JP7082872B2 - High heat resistant polycarbonate resin and molded product - Google Patents

Description

The present invention presents a novel polycarbonate resin having a structural unit derived from 9,9-bis (hydroxyfused polycyclic aryl) fluorene, a method for producing the same, and a molded body (for example, an optical film, an optical lens) formed of the polycarbonate resin. Etc.) and a method of introducing the above-mentioned structural unit to improve heat resistance.

Polycarbonate resin is used as an optical molded material because of its excellent transparency, dimensional stability, and mechanical properties. As a polycarbonate resin having excellent optical properties, Japanese Patent Application Laid-Open No. 10-101787 (Patent Document 1) discloses a polycarbonate resin mainly containing a repeating unit having a 9,9-bisphenylfluorene skeleton. In the examples of Cited Document 1, 2,2'-[9H-fluorene-9-iridenbis (4,1-phenyleneoxy)]-bisethanol [9,9-bis [4- (2-hydroxyethoxy)] as a polymerization component ) Phenyl] Fluorene (abbreviation: BPEF)] and the like are used to prepare a polycarbonate resin.

The glass transition temperature of the polycarbonate resin described in Patent Document 1 is relatively high, about 145 ° C. However, it may not be applicable to applications that are expected to be manufactured or used in a high temperature environment (for example, an in-vehicle lens).

Japanese Patent Application Laid-Open No. 2004-331688 (Patent Document 2) describes a polycarbonate resin having good heat resistance and thermal stability, low birefringence, and excellent transparency as 50 to 95 mol% of the total aromatic dihydroxy component. Is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (BCF), and 50 to 5 mol% is a general bisphenol, and a polycarbonate copolymer is disclosed. In the examples of Patent Document 2, 55 mol% or more of BCF and 2,2-bis (4-hydroxyphenyl) propane (“bisphenol A”) and 1,3-bis [2- (4-hydroxyphenyl) propyl) ] Polycarbonate resin using benzene ("bisphenol M") has been prepared.

According to the polycarbonate resin described in Patent Document 2, the glass transition temperature can be set high. However, for that purpose, it is necessary to introduce a large amount of BCF-derived structural units, and there is a limit to the improvement of the refractive index.

Japanese Unexamined Patent Publication No. 10-101787 Japanese Unexamined Patent Publication No. 2004-331688

An object of the present invention is a polycarbonate resin having high heat resistance and a high refractive index that can withstand production and use in a high temperature environment, a method for producing the same, and a molded body containing the polycarbonate resin (for example, an optical film, optics). Lens etc.) is to be provided.

Another object of the present invention is to provide a polycarbonate resin capable of achieving both high heat resistance and low birefringence, a method for producing the same, and a molded product containing the polycarbonate resin.

Still another object of the present invention includes a polycarbonate resin which can easily form an optical member (lens or the like) even if it has high heat resistance and has high mechanical properties, a method for producing the same, and the polycarbonate resin. The purpose is to provide a molded body.

Another object of the present invention is a polycarbonate resin having high heat resistance even if the number of structural units derived from 9,9-bis (hydroxyphenyl) fluorene is small, a method for producing the same, and a molded product containing the polycarbonate resin (for example, It is an object of the present invention to provide a method for improving heat resistance by introducing an optical film, an optical lens, etc.) and the structural unit.

As a result of diligent studies to achieve the above problems, the present inventors have found that a novel polycarbonate resin containing 9,9-bis (hydroxycondensation polycyclic aryl) fluorene as a polymerization component has high heat resistance and refractive index. And completed the present invention. Further, according to the present invention, it is possible to achieve both high heat resistance and high refractive index and low birefringence, which are contradictory characteristics.

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

(In the formula, ring Z ¹ is a condensed polycyclic arene ring, R ¹ and R ² are substituents, and k and m are integers of 0 or more, respectively).

In the formula (1), the ring Z ¹ may be a naphthalene ring, R ² may be a C _1-6 alkyl group or a C _6-12 aryl group, and m may be an integer of 0 to 2. The ratio of the structural unit represented by the formula (1) may be about 1 to 50 mol% with respect to the entire structural unit of the polycarbonate resin.

The polycarbonate resin may further contain a structural unit represented by the following formulas (2) and / or (3).

