Optical molded article comprising polycarbonate resin

Abstract

To provide an optical molded article comprising a polycarbonate resin that is excellent in heat resistance, dimensional stability, low water absorption property, and light transmitting property.SOLUTION: There is provided an optical molded article comprising a polycarbonate resin that contains a repeating unit A expressed by the following formula (1) and a repeating unit B having a bisphenol structure, wherein the polycarbonate resin in which the ratio of the repeating unit A represented by formula 1 is in the range of 99 to 1 mol% and the content ratio of the repeating unit B is in the range of 1 to 99 mol% based on all repeating units of the polycarbonate resin. (In the formula, ring Z represents a naphthalene ring, and R1 and R2 each independently represent at least one group selected from the group consisting of H, halogen, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an optical molded article made of a polycarbonate resin having excellent heat resistance, dimensional stability, low water absorbency, and optical transparency. [Background technology]

[0002] Optical fiber technology is widely used for high-speed data communication over long and short distances. The optical connectors or transceivers used here function as converters between optical and electrical signals, and these optical components, especially lenses and waveguides, are made of resins with high glass transition temperatures such as polyetherimide. Because they are exposed to high temperatures during the solder reflow process, they are required to maintain their shape at temperatures above 240°C. They are also required to have high optical transparency, low water absorption, and dimensional stability in the range of 600nm to 1700nm, which is the communication wavelength range for optical communication.

[0003] Patent Document 1 describes a method of producing polycarbonates or copolycarbonates with 2,2-bis(4-hydroxy-3-methylphenyl)fluorene as a repeating unit, and proposes that this is effective in achieving high pencil hardness and high heat resistance. However, it has a problem in that it is not possible to satisfy all of the following: heat resistance, dimensional stability, low water absorption, and high light transmittance.

[0004] Therefore, there is a demand for optical molded articles containing polymers that are excellent in heat resistance, high light transmittance in the wavelength range of 600 nm to 1700 nm, low water absorbency, and dimensional stability. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 073508 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide an optical molded article made of a polycarbonate resin having excellent heat resistance, dimensional stability, low water absorbency and optical transparency. [Means for solving the problem]

[0007] As a result of intensive research conducted by the present inventors in order to achieve this object, they discovered that an optical molded article made of a polycarbonate resin having a specific structure can solve the above problems, and arrived at the present invention. That is, the present invention is as follows:

[0008] 1. An optical molded article made of 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), wherein the proportion of the repeating unit (A) represented by formula (1) is 99 to 1 mol % based on all repeating units of the polycarbonate resin, and the content of the repeating unit (B) is in the range of 1 to 99 mol % based on all repeating units.

[0009] [ka]

[0010] (In the above formula (1), ring Z is a naphthalene ring, R 1 and R 2 each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0011] [ka]

[0012] (In the above formula (2), R 3 and R 4 each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each of these groups, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of groups represented by the following formula (3):

[0013] [ka]

[0014] (In the above formula (3), R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 ,R 11 and R 12 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different; R 13 and R 14each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; R 15 ,R 16 ,R 17 and R 18 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, h and i are integers of 1 to 3, and g is an integer of 1 to 100.

[0015] 2. An optical molded article made of the polycarbonate resin according to the above item 1, wherein the repeating unit (B) represented by formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine. 3. An optical molded article made of the polycarbonate resin described in the above item 1 or 2, which has a saturated water absorption rate of 0.5% or less. 4. An optical molded article made of the polycarbonate resin according to any one of items 1 to 3 above, which has a glass transition temperature of 220 to 310°C. 5. An optical molded article made of the polycarbonate resin according to any one of items 1 to 4 above, which has a linear expansion coefficient of 30 to 60 ppm / °C. 6. An optical molded article made of a polycarbonate resin according to any one of items 1 to 5 above, having a spectral light transmittance of 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. Effect of the Invention

[0016] The optical molded article made of the polycarbonate resin of the present invention has excellent heat resistance, dimensional stability, low water absorption, and optical transparency, and is therefore suitable for use as an optical molded article for optical components that require solder reflow resistance, such as optical connectors or transceivers, etc. Therefore, the industrial effects achieved by the optical molded article are exceptional. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] <Polycarbonate resin> The polycarbonate resin in the present invention is a polycarbonate resin containing a repeating unit (A) represented by the following formula (1) and a repeating unit (B) represented by the following formula (2).

