JP2017179323A - High-refractive-index polycarbonate resin and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polycarbonate resin which has excellent heat resistance and can achieve both a high refractive index and a low birefringence.SOLUTION: A polycarbonate resin has a constitutional unit represented by the formula (1) (where ring Zis a naphthalene ring, Ais an alkylene group, Rand Rare a substituent, n is an integer of 0 or more, m is an integer of 0-4, k is an integer of 0-6).SELECTED DRAWING: None

Description

  The present invention relates to a novel polycarbonate-based resin having a 9,9-bisnaphthylfluorene skeleton and a molded body (for example, an optical molded body such as an optical film and an optical lens) formed from the polycarbonate-based resin.

  There is a great need for a high refractive index for resin for optical lenses, and thermoplastic resins having a refractive index of 1.66 are now on the market. However, further higher refractive index (1.66 or more) is required in response to the high demands of recent optical equipment. Among these, polycarbonate is widely used as an optical lens because of its excellent balance between optical properties such as transparency and mechanical properties such as impact resistance. On the other hand, as a high refractive index resin, a resin having a fluorene skeleton (9,9-bisarylfluorene skeleton) or a naphthalene skeleton is known. Polycarbonate also has a high refractive index having a fluorene skeleton or a naphthalene skeleton introduced. Polycarbonate has been proposed.

  WO 2014/073496 (Patent Document 1) discloses a polycarbonate containing a structural unit derived from a diol component having a binaphthyl skeleton. In the examples of this document, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene, 9,9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene, diphenyl carbonate, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, and diphenyl carbonate Polycarbonates obtained by polymerizing polycarbonates obtained by polymerizing are described.

  However, even with this polycarbonate, the increase in the refractive index is not sufficient. For example, in the examples, a polycarbonate having a refractive index exceeding 1.67 is not manufactured, and a polycarbonate having a refractive index exceeding 1.66 is not produced. It was difficult to balance the glass transition temperature and the molecular weight, and it was difficult to achieve both heat resistance and moldability.

  WO2015 / 170691 pamphlet (Patent Document 2) discloses a polycarbonate containing a structural unit derived from a diol component having a binaphthyl skeleton and a structural unit derived from a diol component having a 9,9-bisphenylfluorene skeleton. ing. In the examples of this document, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, diphenyl carbonate, 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene and 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene And a polycarbonate obtained by polymerizing diphenyl carbonate; 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene and 9,9-bis [4- (2-hydroxyethoxy) phenyl] A polyester carbonate obtained by polymerizing fluorene, diphenyl carbonate and dimethyl terephthalate is described. That.

  However, even with this polycarbonate, the increase in the refractive index is not sufficient. For example, in the examples, a polycarbonate having a refractive index exceeding 1.67 is not produced, and a polycarbonate having a refractive index exceeding 1.66 is Glass transition point is low and heat resistance is not sufficient.

  That is, high refractive index, low birefringence, and heat resistance are in a trade-off relationship, and it is extremely difficult to further improve heat resistance, which cannot be realized with conventional polycarbonate.

WO2014 / 073496 pamphlet (Claim 1, Examples, Table 2-1, Table 3-1) WO2015 / 170691 pamphlet (Claim 16, Examples, Tables 1, 4 and 9)

  Accordingly, an object of the present invention is to provide a polycarbonate resin that is excellent in heat resistance and has both a high refractive index and a low birefringence, and a molded body formed from the polycarbonate resin (for example, optical films, optical lenses, etc.). It is to provide a molded article.

  Another object of the present invention is to provide a polycarbonate resin having a low Abbe number and a high molecular weight, and a molded body formed from this polycarbonate resin.

  Still another object of the present invention is to provide a polycarbonate resin excellent in moldability and mechanical properties and a molded body formed from the polycarbonate resin.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that a novel polycarbonate resin having a 9,9-bisnaphthylfluorene skeleton is excellent in heat resistance and conflicts with high refractive index and low birefringence. The present invention has been completed by finding that the characteristics can be compatible.

  That is, the polycarbonate resin of the present invention includes a structural unit represented by the following formula (1).

(In the formula, ring Z ¹ is a naphthalene ring, A ¹ is an alkylene group, R ¹ and R ² are substituents, n is an integer of 0 or more, m is an integer of 0 to 4, and k is an integer of 0 to 6. ).

  The structural unit represented by the formula (1) may be a structural unit represented by the following formula (1a).

(In the formula, A ¹ is an alkylene group, R ¹ and R ^2a are substituents, n is an integer of 0 or more, m is an integer of 0 to 4, and k1 is an integer of 0 to 3).

In the formula (1) or (1a), A ¹ may be a C _2-3 alkylene group, and n may be 1. 30 mol% or more of all the structural units may be sufficient as the structural unit represented by said Formula (1). The polycarbonate resin of the present invention may further contain a structural unit represented by the following formula (2) and / or a structural unit represented by the following formula (3).

(In the formula, ring Z ¹ is a naphthalene ring, A ¹ and A ² are alkylene groups, R ^{1 to} R ³ are substituents, n is an integer of 0 or more, m and p are integers of 0 to 4, and k is 0 to 0. (It is an integer of 6.)

(In the formula, ring Z ¹ is a naphthalene ring, A ¹ and A ³ are alkylene groups, R ¹ , R ² and R ⁴ are substituents, n is an integer of 0 or more, and m, q and r are integers of 0 to 4. , K is an integer from 0 to 6).

  The molar ratio between the structural unit represented by the formula (1) and the structural unit represented by the formula (2) and / or the structural unit represented by the formula (3) is, for example, the former / the latter = It is about 90/10 to 5/95. The polycarbonate resin of the present invention may be a polyester carbonate containing a polyester block unit having the structural unit represented by the formula (2) as a repeating unit.

  The said polycarbonate-type resin may further contain the structural unit represented by following formula (5).

Wherein X is a direct bond or an alkylene group, A ⁴ is an alkylene group, R ⁵ and R ⁶ are substituents, s is an integer of 0 or more, t is an integer of 0 to 2, and u is an integer of 0 to 4. is there).

  The molar ratio between the structural unit represented by the formula (1) and the structural unit represented by the formula (5) may be about the former / the latter = 80/20 to 10/90.

The polycarbonate resin of the present invention has a refractive index of 1.668 to 1.700 at 20 ° C. and a wavelength of 589 nm, an Abbe number of 17 to 23 at 20 ° C., and a temperature 10 ° C. higher than the glass transition point. The absolute value of the birefringence at 20 ° C. and the wavelength of 600 nm in the film stretched three times by may be 0.001 × 10 ⁻⁴ to 75 × 10 ⁻⁴ . The polycarbonate resin of the present invention may have a glass transition point (glass transition temperature) of 160 ° C. or higher.