(In the formula, ring Z ² is an arene ring, R ³ and R ⁴ are substituents, n and p are integers of 0 or more, A ¹ is an alkylene group, and q is an integer of 1 or more).

(In the formula, X is a direct bond or an alkylene group, R ⁵ and R ⁶ are substituents, A ² is an alkylene group, r is an integer of 0 to 4, s is an integer of 0 to 2, and t is an integer of 0 or more. Shows).

In the above formula (2), ring Z ² is a C _6-12 arene ring, R ⁴ is a C _1-6 alkyl group or C _6-12 aryl group, p is an integer of about 0 to 2, and A ¹ is a linear chain. Alternatively, the branched C _2-6 alkylene group and q may be an integer of about 1 to 10.

Further, in the above formula (3), X is a direct bond or an alkylene group, R ⁵ and R ⁶ are a C _1-6 alkyl group or a C _6-12 aryl group, respectively, and A ² is a linear or branched C ₂ . A _-6 alkylene group, r may be an integer of about 0 to 2, s may be 0 or 1, and t may be an integer of about 0 to 10.

The ratio of the structural unit represented by the formula (1) to the total amount of the structural units represented by the formulas (2) and (3) is, for example, the former / the latter (molar ratio) = 5/95 to 25. It may be about / 75. Further, when both the structural unit represented by the formula (2) and the structural unit represented by the formula (3) are included, the structural unit represented by the formula (2) and the structural unit represented by the formula (3) are used. The ratio with the represented structural unit may be, for example, the former / the latter (molar ratio) = about 20/80 to 70/30.

The polycarbonate resin may have a glass transition temperature Tg of about 160 to 200 ° C., a weight average molecular weight Mw of about 2 × 10 ⁴ to 10 × 10 ⁴ , and a temperature of 20 ° C. and a wavelength of 589 nm. The refractive index may be about 1.64 to 1.7, the Abbe number at a temperature of 20 ° C. may be about 17 to 23, and the material is stretched three times at a temperature 10 ° C. higher than the glass transition temperature. The absolute value of the double refraction (triple double refraction) at a temperature of 20 ° C. and a wavelength of 600 nm in the film may be about 0.001 × 10 ^-4 to 75 × 10 ^-4 .

The present invention comprises a method for producing the polycarbonate resin by reacting a diol component containing a first diol component for forming a structural unit represented by the formula (1) with a carbonic acid diester, and the polycarbonate. It includes a molded body containing a resin (for example, an optical film, an optical sheet, an optical lens, etc.). The molded body may be, for example, an optical member such as an in-vehicle optical lens.

In the present specification and claims, the term "polycarbonate resin" means a resin containing a carbonate bond (carbonic acid ester bond) as a linking group of the main chain. That is, the term "polycarbonate resin" is used not only as a polymer formed only by a carbonate bond as a linking group of a main chain, but also as a polymer containing a linking group other than the carbonate bond (for example, an ester bond) in addition to the carbonate bond (for example, an ester bond). , Polyester carbonate, etc.) are also included.

Since the polycarbonate resin of the present invention has a structural unit derived from 9,9-bis (hydroxyfused polycyclic aryl) fluorene, it has high heat resistance and a refractive index.

Generally, in order to improve the heat resistance and the refractive index of a resin, for example, a method of introducing a condensed polycyclic allene ring skeleton is known, but a resin into which such a skeleton is introduced has a birefringence value. Tends to grow. Since such high heat resistance and refractive index and low birefringence have a trade-off relationship with each other, it is extremely difficult to satisfy these characteristics in a well-balanced manner. However, according to the polycarbonate resin of the present invention, these contradictory characteristics can be compatible in a well-balanced manner.

Further, since the glass transition temperature Tg of the polycarbonate resin can be adjusted within a predetermined range, it is possible to maintain a good formability even though the heat resistance is high. Therefore, the optical member (lens or the like) can be easily molded. Furthermore, the molded product containing the polycarbonate resin of the present invention also has high mechanical properties.

According to the present invention, the heat resistance can be improved even if the proportion of the structural unit derived from 9,9-bis (hydroxyphenyl) fluorene is small, so that the optical properties such as the refractive index and birefringence are not impaired (adverse effects). It is also possible to improve heat resistance (without giving).