[0018] [ka]

[0019] (In the above formula (1), ring Z is a naphthalene ring, R 1 and R 2 each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0020] [ka]

[0021] (In the above formula (2), R 3 and R 4 each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each of these groups, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of groups represented by the following formula (3):

[0022] [ka]

[0023] (In the above formula (3), R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 ,R 11 and R 12 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different; R 13 and R 14each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; R 15 ,R 16 ,R 17 and R 18 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, h and i are integers of 1 to 3, and g is an integer of 1 to 100.

[0024] In the formula (1), ring Z is a naphthalene ring. The two rings Z connected to the carbon atom at position 9 of the fluorene ring may be different from each other, but are usually the same in most cases.

[0025] The substitution position of ring Z relative to the 9-position of the fluorene ring is not particularly limited. For example, the substitution may be at either the 1-position or the 2-position of the naphthalene ring relative to the 9-position of the fluorene ring, and substitution at the 2-position is preferred.

[0026] The substitution positions of the oxygen atom (-O-) and the ester bond [-OC(=O)-] which form a carbonate bond for linking the 9,9-bis-fused polycyclic arylfluorene skeleton are not particularly limited as long as they are positions other than the bonding position between the ring Z and the fluorene ring, and usually, they are substituted at any of the 5- to 8-positions of a naphthyl group bonded at the 1- or 2-position to the 9-position of the fluorene ring, and the 1- or 2-position of the naphthalene ring is substituted with respect to the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and with respect to this substitution position, substitution at the 1,5-positions or 2,6-positions is preferred, and substitution at the 2,6-positions is more preferred.

[0027] In the formula (1), R 1 and R 2 each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0028] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0029] 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.

[0030] Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0031] 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.

[0032] Preferred examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyloxy group, etc. A cycloalkoxy group having 6 to 12 carbon atoms is preferred.

[0033] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkenyl group having 2 to 6 carbon atoms is preferred.

[0034] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

[0035] Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group and a naphthyloxy group.

[0036] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0037] Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group and a phenylethyloxy group. Among them, R 1 and R 2 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and particularly preferably a hydrogen atom.

[0038] The content of the repeating unit (A) is 1 to 99 mol %, preferably 5 to 95 mol %, and more preferably 10 to 90 mol %, based on the total repeating units of the polycarbonate resin. Within the above range, excellent heat resistance and dimensional stability are obtained, which is preferable.

[0039] In the formula (2), R 3 and R 4each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each of these groups, they may be the same or different.

[0040] Here, examples of the alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the cycloalkyl group having 6 to 20 carbon atoms, the cycloalkoxy group having 6 to 20 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the aryl group having 6 to 14 carbon atoms, the aryloxy group having 6 to 14 carbon atoms, the aralkyl group having 7 to 20 carbon atoms, and the aralkyloxy group having 7 to 20 carbon atoms include the same groups as described above.

[0041] In the formula (2), W is a single bond or at least one group selected from the group consisting of groups represented by the formula (3).

[0042] In the formula (3), R 5 ,R 6 ,R 7 ,R 8 ,R 9 ,R 10 ,R 11 and R 12 each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different.

[0043] Examples of the alkyl group having 1 to 18 carbon atoms, the aryl group having 6 to 14 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms include the same groups as those mentioned above.

[0044] In the formula (3), R 13 and R 14 each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group.

[0045] 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 described above.

[0046] In the formula (3), R 15 ,R 16 ,R 17 and R 18 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different.

[0047] 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.

[0048] In the formula (3), c is an integer of 1 to 10, preferably an integer of 1 to 4, and more preferably 1. d is an integer of 4 to 7, and preferably 5. h and i are integers of 1 to 3, and preferably 1. g is an integer of 1 to 100, preferably an integer of 10 to 90, and more preferably an integer of 20 to 80.

[0049] It is particularly preferred that the repeating unit (B) represented by the formula (2) contains a repeating unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as BPA), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as BisP-HTG), and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (hereinafter sometimes abbreviated as PPPBP).

[0050] The content of the repeating unit (B) is preferably 1 to 99 mol %, more preferably 5 to 95 mol %, and further preferably 10 to 90 mol %, based on the total repeating units of the polycarbonate resin. Within the above range, excellent heat resistance and dimensional stability are obtained, which is preferable.