  The molded body containing the said polycarbonate-type resin is also contained in this invention. The molded body of the present invention may be an optical member such as an optical film, an optical sheet, or an optical lens.

  In the present specification and claims, the term “polycarbonate” means a polycarbonate whose main chain linking group (linking group to the hydrocarbon group) consists only of carbonate bonds (carbonate ester bonds). The “system resin” means a resin containing a carbonate bond as a main chain linking group. That is, the term “polycarbonate-based resin” refers to a polymer (for example, polyester carbonate) containing not only the polycarbonate but also a linking group (for example, an ester bond) other than a carbonate bond as a linking group in the main chain. It is used in the meaning including.

  In the present invention, since the polycarbonate-based resin has a 9,9-bisnaphthylfluorene skeleton, it has excellent heat resistance and can achieve both high refractive index and low birefringence. In addition, the Abbe number can be reduced and the molecular weight can be improved. Furthermore, when polyester carbonate is polymerized by introducing a specific dicarboxylic acid unit, both high refractive index and low birefringence can be achieved at a high level, and moldability and mechanical properties can also be improved.

  The polycarbonate-based resin of the present invention may be a polycarbonate formed only with carbonate units (or carbonate bond-containing units) such as the structural unit represented by the formula (1), and the carbonate units (or polycarbonate units) and Further, it may be a modified polycarbonate formed with units other than carbonate units (or polymer units other than polycarbonate units).

[Polycarbonate]
(Structural unit represented by formula (1) (first structural unit))
In the formula (1), the naphthalene ring of Z ¹ is substituted at the 1-position or 2-position of the naphthalene ring with respect to the 9-position of the fluorene ring (replaced by the relationship of 1-naphthyl or 2-naphthyl) And may be substituted at the 2-position.

The alkylene group of group A ¹ constituting the oxyalkylene group, such as ethylene, propylene, trimethylene, 1,2-butanediyl group, a C _2-6 alkylene group such as tetramethylene group. The groups A ¹ on both sides may be the same alkylene group or different alkylene groups. Further, when n is a polyoxyalkylene group having 2 or more, the alkylene groups constituting the polyoxyalkylene group may be different alkylene groups, and usually may be the same alkylene group. The group A ¹ is preferably a C _2-4 alkylene group from the viewpoint of optical properties, and particularly preferably a C _2-3 alkylene group (particularly an ethylene group) such as an ethylene group or a propylene group.

The number of repetitions (addition mole number) of the oxyalkylene group A ¹ O (n is the number of repetitions of each group A ¹ O) may be an integer of 0 or more. From the viewpoint of optical properties and polymerizability, for example, 0 -3, preferably 0-2, more preferably 0 or 1 (especially 1).

The oxyalkylene group A ¹ O-containing group for connecting the 9,9-bisnaphthylfluorene skeleton is not particularly limited as long as it is a position other than the bonding position between the naphthalene ring and the fluorene ring. In many cases, the naphthyl group bonded at the position or the 2-position is substituted at any position of the 5- to 8-position. For example, the 1-position or 2-position of the naphthalene ring is compared with the 9-position of the fluorene ring. In many cases, the position is substituted (substituted in the relationship of 1-naphthyl or 2-naphthyl), and the substitution position is substituted in the relationship of 1,5-position, 2,6-position, etc. Substitution is preferably made in the 2,6-position represented by the formula (1a).

Examples of the substituent R ¹ include an alkyl group (for example, a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group). , A hydrocarbon group such as an aryl group (for example, a C _6-10 aryl group such as a phenyl group); a cyano group; a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom) and the like.

These substituents R ¹ can be used alone or in combination of two or more. As the substituent R ¹ , an alkyl group [for example, a linear or branched C _1-4 alkyl group (particularly, a C _1-3 alkyl group such as a methyl group)], a cyano group, and a halogen atom are preferable. An alkyl group (for example, a C _1-2 alkyl group such as a methyl group) is preferred.

The substitution number m of the substituent R ¹ can be selected from an integer of 0 to 4, for example, 0 to 3, preferably 0 to 2, and more preferably 0 or 1 (particularly 0). In the two benzene rings forming the fluorene skeleton, the number m of substitutions may be the same or different from each other, and the types of R ¹ may be the same or different from each other. When m is 2 or more, the two or more types of R ¹ substituted on the same benzene ring may be the same or different from each other. Further, the substitution position of R ¹ is not particularly limited, and may be, for example, 2-position to 7-position (2-position, 3-position, 7-position, etc.) of the fluorene ring.

Examples of the substituent R ² (or R ^2a ) include an alkyl group (for example, a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group), a cycloalkyl group (cycloto C _5-8 cycloalkyl group such as xyl group), aryl group (for example, C _6-10 aryl group such as phenyl group, tolyl group, xylyl group, etc.), aralkyl group (C ₆ such as benzyl group, phenethyl group, etc.) Hydrocarbon groups such as _-10 aryl-C _1-4 alkyl groups); alkoxy groups (such as C _1-6 alkoxy groups such as methoxy groups), cycloalkoxy groups (C _5-10 cycloalkyloxy such as cyclohexyloxy groups) group, etc.), etc. _{C 6-10} aryloxy groups such as an aryloxy group (phenoxy group), aralkyloxy group (benzyl Carboxymethyl including _{C 6-10} aryl _{-C 1-4} alkyl group such group); a _{C 1-6} alkylthio group such as an alkylthio group (methylthio group); an acyl group (such as _{C 1-6} acyl group such as acetyl group) Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); nitro group; cyano group; dialkylamino group ( _diC1-4 alkylamino group such as dimethylamino group); dialkylcarbonylamino group (diacetyl) And di- _C1-4 alkyl-carbonylamino group such as an amino group).

These substituents R ² can be used alone or in combination of two or more. As the substituent R ² , a C _1-6 alkyl group, a C _5-8 cycloalkyl group, and a C _1-4 alkoxy group are preferable, and a C _1-4 alkyl group such as a methyl group is particularly preferable.

The number of substitutions k (or twice the number of substitutions k1) of the substituent R ² can be selected from, for example, an integer of 0 to 6, for example 0 to 4, preferably 0 to 2, more preferably 0 or 1 ( In particular, it may be 0). Incidentally, the substitution number k of different Z ¹ may be the same or different from each other. In addition, when the number of substitutions k is 2 or more, the types of two or more R ² substituted with the same Z may be the same or different. The substitution position of R ² is not particularly limited, and a naphthalene ring Z ^1, it is sufficient to replace the ether bond (-O-) and the position other than the coupling position of the 9-position of the fluorene ring.

(Other structural unit having a fluorene skeleton (second structural unit))
The polycarbonate may further contain other structural units (carbonate units) having a fluorene skeleton. Such a structural unit is not particularly limited as long as it has a fluorene skeleton, but from the viewpoint of optical properties and heat resistance, for example, a structural unit represented by the following formula (4) is preferable.