[Polycarbonate resin]
(Constituent unit represented by equation (1))
The polycarbonate resin of the present invention contains a structural unit represented by the following formula (1) (simply also referred to as a first structural unit (1)).

(In the formula, ring Z ¹ is a condensed polycyclic arene ring, R ¹ and R ² are substituents, and k and m are integers of 0 or more, respectively).

In the above formula (1), the fused polycyclic allene ring represented by the ring Z ¹ is, for example, a fused bicyclic alley ring (for example, a fused bicyclic _allene ring such as a naphthalene ring or an inden ring). Rings), fused bicyclic allene rings such as fused tricyclic allene rings (eg, anthracene rings, phenanthrene rings, etc.) and the like. Preferred ring Z ¹ includes fused polycyclic C _10-16 arene rings such as naphthalene ring and anthracene ring (preferably fused polycyclic C _10-14 arene ring), and naphthalene ring is particularly preferable. The ^two rings Z1 connected to the carbon atom at the 9-position of the fluorene ring may be of different types, but are usually the same.

Further, the substitution position of the ring Z1 with respect to the 9 ^- position of the fluorene ring is not particularly limited. For example, when the ring Z1 is a naphthalene ring, the ¹ -position or the 2-position of the naphthalene ring is relative to the 9-position of the fluorene ring. It may be substituted at any position (replacement in the relationship of 1-naphthyl or 2-naphthyl), and it is preferable to replace it at the 2-position.

The substituent represented by the group ^R1 is a hydrocarbon group [for example, a linear group such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc.) or a linear group. Branched chain C _1-6 alkyl group, etc.), aryl group (eg, C _6-10 aryl group such as phenyl group), etc.], cyano group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.) And so on. Among these groups R ¹ , alkyl groups (for example, linear or branched C _1-4 alkyl groups), cyano groups and halogen atoms are preferable, and alkyl groups (particularly, C _1-3 such as methyl groups) are preferable. Alkyl group) is preferable.

The substitution number k of the group R ¹ is an integer of 0 or more, for example, an integer of about 0 to 4, preferably an integer of about 0 to 2, more preferably 0 or 1, and particularly 0. In the two different benzene rings constituting the fluorene ring, the substitution number k may be the same or different from each other. Further, the type of the group ^R1 may be the same or different from each other in two different benzene rings constituting the fluorene ring, and when k is 2 or more, two or more groups R are substituted with the same benzene ring. The types of ¹ may be the same or different from each other. Further, the substitution position of the group ^R1 is not particularly limited, and may be, for example, the 2nd to 7th positions (2nd position, 3rd position, 7th position, etc.) of the fluorene ring.

Examples of the substituent represented by the group R ² include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom); a hydrocarbon group {for example, an alkyl group (methyl group, ethyl group, propyl group, etc.). A linear or branched C _1-10 alkyl group such as an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, preferably a linear or branched C _1-6 alkyl group, and further. Preferred is a linear or branched C _1-4 alkyl group); cycloalkyl group (eg, C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group); aryl group [eg, phenyl group, alkyl Phenyl group (eg, methylphenyl group (tril group), dimethylphenyl group (chysilyl group), etc.), biphenylyl group, _C6-12aryl group such as naphthyl group, etc.]; Aralkyl group (eg, benzyl group, phenethyl group, etc.) C _6-10 aryl-C _1-4 alkyl group, etc.)}; alkoxy group (eg, methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, etc.) Linear or branched C _1-10 alkoxy group); cycloalkyloxy group (eg, C _5-10 cycloalkyloxy group such as cyclohexyloxy group); aryloxy group (eg, phenoxy group, etc.) C _6-10 aryloxy group, etc.); Aralkyloxy group (eg, C _6-10aryl -C _1-4 alkyloxy group, such as benzyloxy group); Alkylthio group (eg, methylthio group, ethylthio group, propylthio group, etc.) , N-butylthio group, C _1-10 alkylthio group such as t-butylthio group); cycloalkylthio group (eg, C _5-10 cycloalkylthio group such as cyclohexylthio group); arylthio group (eg, thiophenoxy group) C _6-10 arylthio groups such as C 6-10 arylthio groups); aralkylthio groups (eg C _6-10 aryl-C _1-4 alkylthio groups such as benzylthio groups); acyl groups (eg C _1-6 acyls such as acetyl groups) Group; nitro group; cyano group; substituted amino group [eg, dialkylamino group (eg, diC _1-4 alkylamino group such as dimethylamino group); bis (alkylcarbonyl) amino group (eg, diacetylamino) Bis (C _1-4 alkyl-carbonyl) amino group such as group) etc.] etc. Will be.