[0051] The polycarbonate resin of the present invention may contain, in addition to the repeating units (A) and (B), repeating units derived from other dihydroxy compounds or other diol compounds, as described below, to the extent that the properties of the polycarbonate resin are not impaired. The repeating units (C) other than the repeating units (A) and (B) are preferably 30 mol % or less, more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 5 mol % or less, based on the total repeating units.

[0052] <Raw material for polycarbonate resin> The repeating unit (A) represented by the formula (1) is derived from a diol compound, specifically, 9,9-bis(6-hydroxy-2-naphthyl)fluorene or 9,9-bis(6-hydroxy-1-naphthyl)fluorene is preferable, and 9,9-bis(6-hydroxy-2-naphthyl)fluorene is more preferable. These diol compounds may be used alone or in combination of two or more.

[0053] The repeating unit (B) represented by the formula (2) is derived from a diol compound, and examples of such a repeating unit include 2,2-bis(4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 2,2-bis(4-hydroxy-3-ethylphenyl)propane; 2,2-bis(4-hydroxy-3-propylphenyl)propane; 2,2-bis(4-hydroxy-3-butylphenyl)propane; bis(4-hydroxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis (4-hydroxyphenyl)butane;2,2-bis(4-hydroxyphenyl)octane;2,2-bis(4-hydroxyphenyl)phenylmethane;2,2-bis(4-hydroxy-3-methylphenyl)phenylmethane;2,2-bis(4-hydroxy-1-methylphenyl)propane;Bis(4-hydroxyphenyl)naphthylmethane;1,1-bis(4-hydroxy-t-butylphenyl)propane;2,2-bis(4-hydroxy-3-bromophenyl)propane;2,2-bis(4-hydroxy-3,5-tetramethylphenyl)propane Bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxy-3-chlorophenyl)propane; 2,2-bis(4-hydroxy-3,5-tetrachlorophenyl)propane; 2,2-bis(4-hydroxy-3,5-tetrabromophenyl)propane, 4,4'-dihydroxyphenyl ether; 4,4'-dihydroxy-3,3'-dimethylphenyl ether and other dihydroxyaryl ethers, 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxy-3,3'- Dihydroxydiaryl sulfides such as dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone; dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene;Dihydroxydiarylfluorenes such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)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)phthalimidine, etc.;

[0054] Among these, 2,2-bis(4-hydroxyphenyl)propane, (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine are preferred. These diols may be used alone or in combination of two or more.

[0055] The polycarbonate resin in the present invention may be copolymerized with other dihydroxy compounds or diol compounds in addition to the repeating units (A) and (B) to the extent that the properties of the polycarbonate resin are not impaired.

[0056] Other dihydroxy compounds include hydroquinone, resorcinol, orcinol, 2,2-bis(4-hydroxyphenyl)norbornene, 1,3-bis(4-hydroxyphenyl)adamantane; 2,2-bis(4-hydroxyphenyl)adamantane; 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentaenebisphenoxyethanolfluorene, and the like.

[0057] Other diol compounds include isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, and cyclohex-1,4-ylenedimethanol. Examples of such cyclohexanedimethanol include 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).

[0058] <Production method of polycarbonate resin> The polycarbonate resin in the present invention is obtained by reacting the diol compound with the carbonate precursor. The reaction method may include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal terminator of a monohydric phenol is usually used.

[0059] The polycarbonate resin includes polyester carbonates copolymerized with aromatic or aliphatic (including alicyclic) difunctional carboxylic acids. The aliphatic difunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of the aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid. These carboxylic acids may be copolymerized to the extent that the purpose is not hindered. In addition, the polycarbonate resin may be copolymerized with a structural unit containing a polyorganosiloxane unit as necessary.

[0060] The polycarbonate resin can also be made into a branched polycarbonate by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary.

[0061] Suitable examples of trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The constituent units derived from such polyfunctional aromatic compounds preferably account for 0.03 to 1.5 mol %, more preferably 0.1 to 1.2 mol %, and particularly preferably 0.2 to 1.0 mol %, of a total of 100 mol %, including the constituent units from other diol components.

[0062] The branched structural unit may be derived not only from a polyfunctional aromatic compound, but also from a side reaction occurring during a polymerization reaction by a melt transesterification method without using a polyfunctional aromatic compound. 1 It can be calculated by H-NMR measurement.