(In the formula, ring Z ² is an aromatic hydrocarbon ring other than the naphthalene ring, A ¹ is an alkylene group, R ¹ and R ² are substituents, n is an integer of 0 or more, m is an integer of 0 to 4, and k is It is an integer of 0-6).

In the formula (4), examples of the aromatic hydrocarbon ring (arene ring) represented by Z ² include a monocyclic aromatic hydrocarbon ring (monocyclic arene ring) such as a benzene ring, and a polycyclic aromatic ring. An aromatic hydrocarbon ring (polycyclic arene ring), and the like. Examples of the polycyclic aromatic hydrocarbon ring include a condensed polycyclic aromatic hydrocarbon ring (condensed polycyclic arene ring), and a ring assembly aroma. Group hydrocarbon ring (ring assembly arene ring) and the like.

  Examples of the condensed polycyclic arene ring include condensed tricyclic to tetracyclic arene rings such as a condensed tricyclic arene ring (eg, anthracene ring, phenanthrene ring).

Examples of the ring-assembled arene ring include a bialene ring (for example, a bi-C _6-16 arene ring such as a biphenyl ring and a naphthylphenyl ring), a tellarene ring (for example, a ter-C _6-18 arene ring such as a terphenylene ring), and the like. Is mentioned.

Among these Z ² , C _6-12 arene rings such as a benzene ring and a biphenyl ring are preferable, and a benzene ring and a biphenyl ring are particularly preferable. Further, two Z ² may be the same or different from each other.

The repeating number n of the alkylene group A ¹ and the oxyalkylene group A ¹ O, the substituent R ¹ and the number of substitution m thereof, the substituent R ² and the number of substitution k thereof are the same as those in the formula (1), including preferred embodiments. It is. In addition, the substitution number and substitution position of R ² can be appropriately selected according to the type of ring Z ² .

  The proportion of the structural unit represented by the formula (4) may be 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less (particularly 10 mol% or less) with respect to the entire carbonate unit. ). If the proportion of the structural unit represented by formula (4) is too large, the refractive index may be lowered. From the viewpoint of improving the refractive index, the constituent unit represented by the formula (4) may be 0 mol%.

  On the other hand, in applications where low birefringence is important, it is preferable to include a structural unit represented by formula (4), and a structural unit represented by formula (1) and a structural unit represented by formula (4) The molar ratio of, for example, the former / the latter = 100/0 to 10/90, preferably 90/10 to 20/80 (for example, 80/20 to 25/75), and more preferably 70/30 to 30/70 ( In particular, it is about 60/40 to 40/60).

(Structural unit having a bi- or bisnaphthyl skeleton represented by formula (5) (third structural unit))
In the formula (5), examples of the alkylene group represented by X include linear or branched chains such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. C _1-4 alkylene group and the like can be mentioned. X is preferably a direct bond or a C _1-2 alkylene group (for example, a methylene group) from the viewpoint of optical properties (for example, high refractive index, low Abbe number, low birefringence, etc.), and particularly preferably a direct bond. .

The alkylene group represented by group A ⁴ constituting the oxyalkylene group, for example, the preferred embodiment illustrated in the alkylene group A ¹ in the formula (1) is also the same, including.

The repeating number s of the oxyalkylene group A ⁴ O may be an integer of 0 or more, for example, 0 to 3, preferably 0 to 2, more preferably 0 or 1, and optical properties (high refractive index, low Abbe The number of repetitions s is particularly preferably 0 from the viewpoint of the number, low birefringence, etc.) and heat resistance, and the number of repetitions s is particularly preferably 1 from the viewpoint that coloring can be suppressed.

The substitution position of the group —O— (A ⁴ O) _s — and the group —O— (A ⁴ O) _s —CO— that form the main chain of the polycarbonate resin is in the 2-position to the 4-position of the naphthalene ring ( Alternatively, any position from 2′-position to 4′-position) may be used, but the 2-position (or 2′-position) is particularly preferable from the viewpoint that birefringence can be reduced.

The substituents R ⁵ and R ⁶ are the same as those of the substituent R ² exemplified in the formula (1), including preferred embodiments.

Each substitution number t of the substituent R ⁵ can be selected from an integer of 0 to 2, for example, 0 or 1, preferably 0. Each substitution number u of the substituent R ⁶ can be selected from an integer of 0 to 4, and may be, for example, 0 to 3, preferably 0 to 2, more preferably 0 or 1 (particularly 0).

In two different naphthalene rings forming a bi- or bisnaphthyl skeleton, the number of substitutions t and the number of substitutions u may be the same or different from each other, and the types of the groups R ⁵ and R ⁶ are substituted. They may be the same or different from each other depending on the numbers t and u. When two or more groups R ⁵ and / or two or more groups R ⁶ are substituted on the same naphthalene ring (when t is 2 and / or u is 2 or more), the types of the two groups R ⁵ and / Or the types of the two or more groups R ⁶ may be the same or different from each other.

Further, the substitution position of the group R ⁵ is not particularly limited as long as it is a position other than the substitution position of the group —O— (A ⁴ O) _s — and the group —O— (A ⁴ O) _s —CO—. The substitution position of the group R ⁶ is not particularly limited, and may be substituted at any position among the 5-position to 8-position (or 5′-position to 8′-position) of the naphthalene ring.

  The polycarbonate-based resin contains the structural unit represented by the formula (5), so that it maintains (or maintains) high heat resistance while maintaining optical characteristics (for example, high refractive index, low Abbe number, low birefringence, etc.). Can be improved (or improved) in a more balanced manner. The molar ratio between the structural unit represented by the formula (1) and the structural unit represented by the formula (5) is, for example, the former / the latter = 100/0 to 5/95 (for example, 90/10 to 60 / 40), for example, 80/20 to 10/90 (for example, 70/30 to 50/50), preferably 60/40 to 15/85 (for example, 55/45 to 40/60) More preferably, it may be about 50/50 to 20/80 (for example, 45/55 to 30/70), usually 40/60 to 22/78 (for example, 40/60 to 30/70), Preferably it is about 35 / 65-25 / 75.

(Structural unit having no fluorene skeleton and / or bi- or bisnaphthyl skeleton (fourth structural unit))
The polycarbonate may contain a fourth structural unit (a structural unit having no fluorene skeleton and / or bi- or bisnaphthyl skeleton) as a carbonate unit as long as the effects of the present invention are not impaired. Such a structural unit may be a conventional structural unit (carbonate unit) used as a polycarbonate.

Conventional structural units include structural units derived from bisphenols, such as biphenols;
Bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4 And a structural unit derived from bisphenols such as -hydroxyphenyl) sulfone (bisphenol S). These units can be used alone or in combination of two or more.

