and reflow soldering resistance of the molded product were evaluated. The evaluation results are shown in Table 3.

[0363] [Comparative Example B-4]

[0364] Except that 2675 parts by weight of BPA as a diol compound and 23.08 parts by weight of p-tert-butylphenol were used, the same operations as in Comparative Example B-2 were carried out to obtain a powder of polycarbonate resin. The composition ratio, viscosity-average molecular weight, glass transition temperature, saturation water absorption, and linear expansion coefficient of the obtained powder were evaluated. The evaluation results are shown in Table 3.

[0365] Using an exhaust-type twin-screw extruder [KZW15-25MG manufactured by Technovel Corporation], the powder of polycarbonate resin was melt-kneaded together with a cylinder and a mold at 330 °C to obtain pellets. A part of the obtained pellets was dried at 120 °C for 12 hours or more, and then a molded product (thickness 1 mm) was obtained using an injection molding machine (J-75E3 manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 340 °C and a mold temperature of 120 °C. The spectral transmittance and reflow soldering resistance of the molded product were evaluated. The evaluation results are shown in Table 3.

[0366]

[0367] (Method 2)

[0368] (1) Composition ratio

[0369] The composition ratio (mol%) of the polycarbonate resin was calculated by measuring each repeating unit using a proton NMR of JNM-AL400 manufactured by JEOL Ltd.

[0370] (2) Viscosity-average molecular weight

[0371] Using an Ostwald viscometer, the specific viscosity (η SP ) calculated by the following formula was obtained from a solution formed by dissolving 0.7 g of the sample in 100 ml of dichloromethane at 20 °C.

[0372] Specific viscosity (η SP ) = (t - t 0 ) / t 0

[0373] [t 0 is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]

[0374] From the specific viscosity (η SP ), the viscosity-average molecular weight Mv is calculated according to the following mathematical formula.

[0375] η SP / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0376] [η] = 1.23×10 －4 Mv 0.83

[0377] c = 0.7

[0378] (3) Total light transmittance

[0379] After drying the resin particles at 120 °C for 12 hours, an injection molding machine (J-75E3 manufactured by Japan Steel Works, Ltd.) was used, and a three-stage resin plate with a length of 90 mm and thicknesses of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate side was molded at a cylinder temperature of 280 - 340 °C and a mold temperature of 90 - 120 °C. The 2-mm-thick part of the molded three-stage resin plate was measured using a turbidimeter 300A manufactured by Nippon Denshoku Industries Co., Ltd., and evaluated according to the following criteria.

[0380] "〇": Total light transmittance is 85% or more

[0381] "×": Total light transmittance is less than 85%

[0382] (4) Glass transition temperature (Tg)

[0383] Using a DSC 2910 manufactured by TA Instruments Japan, about 10 mg of the sample was heated at a heating rate of 20 °C / min for measurement.

[0384] (5) Heat deflection temperature

[0385] The heat deflection temperature under a load condition of 0.45 MPa was measured according to ISO75.

[0386] (6) Indentation hardness

[0387] Using the 2-mm-thick part of the three-stage resin plate, according to ISO / TS19278, a dynamic ultra-micro hardness tester (Shimadzu Corporation, model DUH-210S) was used to measure the relationship between the load on the surface of the plate and the indentation depth in real time, and the indentation hardness (N / mm2 )。

[0388] (Measurement conditions)

[0389] Indentation indenter: Berkovich indenter (made of diamond)

[0390] Test force: 500 mN

[0391] Minimum test force: 4.9 mN

[0392] Loading / unloading time: 30 sec

[0393] Load holding time: 40 sec

[0394] Unloading holding time: 0 sec

[0395] Number of tests: 5

[0396] (Indentation hardness calculation method)

[0397] The indentation hardness (Hit) measures the resistance to semi-permanent deformation or damage. The indentation hardness is calculated using the following formula.