[0063] In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine, is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. In addition, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction. In this case, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.

[0064] The transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by a method of heating and stirring a predetermined ratio of aromatic diol components with a carbonic acid diester under an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning of the reaction and distilling off the resulting alcohol or phenol. In order to promote the reaction, a catalyst usually used in transesterification reactions can also be used. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.

[0065] Monofunctional phenols that are commonly used as end terminators can be used. In particular, in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as end terminators to adjust molecular weight, and the obtained polycarbonate resin has excellent thermal stability compared to those that are not, since the ends are blocked by groups based on monofunctional phenols. Specific examples of the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long chain alkylphenol.

[0066] (Other Ingredients) The polycarbonate resin in the present invention may contain various additives to give various properties to the resin composition within a range that does not impair the object of the present invention. The additives may include a mold release agent, a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a heat shielding agent, a fluorescent dye (including a fluorescent brightener), a pigment, a light diffusing agent, a reinforcing filler, other resins, elastomers, etc.

[0067] The release agent is preferably one that is composed of 90% by weight or more of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include ester of monohydric alcohol and fatty acid, and partial or complete ester of polyhydric alcohol and fatty acid. Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Stearyl stearate is preferred. Examples of the partial or full ester of a polyhydric alcohol and a saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, and other full or partial esters of dipentaerythritol. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferred, and stearic acid monoglyceride and pentaerythritol tetrastearate are more preferred.

[0068] The amount of the release agent to be added is preferably in the range of 0.05 to 0.5 parts by weight, more preferably in the range of 0.1 to 0.4 parts by weight, and further preferably in the range of 0.12 to 0.3 parts by weight, relative to 100 parts by weight of the polycarbonate resin.

[0069] Examples of the heat stabilizer include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate stearyl, [1,1-biphenyl]-4,4-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], 3,9-bis(2,6-di-tert-butylphenyl)propionate, ... butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is preferred, and tris(2,4-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are more preferred.

[0070] The amount of the heat stabilizer to be added is preferably in the range of 0.001 to 0.5 parts by weight, more preferably in the range of 0.005 to 0.4 parts by weight, and further preferably in the range of 0.01 to 0.3 parts by weight, relative to 100 parts by weight of the polycarbonate resin.

[0071] (viscosity average molecular weight) The viscosity average molecular weight of the polycarbonate resin in the present invention is preferably in the range of 6,000 to 35,000, more preferably in the range of 8,000 to 30,000, still more preferably in the range of 10,000 to 28,000, particularly preferably in the range of 12,000 to 25,000, and most preferably in the range of 13,000 to 22,000. A value within the above range is preferred because of excellent scratch resistance, heat resistance, and moldability.

[0072] The viscosity average molecular weight of the polycarbonate resin in the present invention is calculated by first calculating the specific viscosity (η SP ) was measured at 20°C using an Ostwald viscometer from a solution of 0.7 g of resin in 100 ml of methylene chloride. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0073] (Glass transition temperature: Tg) The glass transition temperature (Tg) of the polycarbonate resin in the present invention is preferably in the range of 220 to 310°C, more preferably in the range of 230 to 307°C, even more preferably in the range of 240 to 305°C, and most preferably in the range of 250 to 300°C. If Tg is within the above range, the heat resistance, dimensional stability, and moldability are good, which is preferable. 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.

[0074] (Linear expansion coefficient) The linear expansion coefficient of the polycarbonate resin in the present invention is preferably in the range of 30 to 60 ppm / °C, more preferably 32 to 58 ppm / °C, even more preferably 34 to 56 ppm / °C, and most preferably 35 to 55 ppm / °C. If the linear expansion coefficient is within the above range, dimensional change due to heat is small, which is preferable. The linear expansion coefficient is measured three times using a thermomechanical analyzer (SS6100 manufactured by SII Nano Technology Co., Ltd.) with a sample of 4 mm width x 20 mm length at a heating rate of 10°C / min and a cooling rate of 50°C / min, and the linear expansion coefficient in the measurement temperature range of 50 to 90°C is calculated, and the average value is calculated.

[0075] (saturated water absorption rate) The saturated water absorption of the polycarbonate resin in the present invention is measured according to JIS K7209:2000 and is preferably 0.50% or less, more preferably 0.49% or less, and even more preferably 0.48% or less. If the saturated water absorption is within the above range, the dimensional change due to water absorption is small, which is preferable. The lower limit of the saturated water absorption is not particularly limited, but 0.1% or more is sufficient.