  The ratio of the fourth structural unit (structural unit having no fluorene skeleton and / or bi- or bisnaphthyl skeleton) may be 50 mol% or less (for example, 0.1 to 50 mol%) with respect to the entire carbonate unit. It is preferably 30 mol% or less, more preferably 10 mol% or less (particularly 5 mol% or less).

  Polycarbonate should just contain 10 mol% or more (for example, 10-100 mol%) of the structural unit represented by said Formula (1) in all the structural units, for example, 30 mol% or more, Preferably it is 50 mol% or more ( (Especially 90 mol% or more) may be contained, and the structural unit represented by the formula (1) may be formed alone.

[Modified polycarbonate]
The polycarbonate-based resin of the present invention may be a modified polycarbonate containing another structural unit having a linking group other than a carbonate bond in addition to the carbonate unit. Examples of the linking group other than the carbonate bond include an ether bond, an ester bond, an amide bond, and a urethane bond. Among these linking groups, an ester bond is preferable from the viewpoint of the productivity of the polycarbonate resin. The other structural unit having an ester bond (ester unit) is not particularly limited as long as it has an ester bond, but from the viewpoint of excellent balance of various properties, the structural unit represented by the formula (2) and / or the above The structural unit represented by Formula (3) is preferable. In the present invention, the carbonate unit having a bulky 9,9-bisnaphthylfluorene skeleton is further combined with a specific structural unit having a fluorene skeleton as an ester unit. In spite of containing a high fluorene skeleton at high density, the moldability can be improved, and the optical properties (high refractive index and low birefringence, particularly low birefringence) and heat resistance can be highly compatible.

In the above formulas (2) and (3), ring Z ¹ , alkylene group A ¹ and oxyalkylene group A ¹ O repeating number n, substituent R ¹ and substitution number m, substituent R ² and substitution number k Is the same as formula (1), including preferred embodiments.

In the formula (2), examples of the alkylene group of the group A ² include a methylene group, an ethylene group, a trimethylene group, a propylene group, a 2-ethylethylene group, and a 2-methylpropane-1,3-diyl group. Examples thereof include a linear or branched C _1-8 alkylene group. Alkylene group A ² may further have a substituent. Examples of the substituent include an aryl group (for example, a phenyl group) and a cycloalkyl group (for example, a cyclohexyl group).

The group A ² is preferably a linear or branched C _1-6 alkylene group, and may be a linear chain such as a methylene group, an ethylene group, a trimethylene group, a propylene group, or a 2-methylpropane-1,3-diyl group. Or a branched _C1-4 alkylene group is particularly preferable, and in many cases, it is a linear or branched _C2-4 alkylene group such as an ethylene group or a propylene group. The alkylene group having a substituent may be, for example, a 1-phenylethylene group, a 1-phenylpropane-1,2-diyl group, or the like.

Examples of the substituent R ³ include the substituents exemplified as the substituent R ¹ in the formula (1). The substituent R ³ is often a halogen atom, a cyano group or an alkyl group (particularly an alkyl group). Examples of the alkyl group include C _1-12 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-8 alkyl group, particularly a C group such as a methyl group). _1-4 alkyl group) and the like.

When p is plural (two or more), the groups R ³ in the same benzene ring in the fluorene skeleton may be the same or different in each benzene ring. Further, the groups R ³ substituted on the two benzene rings constituting the fluorene skeleton may be the same or different. Further, the bonding position (substitution position) of the group R ³ with respect to the two benzene rings constituting the fluorene skeleton is not particularly limited, and examples thereof include the 2-position, 7-position, 2-position and 7-position of the fluorene skeleton. Can be illustrated. The preferred substitution number p is, for example, 0 to 1, in particular 0. In the two benzene rings constituting the fluorene skeleton, the substitution number p may be the same as or different from each other.

In the formula (3), examples of the alkylene group of the group A ³ include the alkylene groups exemplified as the group A ² . The group A ³ is preferably a linear or branched C _1-6 alkylene group, and is a linear chain such as a methylene group, an ethylene group, a trimethylene group, a propylene group, or a 2-methylpropane-1,3-diyl group. Alternatively, a branched C _1-4 alkylene group is particularly preferable, and in many cases, it is a linear or branched C _1-3 alkylene group such as a methylene group or an ethylene group.

  Q which is the repeating number of the methylene group can be selected from integers of 0 to 4, and is, for example, 0 to 2, preferably 0 or 1.

The substituent R ⁴ and the number of substitutions r thereof are the same as the substituents R ³ and p in the formula (2), including preferred embodiments.

  The molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) and / or the structural unit represented by the formula (3) (the total amount when both structural units are combined) is For example, the former / the latter = 90/10 to 5/95, preferably 80/20 to 10/90 (for example, 70/30 to 20/80), more preferably 50/50 to 25/75 (particularly 40/60). About 30/70). If the proportion of the former structural unit is too small, the refractive index may be lowered, and if the proportion of the latter structural unit is too small, the birefringence may be increased or the moldability may be lowered.

  The modified polycarbonate containing the structural unit represented by the formula (2) and / or the structural unit represented by the formula (3) is usually represented by the structural unit represented by the formula (2) and / or the formula (3). Polyester carbonate containing a polyester block unit having a repeating unit as the repeating unit and a polyester block unit having the repeating unit as the repeating unit represented by formula (2) is preferable.

  The proportion of the structural unit represented by the formula (2) and / or the structural unit represented by the formula (3) may be 90 mol% or less in the modified polycarbonate, for example, 10 to 90 mol%, preferably 30 It is about -80 mol%, More preferably, it is about 50-75 mol% (especially 60-70 mol%). If the proportion of these structural units is too small, the birefringence may be lowered. If the proportion is too large, the refractive index may be lowered or the moldability may be lowered.

  The modified polycarbonate may contain other structural units. As other structural units, other carbonate units exemplified in the section of polycarbonate [other structural units having a fluorene skeleton (second structural unit), structures having a bi- or bisnaphthyl skeleton represented by the formula (5) Unit (third structural unit), fluorene skeleton and / or structural unit having no bi- or bisnaphthyl skeleton (fourth structural unit)], conventional ester unit (structural unit containing an ester bond), and the like. .

The conventional ester unit is not particularly limited as long as it has an ester bond. For example, C _2-4 alkylene terephthalate units such as ethylene terephthalate, propylene terephthalate, butylene terephthalate, ethylene naphthalate, propylene naphthalate, butylene naphthalate, etc. And C _2-4 alkylene naphthalate units.

  The proportion of other structural units may be 30 mol% or less (for example, 0.1 to 30 mol%), preferably 20 mol% or less, more preferably 10 mol% or less (particularly, relative to the entire structural unit. 5 mol% or less).