Among these groups ^R2 , representatively, a halogen atom, a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group and the like Can be mentioned. Preferred groups ^R2 include an alkyl group (such as a linear or branched C _1-6 alkyl group such as a methyl group), an aryl group (such as a C _6-12 aryl group such as a phenyl group), and an alkoxy group (methoxy). Linear or branched C _1-4 alkyl groups such as groups), in particular alkyl groups (particularly linear or branched C _1-4 alkyl groups such as methyl groups), aryl groups (phenyl groups). C _6-10 aryl group, etc.).

The substitution number m of the group R ² may be an integer of 0 or more, and can be appropriately selected depending on the type of the ring Z ¹ . For example, it is about 0 to 8, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, particularly preferably 0 or 1, and particularly preferably 0. In the ^two rings Z1 bonded to the carbon at the 9th position of the fluorene ring, the substitution number m of each may be the same or different from each other. Further, the types of the groups R ² substituting for the two different rings Z ¹ may be the same or different from each other. When the number of substitutions m is 2 or more, the types of the ^two or more groups R2 substituted with the same ring Z ¹ may be the same or different from each other. The substitution position of the group R ² is not particularly limited, and may be substituted at a position other than the bond position between the ring Z1 and the 9 ^- position of the oxygen atom (—O—) and the fluorene ring.

The substitution position of the oxygen atom (-O-) and the ester bond [-OC (= O)-] forming a carbonate bond for connecting the 9,9-bis condensed polycyclic arylfluorene skeleton is the ring Z. The position is not particularly limited as long as it is a position ^other than the bonding position between ¹ and the fluorene ring. In many cases, it is substituted at any of the 5th to 8th positions of the fluorene ring, and the 1st or 2nd position of the naphthalene ring is substituted with respect to the 9th position of the fluorene ring (in the relationship of 1-naphthyl or 2-naphthyl). Substitution), it is preferable to replace the replacement position with a relationship of 1,5, 2,6, etc., and in particular, it is preferable to replace with a relationship of 2,6.

As the first structural unit (1), typically, for example, 9,9-bis (hydroxy C _10-14 fused polycyclic aryl) fluorene [for example, 9,9-bis (6-hydroxy-2-). Units derived (or corresponding) from the first diol component such as naphthyl) fluorene, 9,9-bis (hydroxy-1-naphthyl) fluorene and the like 9,9-bis (hydroxynaphthyl) fluorene, etc. Can be mentioned.

These first structural units (1) may be used alone or in combination of two or more. Among these first structural units (1), the unit derived from 9,9-bis (hydroxynaphthyl) fluorene is preferable, and the unit derived from 9,9-bis (6-hydroxy-2-naphthyl) fluorene is particularly preferable. preferable.

The ratio of the first structural unit (1) is not particularly limited, and can be selected from a wide range of, for example, about 0.01 to 100 mol% with respect to the entire structural unit of the polycarbonate resin. The preferred range is as follows, in stages, 0.1 to 90 mol%, 0.5 to 70 mol%, 1 to 50 mol%, 3 to 40 mol%, 5 to 30 mol%, and more preferably. Is 8 to 25 mol%, particularly preferably 10 to 20 mol%.

If the ratio of the first structural unit (1) is too small, the heat resistance and the refractive index may not be improved. However, in the present invention, even if the ratio of the first structural unit (1) is relatively small (configuration). With respect to the entire unit, for example, 50 mol% or less, preferably 30 mol% or less, more preferably 15 mol% or less), surprisingly, the heat resistance can be greatly improved. Therefore, the ratio of the first structural unit (1) is, for example, 2 to 23 mol%, preferably 4 to 18 mol%, and more preferably 7 to 13 mol% with respect to the entire constituent unit of the polycarbonate resin. There may be. The present invention also includes a method of introducing the first structural unit (1) into the polycarbonate resin (for example, at the ratio of the above-mentioned example) to improve the heat resistance of the polycarbonate resin. By such a method, the heat resistance of the polycarbonate resin can be improved even if the proportion of the first structural unit (1) is small, so that the balance of other properties such as the optical properties of the polycarbonate resin (for example, the refractive index) can be improved. Heat resistance can be improved without significantly affecting the balance with birefringence).