[0398] Hit = F max / A p

[0399] F max : Maximum test force

[0400] A p : Projected area where the indenter contacts the test piece

[0401] A p = 23.96 × h c 2 (For a triangular pyramid indenter (115°))

[0402] h c = h max - ε(h max - h r )

[0403] ε = 3 / 4 (for a triangular pyramid)

[0404] h r : Intercept of the tangent to the unloading curve of the F of the test force-depth curve with the depth axis (7) Pencil hardness max Using the 2 mm thick part of a three-segment resin plate formed, according to JIS K5600, in a constant temperature room at an ambient temperature of 23°C, draw a line while holding the pencil at an angle of 45 degrees and applying a load of 750 g to the surface of the resin plate, and evaluate the surface condition by visual observation.

[0405] ​

[0406] Load: 750 g

[0407] Measurement speed: 50 mm / min

[0408] Measurement distance: 7 mm

[0409] Pencil: Hi-uni made by Mitsubishi Pencil

[0410] (8) Notched Charpy impact value

[0411] After drying the particles of the polycarbonate resin composition at 90 - 120 °C for 12 hours, a flexural test piece was molded using JSW J-75EIII manufactured by Japan Steel Works, Ltd. at a cylinder temperature of 230 - 350 °C and a mold temperature of 80 - 120 °C. The notched Charpy impact test was measured according to ISO179.

[0412] (9) Resistance to falling weight test: DuPont impact test

[0413] The DuPont impact deformation test was carried out on the 2 mm thick part of the molded three-section resin plate. Using a DuPont impact deformation tester, with an impact die (radius 6.35 mm) and a receiving die (inner diameter 15.2 mm, outer diameter 25.0 mm), a 2 mm thick resin plate was placed between the receiving die and the impact die, and the failure state when a 1 kg drop hammer was dropped from a height of 1 m was observed visually and evaluated according to the following criteria.

[0414] “〇”: The molded product was not damaged, and no cracks or fractures occurred.

[0415] “×”: The molded product was damaged. Or cracks or fractures occurred on the molded product.

[0416] [Copolymer polycarbonate resin (Component A)]

[0417] Resin - 1: Copolymerization composition BNF / BPC = 38 / 62 mol%, viscosity-average molecular weight = 17200, glass transition temperature = 180 °C.

[0418] Resin - 2: Copolymerization composition BNF / OCZ = 38 / 62 mol%, viscosity-average molecular weight = 17300, glass transition temperature = 192 °C.

[0419] Resin - 3: Copolymerization composition BNF / BPC = 50 / 50 mol%, viscosity-average molecular weight = 17200, glass transition temperature = 205 °C.

[0420] Resin - 4: Copolymerization composition BNF / BPC = 20 / 80 mol%, viscosity-average molecular weight = 17200, glass transition temperature = 155 °C.

[0421] Resin - 5: Copolymer composition BNF / BPC = 10 / 90 mol%, viscosity-average molecular weight = 17,100, glass transition temperature = 137 °C.

[0422] [Aromatic polycarbonate resin (Component B)]

[0423] Resin - 7: PANLITE L - 1250 manufactured by Teijin Limited (composition bisphenol A 100 mol%, viscosity-average molecular weight = 24,000)

[0424] Resin - 8: PANLITE K - 1300 manufactured by Teijin Limited (composition bisphenol A 100 mol%, viscosity-average molecular weight = 30,000)

[0425] [Other resins]

[0426] Resin - 9: ACRYPET VH - 001 manufactured by Mitsubishi Chemical Corporation

[0427] [Example C - 1]