[Characteristics of polycarbonate resin]
The polycarbonate-based resin of the present invention is a resin having a 9,9-bisnaphthylfluorene skeleton. Specifically, the structural unit represented by the formula (1) is 10 mol% or more (particularly 30%) of all the structural units. For example, 15 to 90 mol%, preferably 20 to 80 mol%, more preferably 25 to 75 mol% (especially 30 to 40 mol%). The structural unit represented by 1) may be formed alone. Therefore, it is excellent in various characteristics (for example, optical characteristics, mechanical characteristics, thermal characteristics, etc.), particularly excellent in heat resistance, and has both high refractive index and low birefringence. Further, a carbonate unit having a 9,9-bisnaphthylfluorene skeleton and a structural unit represented by the formula (2) and / or a polyester block unit containing the structural unit represented by the formula (3) are combined. Therefore, while maintaining a high refractive index, molecular weight, heat resistance and a low Abbe number, the moldability can be improved and the birefringence can be reduced.

  The refractive index of the polycarbonate resin of the present invention at 20 ° C. and a wavelength of 589 nm can be selected from the range of, for example, 1.660 or more (for example, about 1.660 to 1.750), for example, 1.665 or more (for example, 1.665). ˜1.720), preferably 1.668 or more (for example, about 1.670 to 1.700), more preferably 1.670 or more (for example, about 1.675 to 1.695), and particularly high refractive index is required. In applications to be used, for example, 1.675 or more (for example, about 1.680 to 1.692), preferably 1.680 or more (for example, about 1.680 to 1.690), and more preferably 1.675 or more (for example, 1 .685 to 1.691).

  The Abbe number at 20 ° C. of the polycarbonate resin of the present invention can be selected from a range of 23.0 or less (for example, about 17.0 to 23.0), for example, 21.0 or less (for example, 17.0 to 21.20). 0), preferably 20.0 or less (for example, about 17.0 to 20.0), more preferably 19.5 or less (for example, about 17.0 to 19.5), and particularly 19.0 or less (for example, 17. 0 to 19.0) or 18.5 or less (for example, about 17.0 to 18.3).

The absolute value of birefringence (birefringence in a film uniaxially stretched three times at a temperature 10 ° C. higher than the glass transition point) at 20 ° C. and a wavelength of 600 nm of the polycarbonate resin of the present invention is, for example, 75 × 10 ^−4. Can be selected from the following range (for example, about 0.001 × 10 ⁻⁴ to 75 × 10 ⁻⁴ ), for example, 60 × 10 ⁻⁴ or less (for example, about 0.005 × 10 ^{−4 to} 60 × 10 ⁻⁴ ), Preferably it is 50 × 10 ⁻⁴ or less (for example, about 0.01 × 10 ⁻⁴ to 50 × 10 ⁻⁴ ), more preferably 40 × 10 ⁻⁴ or less (for example, 0.1 × 10 ⁻⁴ to 40 × 10 ^−4). About 30 × 10 ⁻⁴ or less (for example, about 1 × 10 ⁻⁴ to 30 × 10 ⁻⁴ ) or 25 × 10 ⁻⁴ or less (for example 5 × 10 ^{−4 to} 25 × 10 ^−4). Degree). In addition, in this specification and a claim, this birefringence can be measured by the method as described in the Example mentioned later.

  The glass transition point (Tg) of the polycarbonate resin of the present invention is high, and can be selected, for example, from a range of about Tg 130 to 250 ° C. (for example, 150 to 250 ° C.), for example, 160 ° C. or higher (for example, about 160 to 230 ° C.), preferably 165 degreeC or more (for example, about 165-220 degreeC), More preferably, 170 degreeC or more (for example, about 170-210 degreeC), Especially 180 degreeC or more (for example, about 180-200 degreeC) may be sufficient.

The weight average molecular weight (Mw) of the polycarbonate-based resin of the present invention can be selected from a range of, for example, about 1.5 × 10 ⁴ to 50 × 10 ^{4 in} terms of polystyrene in gel permeation chromatography (GPC). × 10 ⁴ to 30 × 10 ⁴ , preferably 2 × 10 ^{4 to} 20 × 10 ⁴ , more preferably about 2.5 × 10 ⁴ to 10 × 10 ⁴ , especially about 3 × 10 ^{4 to} 5 × 10 ^4. May be.

[Production method of polycarbonate resin]
The polycarbonate resin of the present invention contains a diol for forming at least the structural unit represented by the formula (1) by a conventional method, for example, a phosgene method (solvent method) or a transesterification method (melting method). It can be produced by reacting (polymerizing or condensing) with phosgene or a carbonic acid diester (such as diphenyl carbonate). If necessary, the diol component may further contain a diol for forming the structural unit represented by the formula (4) and / or (5). Among these methods, a transesterification method is preferable because a solvent is unnecessary and polyester carbonate can be easily produced. In the transesterification method, in addition to the diol, a dicarboxylic acid for forming the structural unit represented by the formula (2) and / or (3) is added and reacted at the same time, and the pressure is reduced during the polymerization. The polyester carbonate containing the polyester block unit which makes the structural unit represented by the said Formula (2) and / or (3) a repeating unit can be manufactured easily.

The transesterification reaction may be performed in the presence of a catalyst. As the catalyst, various catalysts used for the transesterification reaction, such as a metal catalyst, can be used. Examples of the metal catalyst include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, titanium, etc.), periodic table group 13 metals. A metal compound containing (such as aluminum), a periodic table group 14 metal (such as germanium), a periodic table group 15 metal (such as antimony), or the like is used. Examples of the metal compound include alkoxides, organic acid salts (such as acetates and propionates), inorganic acid salts (such as borates and carbonates), and metal oxides. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used may be, for example, about 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably about 0.1 × 10 ⁻⁴ to 40 × 10 ⁻⁴ mol, relative to 1 mol of the diol. Good.

  Moreover, you may perform reaction in presence of additives, such as stabilizers (an antioxidant, a heat stabilizer, etc.) as needed.

The reaction can usually be performed in an inert gas (nitrogen, helium, etc.) atmosphere. The reaction can also be performed under reduced pressure (for example, about 1 × 10 ² to 1 × 10 ⁴ Pa). The reaction temperature can be selected according to the polymerization method. For example, the reaction temperature in the transesterification method may be, for example, 150 to 320 ° C, preferably 200 to 310 ° C, and more preferably about 250 to 300 ° C. In particular, when diphenyl carbonate is used as the carbonic acid diester, it is effective to perform polycondensation while distilling off phenol under high temperature and reduced pressure, and as described above, polyester carbonate can be easily produced by reducing the pressure during polymerization. .

Examples of the monomer for forming the structural unit represented by the formula (1) include 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-). Bis (hydroxynaphthyl) fluorene such as naphthyl) fluorene; 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1- Naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (2-hydroxyethoxy) ethoxy) -2-naphthyl] fluorene 9,9-bis [hydroxy (poly) C _2-4 a, such as 9,9-bis [5- (2- (2-hydroxyethoxy) ethoxy) -1-naphthyl] fluorene Diols such as lucoxynaphthyl) fluorene.