(Constituent unit represented by equation (2))
In addition to the first structural unit (1), the polycarbonate resin may further contain a structural unit represented by the following formula (2) (simply also referred to as a second structural unit (2)). By including the second structural unit (2), not only the polymerization reactivity but also the heat resistance and optical properties (high refractive index, low birefringence, etc.), moldability, mechanical properties, etc. of the obtained polycarbonate resin can be obtained. The characteristics can be improved.

(In the formula, ring Z ² is an arene ring, R ³ and R ⁴ are substituents, n and p are integers of 0 or more, A ¹ is an alkylene group, and q is an integer of 1 or more).

In the above formula (2), examples of the arene ring (aromatic hydrocarbon ring) represented by ring Z ² include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like. The formula arene ring includes a fused polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-aggregated aromatic hydrocarbon ring), and the like.

Examples of the fused polycyclic arene ring include a fused bicyclic arene ring (for example, a fused bicyclic _C10-16 arene ring such as a naphthalene ring and an inden ring) and a fused tricyclic arene ring (for example, an anthracene ring). , Phenantren ring, etc.) and other fused two- to four-cyclic arene rings. Preferred fused polycyclic arene rings include fused polycyclic C _10-16 arene rings (preferably fused polycyclic C _10-14 arene rings) such as naphthalene rings and anthracene rings, and naphthalene rings are particularly preferable. preferable.

The ring-assembled arene ring includes a bi-C 6-12 arene ring such as a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.), and a tellarene ring (for example, a biphenyl ring, a bi-C _6-12 arene ring, etc.). For example, a tel C _6-12 arene ring such as a terphenylene ring) can be exemplified. Preferred ring-set arene rings include biC _6-10 arene rings and the like, with biphenyl rings being particularly preferred.

The types of the two rings Z ² may be the same or different from each other and are usually often the same. Of the ring Z2, a ^C _6-12 arene ring such as a benzene ring, a naphthalene ring, and a biphenyl ring is preferable, and a C _6-10 arene ring such as a benzene ring and a naphthalene ring is preferable. A benzene ring is preferable from the viewpoint of easy reduction, and a naphthalene ring is preferable from the viewpoint of further improving the glass transition temperature and increasing the refractive index. In particular, a benzene ring is preferable because it has an excellent balance between high heat resistance and low birefringence.

The substitution position of the ring Z ² bonded to the 9-position of the fluorene ring is not particularly limited. For example, when the ring Z ² is a benzene ring, it may be at any of the 1st to 6th positions, and when the ring Z ² is a naphthalene ring, it may be at either the 1st or 2nd position. , When the ring Z ² is a biphenyl ring, it may be at any of the 2-position, 3-position, and 4-position.

In the above formula (2), the group R ³ corresponds to the group R ¹ , the group R ⁴ corresponds to the group R ² , the number of substitutions n corresponds to the number of substitutions k, and p corresponds to the number of substitutions m, respectively. The same groups and numerical ranges as those illustrated in the section of the structural unit represented by the above can be exemplified, and they may be the same including preferred embodiments.

Examples of the alkylene group represented by the group A ¹ include an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, a tetramethylene group, and a 2,2-dimethyl-1,3-propanediyl group. Examples thereof include a chain-shaped or branched chain-shaped C _2-6 alkylene group, and from the viewpoint of optical properties, a linear or branched C _2-4 alkylene group is preferable, and an ethylene group, a propylene group and the like are more preferable. Examples thereof include linear or branched C _2-3 alkylene groups (particularly ethylene groups).

The q (number of repetitions of each group OA ¹ ), which is the number of repetitions (number of addition moles) of the oxyalkylene group OA ¹ , may be an integer of 1 or more (for example, an integer of 1 to 10), but the optical characteristics and From the viewpoint of polymerizable property, it may be, for example, 1 to 3, preferably 1 to 2, and more preferably 1.

^The groups A1 on both sides may be the same alkylene group or different alkylene groups. Further, when q is ² or more polyoxyalkylene groups, the plurality of groups A1 constituting the polyoxyalkylene group may be different alkylene groups, or may be usually the same alkylene group.