[0428] <Manufacture of copolycarbonate resin (Component A)>

[0429] Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 19,636 parts by weight of ion-exchanged water and 6,012 parts by weight of a 25% aqueous sodium hydroxide solution were added. After dissolving 1,911 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 2,017 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC, manufactured by Honshu Chemical Co., Ltd.), and 7.86 parts by weight of sodium dithionite, 15,455 parts by weight of dichloromethane were added. While stirring, 1,500 parts by weight of phosgene was blown in at 16 - 24 °C over 80 minutes. Then, a solution formed by dissolving 970 parts by weight of a 25% aqueous sodium hydroxide solution and 61.82 parts by weight of p-tert-butylphenol in 618 parts by weight of dichloromethane was added and stirred to form an emulsified state. While stirring, 3.06 parts by weight of triethylamine was added at a state where the reaction solution was at 28 °C, and stirring was continued at a temperature of 26 - 31 °C for 1 hour to end the reaction. After the reaction ended, the organic phase was separated, diluted with dichloromethane, washed repeatedly with ion-exchanged water, and hydrochloric acid was added when the washing solution became neutral. Then, it was washed repeatedly with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a dichloromethane solution of polycarbonate was obtained. Next, the obtained dichloromethane solution was dropped into warm water maintained at 50 - 80 °C, and the solvent was evaporated to obtain a powdery solid. The obtained solid was dried at 120 °C for 24 hours to obtain a white powdery copolycarbonate resin (Resin - 1).

[0430] <Manufacture of Polycarbonate Resin Composition>

[0431] Resin-1 (Component A) and Resin-7 (Component B) were mixed at a mixing weight ratio of 90:10, and then melt-kneaded at 320 °C using an exhaust-type twin-screw extruder [KZW15-25MG manufactured by Technovel Corporation] together with a cylinder and a die to obtain mixed pellets of a copolycarbonate resin and an aromatic polycarbonate resin. A part of the obtained pellets was dried at 120 °C for 12 hours or more, and then molded into test pieces for various evaluations using an injection molding machine (J-75E3 manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 320 °C and a mold temperature of 100 °C. The evaluation results are shown in Table 4. It should be noted that the glass transition temperature of the obtained mixed pellets is single.

[0432] [Example C-2]

[0433] <Manufacture of Polycarbonate Resin Composition>

[0434] Except that the mixing weight ratio was Resin-1 / Resin-7 = 80:20, the same operations as in Example C-1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the glass transition temperature of the obtained mixed pellets is single.

[0435] [Example C-3]

[0436] <Manufacture of Polycarbonate Resin Composition>

[0437] Except that Resin-8 was used as the aromatic polycarbonate resin (Component B) instead of Resin-7 and the mixing weight ratio was Resin-1 / Resin-8 = 70:30, the same operations as in Example C-1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the glass transition temperature of the obtained mixed pellets is single.

[0438] [Example C-4]

[0439] <Manufacture of Polycarbonate Resin Composition>

[0440] Except that the mixing weight ratio was Resin-1 / Resin-7 = 70:30, the same operations as in Example C-1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the glass transition temperature of the obtained mixed pellets is single.

[0441] [Example C-5]

[0442] <Manufacture of Polycarbonate Resin Composition>

[0443] Except that the mixing weight ratio was resin - 1 / resin - 7 = 60:40, the same operations as in Example C - 1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the obtained mixed particles had a single glass transition temperature.

[0444] [Example C - 6]

[0445] <Manufacture of polycarbonate resin composition>

[0446] Except that the mixing weight ratio was resin - 1 / resin - 7 = 50:50, the same operations as in Example C - 1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the obtained mixed particles had a single glass transition temperature.

[0447] [Example C - 7]

[0448] <Manufacture of polycarbonate resin composition>

[0449] Except that the mixing weight ratio was resin - 1 / resin - 7 = 10:90, the same operations as in Example C - 1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the obtained mixed particles had a single glass transition temperature.

[0450] [Example C - 8]

[0451] <Manufacture of copolycarbonate resin (Component A)>

[0452] Except that 9,9 - bis(6 - hydroxy - 2 - naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound was 1911 parts by weight, 1,1 - bis(4 - hydroxy - 3 - methylphenyl)cyclohexane (OCZ, manufactured by Honshu Chemical Co., Ltd.) was 2335 parts by weight, and sodium dithionite was 8.49 parts by weight, the same operations as in Example C - 1 were carried out to obtain a white powdery copolycarbonate resin (resin - 2).