As a monomer for forming the structural unit represented by the formula (4), for example, 9,9-bis [hydroxy (poly (9)) such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene. ) C _2-4 alkoxyphenyl] fluorene; 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenyl And diols such as 9,9-bis [hydroxy (poly) C _2-4 alkoxy-C _6-10 aryl-phenyl] fluorene such as phenyl] fluorene.

Examples of the monomer for forming the structural unit represented by the formula (5) include 2,2′-dihydroxy-1,1′-binaphthalene; 2,2′-bis (2-hydroxyethoxy) -1 , 1′-Binaphthalene, 2,2′-bis (2-hydroxypropoxy) -1,1′-binaphthalene, 2,2′-bis [2- (2-hydroxyethoxy) ethoxy] -1,1′-binaphthalene And diols such as 2,2′-bis [hydroxy- (poly) C _2-4 alkoxy) -1,1′-binaphthalene. The monomer for forming the structural unit represented by the formula (5) may be an optically active substance or a racemate.

As a typical monomer for forming the structural unit represented by the formulas (2) and (3), for example, a diol for forming the structural unit represented by the formula (1), for example, 9,9-bis (carboxy C _2-6 alkyl) fluorene such as 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis (2-carboxypropyl) fluorene; 9- (1-carboxy-2 -Carboxyethyl) fluorene, combinations with dicarboxylic acids such as 9- (carboxy-carboxy C _2-6 alkyl) fluorene such as 9- (2-carboxy-3-carboxypropyl) fluorene, and the like.

The dicarboxylic acid may be an ester-forming derivative. Examples of ester-forming derivatives include esters [eg, alkyl esters [eg, lower alkyl esters such as methyl esters and ethyl esters (eg, C _1-4 alkyl esters, particularly C _1-2 alkyl esters), etc.], etc.]] And acid halides (for example, acid chlorides), acid anhydrides and the like. The ester-forming derivative may be a monoester (half ester) or a diester.

[Molded body]
The molded article of the present invention contains the polycarbonate resin, and has excellent optical properties (high refractive index, low birefringence, etc.), mechanical properties, and high heat resistance, so an optical film, an optical lens, It can be used as an optical member such as an optical sheet. The shape of the shape is not particularly limited, and for example, a two-dimensional structure (for example, a film shape, a sheet shape, a plate shape, etc.), a three-dimensional structure (for example, a concave or convex lens shape, a tubular shape, a rod shape, a tube shape, a hollow shape) Etc.).

  The molded article of the present invention has various additives [for example, fillers or reinforcing agents, colorants (for example, dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (for example, antioxidants, ultraviolet rays). Absorbents, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents (eg silicone oil, silicone rubber, various types) Plastic powder, various engineering plastic powders, carbon materials, etc.]. These additives may be used alone or in combination of two or more.

  The molded body can be manufactured using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, and the like.

  In particular, the polycarbonate-based resin of the present invention is useful for forming a film (particularly an optical film) because it is excellent in various optical properties. Therefore, the present invention also includes a film (optical film) formed of the polycarbonate resin.

  The thickness (average thickness) of such a film can be selected from the range of about 1 to 1000 μm depending on the application, and may be, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably about 10 to 120 μm.

  Such a film (optical film) is manufactured by forming (or molding) the polycarbonate resin using a conventional film forming method, a casting method (solvent casting method), a melt extrusion method, a calendar method, or the like. it can.

  The film may be a stretched film. Even if the film of the present invention is a stretched film, low birefringence can be maintained. Such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

  The stretching ratio may be about 1.1 to 10 times (preferably 1.2 to 8 times, more preferably 1.5 to 6 times) in each direction in uniaxial stretching or biaxial stretching. It may be about 1 to 2.5 times (preferably 1.2 to 2.3 times, more preferably 1.5 to 2.2 times). In the case of biaxial stretching, even stretching (for example, stretching 1.5 to 5 times in both longitudinal and transverse directions) is uneven stretching (for example, 1.1 to 4 times in the longitudinal direction and 2 to 6 in the lateral direction). Double stretching). In the case of uniaxial stretching, the stretching may be longitudinal stretching (for example, 2.5 to 8 times stretching in the longitudinal direction) or lateral stretching (for example, 1.2 to 5 times stretching in the transverse direction).

  The stretched film may have a thickness (average thickness) of, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably about 5 to 100 μm.

  Such a stretched film can be obtained by subjecting a film after film formation (or an unstretched film) to a stretching treatment. The stretching method is not particularly limited. In the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used. In the case of biaxial stretching, a tenter method (also called a flat method) may be used. However, a tenter method that is excellent in uniformity of stretch thickness is preferable.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The abbreviations and details of the raw materials used are shown below. Moreover, the measurement and evaluation of the characteristic of resin or a film were performed with the following method.

[material]
BNEF: 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (synthesized according to Synthesis Example 1 described later)
BOPPEF: 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, Osaka Gas Chemical Co., Ltd. BPEF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene FDPM manufactured by Osaka Gas Chemical Co., Ltd .: 9,9-bis (2-methoxycarbonylethyl) fluorene (dimethyl ester of fluorene-9,9-propionic acid), acrylic of Example 1 of JP-A-2005-89422 Synthesis was performed in the same manner except that t-butyl acid was changed to 37.9 g (0.44 mol) of methyl acrylate. DPC: Diphenyl carbonate BINOL: 2,2′-dihydroxy-1,1′-binaphthalene, Tokyo Chemical Industry ( BINOL-2EO: 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene Synthesis Synthesis Example 2 below).

[Molecular weight]
The sample was dissolved in chloroform, and the weight average molecular weight (Mw) in terms of polystyrene was determined using gel permeation chromatography (“HLC-8120GPC” manufactured by Tosoh Corporation).

[Glass transition point (Tg)]
Using a differential scanning calorimeter (“DSC 6220” manufactured by Seiko Instruments Inc.), a sample was put in an aluminum pan, and the glass transition point (Tg) was measured in the range of 30 ° C. to 200 ° C.

[Refractive index (nD)]
A film having a thickness of 200 to 300 μm was formed by hot pressing the sample at 200 to 240 ° C. This film was cut into a strip shape having a length of 20 to 30 mm and a width of 10 mm to obtain a test piece. About the obtained test body, using a multiwavelength Abbe refractometer ("DR-M2 / 1500" manufactured by Atago Co., Ltd.), using a diiodomethane as a contact liquid at a measurement temperature of 20 ° C, 589 nm (D line) The refractive index nD of was measured.

[Abbe number]
Using a multi-wavelength Abbe refractometer ("DR-M4 (Circulation type constant temperature water bath 60-C3)" manufactured by Atago Co., Ltd.), using a diiodomethane as a contact liquid at a measurement temperature of 20 ° C, a measurement wavelength of 486 nm (F Line), refractive indexes nF, nD, and nC of 589 nm (D line) and 656 nm (C line) were measured and calculated by the following formulas.