The substitution position of the oxyalkylene group (OA ¹ ) -containing group for forming the main chain of the polycarbonate resin is not particularly limited as long as it is a position other than the bond position between the ring Z ² and the fluorene ring, and is not particularly limited, for example, the ring Z. When ² is a benzene ring, it may be substituted at any position of the 2nd to 6th positions of the phenyl group bonded to the 9th position of the fluorene ring, and it may be replaced with the 3rd to 5th position (preferably the 4th position). In many cases. When the ring Z ² is a naphthalene ring, it is usually substituted at any position of the 5 to 8 positions of the naphthyl group bonded to the 9-position of the fluorene ring at the 1-position or the 2-position, and the fluorene ring has a fluorene ring. The 1st or 2nd position of the naphthalene ring is substituted for the 9th position (substituted in the relation of 1-naphthyl or 2-naphthyl), and the 1st, 5th and 2nd and 6th positions (particularly) are substituted for this substitution position. , 2nd and 6th positions), etc. are preferable. When ring Z ² is a biphenyl ring, it is usually substituted at any of the 2-position, 6-position and 3'-5'-position of the biphenylyl group bonded to the 9-position of the fluorene ring at the 3-5-position. In many cases, the 9-position of the fluorene ring is replaced by the 3- or 4-position of the biphenyl ring (replaced by the relationship of 3-biphenylyl or 4-biphenylyl), and the 3rd and 6th positions are substituted with respect to this substitution position. , 2nd and 4th positions (particularly, 3rd and 6th positions) are preferably substituted.

As the second structural unit (2), typically, for example, 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes in which ring Z ² is a benzene ring {for example, 9,9-bis [hydroxyl]. (Poly) alkoxyphenyl] fluorene [eg, 9,9-bis [4- (2-hydroxyethoxy) -phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -phenyl] fluorene, 9, 9-bis [4- (2- (2-hydroxyethoxy) ethoxy) -phenyl] fluorene, etc. 9,9-bis [hydroxy (poly) C _2-4 alkoxyphenyl] fluorene, etc.]; 9,9-bis [ Hydroxy (poly) alkoxy-alkylphenyl] fluorene [eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy)- 9,9-bis [hydroxy (poly) C _2-4 alkoxy- (mono or di) C _1-4 alkylphenyl] fluorene, etc., such as 3,5-dimethylphenyl] fluorene; 9,9-bis [hydroxy (hydroxy () Poly) alkoxy-arylphenyl] fluorene [eg, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, etc. 9,9-bis [hydroxy (poly) C _2-4 alkoxy- C _6-10 arylphenyl] fluorene, etc.], etc.}; 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes in which ring Z2 is a naphthalene ring ^{ for example, 9,9-bis [hydroxy (poly) alkoxy) Naftil] Fluoren [eg, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluoren, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluoren, 9, 9,9- bis [6- (2- (2-hydroxyethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, etc. Units derived (or corresponding to) from the second diol component such as bis [hydroxy (poly) C _2-4 alkoxynaphthyl] fluorene, etc.] and the like can be mentioned.

In the present specification and claims, "(poly) alkoxy" is used to mean that both an alkoxy group and a polyalkoxy group are included.

These second structural units (2) may be used alone or in combination of two or more. Of these second structural units (2), 9,9-bis [hydroxy (poly) C _2-4 alkoxyphenyl] fluorene and 9,9-bis [hydroxy (poly) C _2-4 alkoxynaphthyl] fluorene. Units derived from such substances are preferable, and in particular, 9,9-bis [hydroxy (mono to deca) C _2-3 alkoxyphenyl] fluorene (particularly 9,9-bis) is preferable because it is easier to reduce double refraction. Units derived from [4- (2-hydroxyethoxy) -phenyl] fluorene, etc.) are preferable, and from the viewpoint of further improving the glass transition temperature and increasing the refractive index, 9,9-bis [hydroxy (mono to deca) ) C _2-3 Alkoxynaphthyl] fluorene (particularly, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, etc.)-derived units are preferred.