[0076] (spectral light transmittance) The spectral light transmittance at a thickness of 1 mm of the optical molded article using the polycarbonate resin of the present invention is preferably 85% or more at the measurement wavelengths of 850 nm, 1310 nm, and 1550 nm, 82% or more at the measurement wavelength of 1610 nm, and 78% or more at the measurement wavelength of 1625 nm. If the spectral light transmittance is within the above range, the attenuation of signals in optical communication is small, which is preferable.

[0077] (Solder reflow resistance) The optical parts were subjected to a solder reflow test temperature profile according to IPC / JEDEC J-STD-020C "Moisture / Reflow Sensitivity Classification of Non-Hermetically Sealed Solid-State Surface Mount Devices". The parts were conditioned in a humidity chamber at 60°C / 60% RH (relative humidity) for 120 hours, then placed in an oven and heated according to the IPC / JEDEC J-STD-020C temperature profile (peak temperature 240°C or 260°C). It is preferable that the part exhibit no change in transparency or shape at a peak temperature of 240°C, and more preferable that the part exhibit no change in transparency or shape at a peak temperature of 260°C.

[0078] (Molding method and optical molded product) As a method for molding the polycarbonate resin in the present invention, a general method for molding a polycarbonate resin can be used, such as injection molding, extrusion molding, compression molding, solution casting, etc. In particular, a method for molding a molded product by injection molding or a method for molding a sheet or film by extrusion molding is preferably used.

[0079] The polycarbonate resin of the present invention has excellent heat resistance, light transmittance, dimensional stability, and low water absorption, and can be used as various optical molded products. In particular, because of its excellent heat resistance, it can be suitably used as optical molded products for optical components such as optical connectors and transceivers that require solder reflow resistance.

[0080] Examples of optical molded products include various lenses such as sensor lenses, condenser lenses, collimator lenses, and lens arrays, mirrors, optical waveguides, and wide-angle diffusion elements. EXAMPLES

[0081] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The evaluation was performed according to the following methods.

[0082] (1) Composition ratio Each repeating unit was measured by proton NMR using JNM-AL400 manufactured by JEOL Ltd., and the composition ratio (mol %) of the polycarbonate resin was calculated.

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

[0084] (3) Glass transition temperature (Tg) The measurements were performed using a TA Instruments Japan Co., Ltd. Model 2910 DSC, with approximately 10 mg of sample heated at a heating rate of 20°C / min.

[0085] (4) Saturated water absorption rate In accordance with JIS K7209:2000, 3 g of a sample was dissolved in methylene chloride, and the methylene chloride was evaporated to obtain a cast film. The film was dried at 50°C for 24 hours and then immersed in water at 25°C. The weight was then measured and the water absorption rate was calculated using the following formula. Water absorption rate (%) = {(resin weight after water absorption - resin weight before water absorption) / resin weight before water absorption} x 100 The water absorption rate was measured over time, and the water absorption rate at which the equilibrium value was reached was determined as the saturated water absorption rate.

[0086] (5) Linear expansion coefficient After dissolving 3 g of sample in methylene chloride, the methylene chloride was evaporated to obtain a cast film. Using a thermomechanical analyzer (SS6100 manufactured by SII Nanotechnology), a sample with a length of 4 mm and a width of 20 mm was measured three times at a heating rate of 10°C / min and a cooling rate of 50°C / min to calculate the linear expansion coefficient in the measurement temperature range of 50 to 90°C and obtain the average value.

[0087] (6) Spectral light transmittance The polycarbonate resin powder was melt-kneaded at 350-450°C using a twin-screw extruder (OMEGA30H manufactured by STEER) to obtain pellets. The pellets were dried at 140°C for 5-10 hours, and then molded at 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 spectral light transmittance was measured at a wavelength range of 250-2500 nm at a thickness of 1 mm of the molded product using a UV-Vis-Infrared Spectrophotometer (V-770DS manufactured by JASCO Corporation).