[0453] <Manufacture of polycarbonate resin composition>

[0454] Except that the mixing weight ratio was resin - 2 / resin - 7 = 50:50, the same operations as in Example C - 1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the obtained mixed particles had a single glass transition temperature.

[0455] [Example C - 9]

[0456] <Manufacture of copolycarbonate resin (Component A)>

[0457] Except that 2730 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 1551 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC, manufactured by Honshu Chemical Co., Ltd.), and 8.56 parts by weight of sodium dithionite were used, the same operations as in Example C-1 were carried out to obtain a white powdery copolycarbonate resin (Resin-3).

[0458] <Manufacture of Polycarbonate Resin Composition>

[0459] Except that the mixing weight ratio was Resin-3 / Resin-7 = 50:50, the same operations as in Example C-1 were carried out and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the obtained mixed particles had a single glass transition temperature.

[0460] [Example C-10]

[0461] <Manufacture of Copolycarbonate Resin (Component A)>

[0462] Except that 1092 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 2482 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC, manufactured by Honshu Chemical Co., Ltd.), and 7.15 parts by weight of sodium dithionite were used, the same operations as in Example C-1 were carried out to obtain a white powdery copolycarbonate resin (Resin-4).

[0463] <Manufacture of Polycarbonate Resin Composition>

[0464] Except that the mixing weight ratio was Resin-4 / Resin-7 = 50:50, the same operations as in Example C-1 were carried out and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the obtained mixed particles had a single glass transition temperature.

[0465] [Example C-11]

[0466] <Manufacture of Copolycarbonate Resin (Component A)>

[0467] Except that 546 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF, manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 2792 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC, manufactured by Honshu Chemical Co., Ltd.), and 6.68 parts by weight of sodium dithionite were used, the same operations as in Example C-1 were carried out to obtain a white powdery copolycarbonate resin (Resin-5).

[0468] <Manufacture of polycarbonate resin composition>

[0469] Except that the mixing weight ratio was resin-5 / resin-7 = 50:50, the same operations as in Example C-1 were carried out, and the same evaluations were made. The evaluation results are shown in Table 4. It should be noted that the glass transition temperature of the obtained mixed particles was single.

[0470] [Comparative Example C-1]

[0471] The particles of resin-7 were dried at 120 °C for more than 12 hours, and then molded into various test pieces for evaluation using an injection molding machine (J-75E3 manufactured by Japan Steel Works) under the conditions of a cylinder temperature of 350 °C and a mold temperature of 120 °C. The evaluation results are shown in Table 4.

[0472] [Comparative Example C-2]

[0473] The particles of resin-9 were dried at 90 °C for more than 12 hours, and then molded into various test pieces for evaluation using an injection molding machine (J-75E3 manufactured by Japan Steel Works) under the conditions of a cylinder temperature of 230 °C and a mold temperature of 80 °C. The evaluation results are shown in Table 4.

[0474]

[0475] Industrial applicability

[0476] The polycarbonate resin of the present invention has excellent scratch resistance and heat resistance, so no coating treatment is required, and it can be used for various display devices such as indoor lighting lamp lenses, display instrument covers, instrument nameplates, various switch covers, display covers, heat control panels, instrument panels, central instrument clusters, central panels, in-vehicle lamp lenses, head-up displays, protection components, and light-transmitting components for automotive interior decoration. In addition, the polycarbonate resin of the present invention has small dimensional changes due to heat and water absorption, and excellent light transmittance and heat resistance, so it can be used for optical components such as connectors and lenses used in high-temperature environments, and electrical and electronic components such as switches, plugs, sensor housings, and flexible films.