When the second structural unit (2) is included, the ratio of the first structural unit (1) to the second structural unit (2) is, for example, 0.1/99 as the former / latter (molar ratio). You can select from a wide range of about 9.9 to 90/10. The preferred range is as follows, in stages, 0.5 / 99.5 to 70/30, 1/99 to 50/50, 2/98 to 40/60, 3/97 to 30/70, 4/96. It is from 25/75 to 5/95 to 20/80, more preferably 5/95 to 15/85, and even more preferably 7/93 to 13/87. If the number of the first structural unit (1) is too large, the polymerization reactivity may decrease, and if the number of the second structural unit (2) is too large, the heat resistance and the refractive index may decrease.

(Constituent unit represented by equation (3))
The polycarbonate resin may further contain a structural unit represented by the following formula (3) (simply also referred to as a third structural unit (3)) as necessary, as long as the effect of the present invention is not impaired. good. By including the third structural unit (3), it becomes easy to improve the optical characteristics (high refractive index and the like) of the obtained polycarbonate resin.

(In the formula, X is a direct bond or an alkylene group, R ⁵ and R ⁶ are substituents, A ² is an alkylene group, r is an integer of 0 to 4, s is an integer of 0 to 2, and t is an integer of 0 or more. Shows).

In the above formula (3), examples of the alkylene group represented by X include a linear or branched chain such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a 1,2-butanjiyl group and a tetramethylene group. C _1-4 alkylene group and the like can be mentioned. As X, a direct bond or a _C1-2 alkylene group (for example, a methylene group) is preferable, and a direct bond is particularly preferable, from the viewpoint of optical properties (for example, high refractive index, low Abbe number, low birefringence, etc.). ..

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

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

In the two different naphthalene rings constituting the formula ( ³ ), the substitution number r and the substitution number s may be the ^same or different from each other, and the types of the groups R5 and R6 are the substitution number r, respectively. They may be the same or different from each other depending on s. Further, when two or more groups R5 and / or ^two or more groups R6 are substituted in the ^same naphthalene ring (when r is 2 or more and / or s is ² ), types of two or more groups R5. And / or the types of the ^two groups R6 may be the same or different from each other.

Further, the substitution position of the group R5 is not particularly limited, and may be substituted at any position among the ^5th to 8th positions (or the 5'to 8'positions) of the naphthalene ring. The substitution position of the group R ⁶ is not particularly limited as long as it is a position other than the substitution position of the oxyalkylene group (OA ² ) -containing group and the linking group X.

The alkylene group represented by the group A ² constituting the oxyalkylene group (OA ² ) is, for example, the same as the alkylene group A ¹ exemplified in the above formula (2), including a preferable embodiment.

The number of repetitions t of the oxyalkylene group (OA ² ) may be an integer of 0 or more, and the preferred range is as follows, stepwise, 0 to 10, 0 to 3, 0 to 2, and more preferably. Is 0 or 1. From the viewpoint of optical characteristics (high refractive index, low Abbe number, low birefringence, etc.) and heat resistance, the repetition number t is particularly preferably 0, and from the viewpoint of suppressing coloring, the repetition number t is particularly 1. Is preferable.

The substitution position of the oxyalkylene group (OA ² ) -containing group forming the main chain of the polycarbonate resin may be any of the 2nd to 4th positions (or 2'to 4'positions) of the naphthalene ring. The 2nd position (or 2'position) is particularly preferable from the viewpoint of reducing birefringence.

As the third structural unit (3), typically, for example, dihydroxy-1,1'-vinaphthalenes to which X is directly bonded {for example, dihydroxy-1,1'-vinaphthalene (for example, 2,2'). -Dihydroxy-1,1'-Binaphthalene, etc.); Bis [hydroxy (poly) alkoxy] -1,1'-Binaphthalene [for example, 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, etc. 2,2' -Units derived (or corresponding to) from the third diol component such as bis [hydroxy (mono to deca) C _2-4 alkoxy] -1,1'-vinaphthalene, etc.} can be mentioned.

These third structural units (3) may be used alone or in combination of two or more. Of these third structural units (3), dihydroxy-1,1'-vinaphthalene (particularly 2,2) is used from the viewpoint of easily improving optical characteristics (high refractive index, low Abbe number, etc.) and heat resistance. Units derived from'-dihydroxy-1,1'-vinaphthalene, etc.) are preferable, and from the viewpoint of suppressing coloring, 2,2'-bis [hydroxy (mono to deca) C _2-4 alkoxy] -1,1 '-Vinaphthalene (particularly 2,2'-bis (2-hydroxyethoxy) -1,1'-, such as vinaphthalene, 2,2'-bis [hydroxy (mono to tri) C _2-3 alkoxy] -1,1 '-Units derived from (such as vinaphthalene) are preferred.