[0088] (7) Solder reflow resistance The molded product (thickness 1 mm) obtained above was placed in a humidity chamber at 60°C / 60% RH (relative humidity) for 120 hours to condition the humidity, and then placed in an oven and heated according to the IPC / JEDEC J-STD-020C temperature profile (peak temperature 240°C or 260°C).Then, the appearance was observed and the solder reflow resistance was judged according to the following criteria. No change in transparency or shape of molded product: "Good" Changes in transparency or shape of the molded product are observed: "X"

[0089] [Example 1] In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 19176 parts by weight of ion-exchanged water and 7575 parts by weight of 25% aqueous sodium hydroxide solution were placed, and 4533 parts by weight of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF; manufactured by Osaka Gas Chemical Co., Ltd.) as a diol compound, 2017 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 hydrosulfite were dissolved, and then 30184 parts by weight of methylene chloride was added, and 1500 parts by weight of phosgene was blown in over 80 minutes at 16 to 24 ° C. with stirring. Then, a solution of 947 parts by weight of 25% aqueous sodium hydroxide solution and 53.27 parts by weight of p-tert-butylphenol dissolved in 530 parts by weight of methylene chloride was added and stirred to form an emulsion. Under such stirring, 2.99 parts by weight of triethylamine was added when the reaction solution was at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water, and when the washing solution became neutral, hydrochloric acid was added. Then, the mixture was repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase was almost the same as that of the ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained. Next, the obtained methylene chloride solution was dropped into warm water kept at 80°C, and the solvent was evaporated and removed to obtain a powder-like solid. The obtained solid was dried at 120°C for 24 hours to obtain a white powder-like 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 1.

[0090] The polycarbonate resin powder was melt-kneaded in a twin-screw extruder (OMEGA30H manufactured by STEER) at a cylinder and die temperature of 350 to 420°C to obtain pellets. The pellets were dried at 140°C for 10 hours, and then molded at a cylinder temperature of 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). The molded product was used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 1.

[0091] [Example 2] Except for using 3,466 parts by weight of BNF and 1,286 parts by weight of BisP-HTG as the diol compound, the same operation as in Example 1 was carried out. The evaluation results are shown in Table 1.

[0092] [Example 3] The same procedure as in Example 1 was carried out except that the diol compounds were 2666 parts by weight of BNF, 1837 parts by weight of BisP-HTG, and 79.90 parts by weight of p-tert-butylphenol. The evaluation results are shown in Table 1.

[0093] [Example 4] The same procedure as in Example 1 was carried out, except that 4533 parts by weight of BNF and 697 parts by weight of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (PPPBP; manufactured by Sakai Kogyo Co., Ltd.) were used as the diol compound. The evaluation results are shown in Table 1.

[0094] [Example 5] The same operations as in Example 1 were carried out except that the diol compounds were 2666 parts by weight of BNF, 697 parts by weight of PPPBP, and 1284 parts by weight of BisP-HTG. The evaluation results are shown in Table 1.

[0095] [Example 6] The same operations as in Example 1 were carried out except that the diol compound was BNF4266 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 evaluation results are shown in Table 1.

[0096] [Example 7] Except for using 3733 parts by weight of BNF and 802 parts by weight of BPA as the diol compound, the same operation as in Example 1 was carried out. The evaluation results are shown in Table 1.

[0097] [Example 8] Except for using 266 parts by weight of BNF and 3490 parts by weight of BisP-HTG as the diol compound, the same operation as in Example 1 was carried out. The evaluation results are shown in Table 1.

[0098] [Comparative Example 1] Except for using 4 parts by weight of BisP-HTG367 as the diol compound, the same procedure as in Example 1 was carried out. The evaluation results are shown in Table 1.

[0099] [Comparative Example 2] In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 12784 parts by weight of ion-exchanged water and 6628 parts by weight of 25% aqueous sodium hydroxide solution were placed, and 1738 parts by weight of BPA, 1286 parts by weight of BisP-HTG, and 6.05 parts by weight of hydrosulfite were dissolved as diol compounds. Then, 15092 parts by weight of methylene chloride was added, and 1500 parts by weight of phosgene was blown in over 80 minutes at 16 to 24°C under stirring. Then, a solution in which 947 parts by weight of 25% aqueous sodium hydroxide solution and 53.27 parts by weight of p-tert-butylphenol were dissolved in 530 parts by weight of methylene chloride was added and stirred to form an emulsion. Under such stirring, 2.99 parts by weight of triethylamine was added when the reaction solution was at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washing solution became neutral, hydrochloric acid was added. The product was then repeatedly washed with ion-exchanged water until the electrical conductivity of the aqueous phase was nearly the same as that of the ion-exchanged water, yielding a methylene chloride solution of polycarbonate. The methylene chloride solution was then dropped into warm water kept at 80°C, and the solvent was evaporated to obtain a powder-like solid. The solid was dried at 120°C for 24 hours to obtain a white powder-like polycarbonate resin. The resulting 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 1.