Claims

1. A polycarbonate resin comprising a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2), wherein the proportion of the repeating unit (A) represented by the formula (1) is 1 to 99 mol% relative to the total repeating units of the polycarbonate resin. In the formula (1), ring Z represents a fused polycyclic aromatic hydrocarbon ring, R 1 and R 2 each independently represents at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, In the formula (2), R 3 and R 4 each independently represents at least one group selected from 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 aralkoxy 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 them respectively, they may be the same or different. e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the groups represented by the following formula (3). In the formula (3), R 5 and R 6 and R 7 and R 8 and R 9 and R 10 and R 11 and R 12 each independently represents at least one group selected from 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. When there are a plurality of them, they may be the same or different. R 13 and R 14 each independently represents at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. R 15 and R 16 and R 17 and R 18 each independently represents at least one group selected from 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. When there are a plurality of them, they may be the same or different. c is an integer from 1 to 10, d is an integer from 4 to 7, h and i are integers from 1 to 3, and g is an integer from 1 to 100.

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

3. The polycarbonate resin according to claim 1, wherein the content ratio of the repeating unit (B) is in the range of 1 to 99 mol% relative to the total repeating units.

4. The polycarbonate resin according to claim 1, wherein W in the formula (2) contains at least one group selected from the groups represented by the following formula (4). In the formula (4), R 29 , R 30 , R 31 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and when there are a plurality of them respectively, they may be the same or different, and k is an integer of 1 to 3.

5. The polycarbonate resin according to claim 1, wherein the repeating unit (B) represented by the formula (2) contains a repeating unit derived from at least one compound selected from 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimididine.

6. The polycarbonate resin according to claim 1, wherein the glass transition temperature is 125 to 310 °C.

7. The polycarbonate resin according to claim 1, wherein The indentation hardness measured according to ISO / TS 19278 is 235 to 450 (N / mm 2 ).

8. The polycarbonate resin according to claim 1, wherein the pencil hardness measured according to JIS K5600 is 2H or more.

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

10. The polycarbonate resin according to claim 1, wherein the saturated water absorption rate is 0.5% or less.

11. The polycarbonate resin according to claim 1, wherein the linear expansion coefficient is 30 to 60 ppm / °C.

12. A molded article composed of the polycarbonate resin according to any one of claims 1 to 11.

13. The molded article according to claim 12, wherein the molded article is an automotive interior trim part.

14. The molded article according to claim 12, wherein the molded article is an optical molded article.

15. The molded article according to claim 14, wherein the spectral transmittance is 85% or more at wavelengths of 850 nm, 1310 nm, and 1550 nm, 82% or more at a wavelength of 1610 nm, and 78% or more at a wavelength of 1625 nm.

16. A polycarbonate resin composition containing 1 to 99 parts by weight of a copolymerized polycarbonate resin (component A) and 99 to 1 part by weight of an aromatic polycarbonate resin (component B). In the copolymerized polycarbonate resin, the content ratio of the repeating unit (a) represented by the following formula (1) is 5 to 95 mol%, and the content ratio of the repeating unit (b) represented by the following formula (2) is 95 to 5 mol%. In the formula (1), ring Z represents a fused polycyclic aromatic hydrocarbon ring, R 1 and R 2 each independently represents at least one group selected from 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 aralkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, In the formula (2), R 3 and R 4 each independently represents at least one group selected from 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 aralkoxy 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 them respectively, they may be the same or different. e and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the groups represented by the following formula (3). 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 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. When there are a plurality of them, they may be the same or different. R 13 and R 14 each independently represents at least one group selected from 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 aralkoxy 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 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. When there are a plurality of them, they may be the same or different. c is an integer from 1 to 10, d is an integer from 4 to 7, h and i are integers from 1 to 3, and g is an integer from 1 to 100.

17. The polycarbonate resin composition according to claim 16, wherein The aromatic polycarbonate resin (Component B) is an aromatic polycarbonate resin containing repeating units derived from bisphenol A.

18. The polycarbonate resin composition according to claim 16, wherein, the glass transition temperature is single.

19. A molded article comprising the polycarbonate resin according to any one of claims 16 to 18.

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