    Abbe number = (nD-1) / (nF-nC).

[Birefringence (or triple birefringence)]
A film having a thickness of 200 to 600 μm was formed by hot pressing the sample at 200 to 240 ° C. This film was cut into a strip of 10 mm × 50 mm, and uniaxially stretched at 25 mm / min and a stretching ratio of 3 times under a temperature condition of Tg + 10 ° C. to obtain a test piece. Using the retardation film / optical material inspection device ("RETS-100" manufactured by Otsuka Electronics Co., Ltd.), the stretched test piece was subjected to the parallel Nicol rotation method (rotation test) under the conditions of a measurement temperature of 20 ° C and a measurement wavelength of 600 nm. The retardation was measured by the photon method, and the value was calculated by dividing the value by the thickness of the measurement site.

[Synthesis of BNEF (Synthesis Example 1)]
A 1-L separable flask was charged with 45 g of 9-fluorenone (0.25 mol, manufactured by Osaka Gas Chemical Co., Ltd.), 188 g (1 mol) of ethylene glycol mono (2-naphthyl) ether, and 1 g of 3-mercaptopropionic acid. Later, it was heated to 60 ° C. and completely dissolved. Thereafter, 54 g of sulfuric acid was gradually added and stirred for 5 hours while maintaining 60 ° C., and it was confirmed by HPLC (High Performance Liquid Chromatography) that the conversion of 9-fluorenone was 99% or more. After 48% caustic soda water was added to the obtained reaction solution for neutralization, 400 g of xylene was added, washed several times with distilled water, and cooled to precipitate crystals. Furthermore, when filtered and dried, the desired 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF) was obtained as 87 g (yield 67%) of crystals. When the HPLC purity of the obtained crystal was measured, the purity was 98.3%. The obtained sample was confirmed to be 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF) by ¹ H-NMR and mass spectrum.

[Synthesis of BINOL-2EO (Synthesis Example 2)]
A 1 L separable flask was charged with 89 g of BINOL (0.31 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 86 g (0.62 mol) of potassium carbonate, and 295 g of N, N-dimethylformamide (DMF), and 100 ° C. Then, a solution prepared by dissolving 110 g of ethylene carbonate in 112 g of DMF was gradually added, and the mixture was stirred for 2 hours while maintaining 100 ° C. It was confirmed by HPLC (high performance liquid chromatography) that the conversion rate of BINOL was 99% or more. Distilled water (800 g) and ethyl acetate (900 g) were added to the resulting reaction solution, washed several times with distilled water, concentrated under reduced pressure, and recrystallized with an ethyl acetate / ethanol mixed solvent. When the precipitate was filtered and dried, the desired 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene (BINOL-2EO) was obtained as 67 g (yield 58%) of crystals. It was. When the HPLC purity of the obtained crystal was measured, the purity was 94.8%. The obtained sample was confirmed to be 2,2′-bis (2-hydroxyethoxy) -1,1′-binaphthalene (BINOL-2EO) by ¹ H-NMR and mass spectrum.

[Example 1]
A reactor was charged with 1 mol of BNEF, 1.05 mol of DPC, and 2 × 10 ⁻⁴ mol of titanium tetraisopropoxide as a transesterification catalyst, gradually heated and melted with stirring, heated to 250 ° C., and then 10 kPa The pressure was reduced step by step. Phenol was removed while gradually raising the temperature and reducing the pressure until reaching 270 ° C. and 0.13 kPa or less. After reaching a predetermined stirring torque, the contents were taken out of the reactor to obtain polycarbonate pellets. When the obtained pellet was analyzed by ¹ H-NMR, 100 mol% of the monomer introduced into the polycarbonate was derived from BNEF.

[Example 2]
A reactor was charged with 0.8 mol of BNEF, 0.2 mol of FDPM, 0.63 mol of DPC, and 2 × 10 ⁻⁴ mol of titanium tetraisopropoxide as a transesterification catalyst. After raising the temperature to ° C., the pressure was reduced stepwise up to 10 kPa. Phenol was removed while gradually raising the temperature and reducing the pressure until reaching 270 ° C. and 0.13 kPa or less. After reaching a predetermined stirring torque, the contents were taken out of the reactor to obtain polyester carbonate pellets. When the obtained pellet was analyzed by ¹ H-NMR, 80 mol% of the monomer introduced into the polyester carbonate was derived from BNEF, and 20 mol% was derived from FDPM.

[Example 3]
Polyester carbonate pellets were obtained in the same manner as in Example 2 except that the amount of raw materials charged was changed to 0.6 mol of BNEF, 0.4 mol of FDPM, and 0.21 mol of DPC. When the obtained pellet was analyzed by ¹ H-NMR, 60 mol% of the monomer introduced into the polyester carbonate was derived from BNEF, and 40 mol% was derived from FDPM.

[Example 4]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.5 mol of BNEF and 0.5 mol of BOPPEF were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 50 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 50 mol% was derived from BOPPEF.

[Example 5]
A polycarbonate pellet was obtained in the same manner as in Example 1 except that 0.5 mol of BNEF and 0.5 mol of BPEF were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 50 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 50 mol% was derived from BPEF.

[Comparative Example 1]
A polycarbonate pellet was obtained in the same manner as in Example 1 except that 1 mol of BOPPEF was used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 100 mol% of the monomer introduced into the polycarbonate was derived from BOPPEF.

[Comparative Example 2]
Polycarbonate pellets were obtained in the same manner as in Example 1, except that 0.5 mol of BOPPEF and 0.5 mol of BPEF were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 50 mol% of the monomer introduced into the polycarbonate was derived from BOPPEF, and 50 mol% was derived from BPEF.

[Comparative Example 3]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 1 mol of BPEF was used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 100 mol% of the monomer introduced into the polycarbonate was derived from BPEF.

[Example 6]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.55 mol of BNEF and 0.45 mol of BINOL were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 55 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 45 mol% was derived from BINOL.

[Example 7]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.45 mol of BNEF and 0.55 mol of BINOL were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 45 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 55 mol% was derived from BINOL.

[Example 8]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.4 mol of BNEF and 0.6 mol of BINOL were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 40 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 60 mol% was derived from BINOL.

[Example 9]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.35 mol of BNEF and 0.65 mol of BINOL were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 35 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 65 mol% was derived from BINOL.

[Example 10]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.3 mol of BNEF and 0.7 mol of BINOL were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 30 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 70 mol% was derived from BINOL.

[Example 11]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.7 mol of BNEF and 0.3 mol of BINOL-2EO were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 70 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 30 mol% was derived from BINOL-2EO.

[Example 12]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.55 mol of BNEF and 0.45 mol of BINOL-2EO were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 55 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 45 mol% was derived from BINOL-2EO.