[0100] The polycarbonate resin powder was melt-kneaded in a vented twin-screw extruder [KZW15-25MG, Technobel Co., Ltd.] with both the cylinder and the die at 320°C to obtain pellets. A portion of the obtained pellets was dried at 120°C for 12 hours or more, and then molded (thickness 1 mm) was obtained using an injection molding machine (J-75E3, Japan Steel Works) under conditions of a cylinder temperature of 320°C and a mold temperature of 100°C. The molded product was used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 1.

[0101] [Comparative Example 3] Except for using 2140 parts by weight of BPA and 939 parts by weight of PPPBP as the diol compound, the same procedure as in Comparative Example 2 was carried out to obtain a polycarbonate resin powder. 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 1.

[0102] The polycarbonate resin powder was melt-kneaded in a vented twin-screw extruder [KZW15-25MG, Technobel Co., Ltd.] with both the cylinder and the die at 320°C to obtain pellets. A portion of the obtained pellets was dried at 120°C for 12 hours or more, and then molded (thickness 1 mm) was obtained using an injection molding machine (J-75E3, Japan Steel Works) under conditions of a cylinder temperature of 320°C and a mold temperature of 100°C. The molded product was used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 1.

[0103] [Comparative Example 4] Except for using 2675 parts by weight of BPA and 23.08 parts by weight of p-tert-butylphenol as the diol compound, the same procedure as in Comparative Example 2 was carried out to obtain a polycarbonate resin powder. 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 1.

[0104] The polycarbonate resin powder was melt-kneaded in a vented twin-screw extruder [KZW15-25MG, Technobel Co., Ltd.] with both the cylinder and the die at 330°C to obtain pellets. A part of the obtained pellets was dried at 120°C for 12 hours or more, and then molded (thickness 1 mm) was obtained using an injection molding machine (J-75E3, Japan Steel Works) under conditions of a cylinder temperature of 340°C and a mold temperature of 120°C. The molded product was used to evaluate the spectral light transmittance and solder reflow resistance. The evaluation results are shown in Table 1.

[0105] [Table 1] [Industrial Applicability]

[0106] The optical molded articles made of the polycarbonate resin of the present invention are subject to minimal dimensional change due to heat or water absorption and have excellent light transmittance and heat resistance, and therefore can be used in optical components such as connectors and lenses that are used in high-temperature environments, as well as electric and electronic components such as switches, sockets, sensor cases, and flexible films.

Claims

1. An optical molded article made of 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), wherein the proportion of the repeating unit (A) represented by formula (1) is 99 to 1 mol % based on all repeating units of the polycarbonate resin, and the content of the repeating unit (B) is in the range of 1 to 99 mol % based on all repeating units of the polycarbonate resin. 【Chemistry 1】 (In the above formula (1), ring Z is a naphthalene ring, R １ and R ２ each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 【Chemistry 2】 (In the above formula (2), R ３ and R ４ each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of each of these groups, they may be the same or different, e and f each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of groups represented by the following formula (3): 【Chemistry 3】 (In the above formula (3), R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different; R １３ and R １４ each independently represents at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; R １５ , R １６ , R １７ and R １８ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, h and i are integers of 1 to 3, and g is an integer of 1 to 100.

2. 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 the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine.

3. 2. An optical molded article made of the polycarbonate resin according to claim 1, which has a saturated water absorption of 0.5% or less.

4. 2. An optical molded article made of the polycarbonate resin according to claim 1, which has a glass transition temperature of 220 to 310°C.

5. 2. An optical molded article made of the polycarbonate resin according to claim 1, which has a linear expansion coefficient of 30 to 60 ppm / °C.

6. 2. An optical molded article made of the polycarbonate resin according to claim 1, which has a spectral light transmittance of 85% or more at wavelengths of 850 nm, 1310 nm and 1550 nm, 82% or more at wavelength 1610 nm and 78% or more at wavelength 1625 nm.

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