[Example 13]
Instead of 1 mol of BNEF, polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.5 mol of BNEF and 0.5 mol of BINOL-2EO were used. When the obtained pellet was analyzed by ¹ H-NMR, 50 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 50 mol% was derived from BINOL-2EO.

[Example 14]
Polycarbonate pellets were obtained in the same manner as in Example 1 except that 0.3 mol of BNEF and 0.7 mol of BINOL-2EO were used instead of 1 mol of BNEF. When the obtained pellet was analyzed by ¹ H-NMR, 30 mol% of the monomer introduced into the polycarbonate was derived from BNEF, and 70 mol% was derived from BINOL-2EO.

  Tables 1 and 2 show the weight average molecular weight Mw, glass transition point Tg, refractive index, Abbe number, and triple birefringence of the polycarbonates and polyester carbonates obtained in Examples and Comparative Examples.

  As is apparent from Tables 1 and 2, in the examples, high heat resistance, high refractive index, low Abbe number, and low birefringence could be satisfied. In particular, Examples 2 and 3 were highly satisfactory. On the other hand, in the comparative example, the refractive index was less than 1.66.

  The polycarbonate-based resin of the present invention has excellent optical properties such as high refractive index, low birefringence, and high transparency, and is also excellent in various properties such as heat resistance and mechanical properties. Therefore, the polycarbonate-based resin (or resin composition thereof) of the present invention can be suitably used for optical lenses, optical films, optical sheets, pickup lenses, prisms, holograms, liquid crystal films, organic EL films, and the like. In addition, the polycarbonate-based resin (or resin composition thereof) of the present invention includes paint, antistatic agent, ink, adhesive, pressure-sensitive adhesive, resin filler, charging tray, conductive sheet, protective film (for example, electronic equipment, liquid crystal Protective films for members, etc.), electrical / electronic materials (for example, carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, hologram recording materials, etc.), electrical / electronic components or equipment (for example, optical disks, inkjet printers, Resins for digital paper, organic semiconductor lasers, dye-sensitized solar cells, EMI shield films, photochromic materials, organic EL elements, color filters, etc.), mechanical parts or equipment (for example, automobiles, aerospace materials, sensors, sliding) It can be suitably used for a resin for a member.

  In particular, since the polycarbonate-based resin of the present invention is excellent in optical characteristics, it is useful for forming a molded article for optical use (optical molded article). Examples of the molded article for optics composed of the polycarbonate-based resin include an optical film, an optical lens, and an optical sheet.

  As an optical film, a polarizing film (and a polarizing element and a polarizing plate protective film constituting it), a retardation film, an alignment film (alignment film), a viewing angle expansion (compensation) film, a diffusion plate (film), a prism sheet, Light guide plate, brightness enhancement film, near infrared absorption film, reflection film, antireflection (AR) film, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, anisotropic conductive film (ACF) ), Electromagnetic wave shielding (EMI) film, film for electrode substrate, film for color filter substrate, barrier film, color filter layer, black matrix layer, adhesive layer or release layer between optical films. In particular, the film of the present invention is useful as an optical film for use in an apparatus display. Specific examples of the display member (or display) including the optical film of the present invention include personal computer monitors, televisions, and information terminals (for example, mobile phones such as smartphones, tablet terminals, etc.). FPD devices (for example, LCD, PDP, etc.) such as game machines, car navigation systems, and touch panels.

  As an optical lens, for example, a lens that requires a low Abbe number such as a camera lens [for example, a lens mounted on a small device having a camera function (or a mobile device such as a mobile phone, a digital camera, or the like)] Etc.

Claims (14)

Polycarbonate-type resin containing the structural unit represented by following formula (1).

(In the formula, ring Z ¹ is a naphthalene ring, A ¹ is an alkylene group, R ¹ and R ² are substituents, n is an integer of 0 or more, m is an integer of 0 to 4, and k is an integer of 0 to 6. ) The polycarbonate-type resin of Claim 1 whose structural unit represented by Formula (1) is a structural unit represented by following formula (1a).

(In the formula, A ¹ is an alkylene group, R ¹ and R ^2a are substituents, n is an integer of 0 or more, m is an integer of 0 to 4, and k1 is an integer of 0 to 3) The polycarbonate resin according to claim 1 or 2, wherein in formula (1) or (1a), A ¹ is a C _2-3 alkylene group and n is 1.   The polycarbonate-type resin in any one of Claims 1-3 whose structural unit represented by Formula (1) is 30 mol% or more in all the structural units. The polycarbonate-type resin in any one of Claims 1-4 which further contains the structural unit represented by following formula (2) and / or the structural unit represented by following formula (3).

(In the formula, ring Z ¹ is a naphthalene ring, A ¹ and A ² are alkylene groups, R ^{1 to} R ³ are substituents, n is an integer of 0 or more, m and p are integers of 0 to 4, and k is 0 to 0. (It is an integer of 6.)

(In the formula, ring Z ¹ is a naphthalene ring, A ¹ and A ³ are alkylene groups, R ¹ , R ² and R ⁴ are substituents, n is an integer of 0 or more, and m, q and r are integers of 0 to 4. , K is an integer from 0 to 6)   The molar ratio between the structural unit represented by the formula (1) and the structural unit represented by the formula (2) and / or the structural unit represented by the formula (3) is the former / the latter = 90 / 10-5. The polycarbonate resin according to claim 5, which is / 95.   The polycarbonate-type resin of Claim 5 or 6 which is a polyester carbonate containing the polyester block unit which makes the structural unit represented by Formula (2) a repeating unit. The polycarbonate-type resin in any one of Claims 1-7 which further contains the structural unit represented by following formula (5).

Wherein X is a direct bond or an alkylene group, A ⁴ is an alkylene group, R ⁵ and R ⁶ are substituents, s is an integer of 0 or more, t is an integer of 0 to 2, and u is an integer of 0 to 4. is there)   The polycarbonate resin according to claim 8, wherein the molar ratio between the structural unit represented by the formula (1) and the structural unit represented by the formula (5) is the former / the latter = 80/20 to 10/90. In a film stretched three times at a temperature of 20 ° C., a refractive index of 1.668 to 1.700 at a wavelength of 589 nm, an Abbe number of 17 to 23 at 20 ° C., and 10 ° C. higher than the glass transition point. 10. The polycarbonate resin according to claim 1, wherein the absolute value of birefringence at 20 ° C. and a wavelength of 600 nm is 0.001 × 10 ⁻⁴ to 75 × 10 ⁻⁴ .   The polycarbonate resin according to any one of claims 1 to 10, which has a glass transition point of 160 ° C or higher.   The molded object containing the polycarbonate-type resin in any one of Claims 1-11.   The molded article according to claim 12, which is an optical member.   The molded article according to claim 12 or 13, which is an optical film, an optical sheet, or an optical lens.