When the third structural unit (3) is included, the ratio of the first structural unit (1) to the third structural unit (3) is, for example, 0.1/99 as the former / latter (molar ratio). You can select from a wide range of about 9.9 to 90/10. The preferred ranges are as follows, in stages, 0.5 / 99.5 to 70/30, 1/99 to 50/50, 5/95 to 45/55, 10/90 to 40/60, 12/88. It is ~ 35/65, 15/85 to 30/70, 8/92 to 35/65, more preferably 10/90 to 25/75, and even more preferably 12/88 to 20/80. If the ratio of the third structural unit (3) is too large, the heat resistance may decrease.

The polycarbonate resin of the present invention contains at least the first structural unit (1), and the other structural units are not particularly limited, but for example, the second structural unit (2) and / or the third structural unit ( 3) is preferably contained.

The ratio of the first constituent unit (1) to the total amount of the second constituent unit (2) and the third constituent unit (3) is, for example, 0.1/99 as the former / latter (molar ratio). You can select from a wide range of about 9.9 to 99/1. The preferred range is as follows, in stages, 0.5 / 99.5 to 90/10, 1/99 to 70/20, 2/98 to 50/50, 3/97 to 30/70, 5/95. It is ~ 25/75, more preferably 7/93 to 20/80, and even more preferably 9/91 to 15/85. If the number of the first structural unit (1) is too small, the heat resistance and the refractive index may decrease. In the present invention, even if the ratio of the first structural unit (1) is relatively small, it is easy to improve the characteristics such as heat resistance and the refractive index. Therefore, even if the ratio is about 6/94 to 13/87. good.

Only one of the second structural unit (2) and the third structural unit (3) may be contained, or both may be contained, but the heat resistance and the refractive index are high and the compound is low. It is particularly preferable to include the second structural unit (2) from the viewpoint that the refraction can be satisfied in a highly balanced manner.

When both the second structural unit (2) and the third structural unit (3) are included, the ratio between the second structural unit (2) and the third structural unit (3) is, for example, the former. / The latter (molar ratio) can be selected from a wide range of about 1/99 to 99/1. The preferred ranges are as follows, step by step, 5/95 to 90/10, 10/90 to 80/20, 20/80 to 70/30, 30/70 to 60/40, 35/65 to 55/45. , 25/75 to 45/55, more preferably 28/72 to 40/60, and even more preferably 30/70 to 35/65. If the ratio of the third structural unit (3) is too large, the heat resistance may decrease. When both the second structural unit (2) and the third structural unit (3) are included in the ratio as described above in addition to the first structural unit (1), the heat resistance, the refractive index and the birefringence are reduced. The balance can be easily adjusted.

(Other building blocks)
The polycarbonate resin is another structural unit not included in the range of the structural units represented by the above formulas (1) to (3) as long as the effect of the present invention is not impaired (simply, the fourth structural unit (simply, the fourth structural unit (simply)). 4) may also be included. Typically, as the fourth structural unit (4), for example, in the above formula (1), the ring Z ¹ is an allene ring other than the fused polycyclic alley ring (monocyclic alley ring such as benzene ring, biphenyl ring). , Etc.), which is a structural unit [9,9-bis (hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxyphenyl) fluorene; 9,9-bis (4-hydroxy-3-). 9,9-bis (hydroxy- (mono or di) alkylphenyl) fluorene such as methylphenyl) fluorene; 9,9-bis (hydroxy-) such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene. Arylphenyl) Structural units derived from (or corresponding to) fluorene, etc.]; Conventional structural units used as polycarbonate resins [biphenol; bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4) -Constituent units derived from bisphenols such as -hydroxyphenyl) ethane (bisphenol AD), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) sulfone (bisphenol S), etc. ] And so on.

These fourth structural units (4) (constituent units derived from the fourth diol component) may be used alone or in combination of two or more. The ratio of the fourth structural unit (4) may be, for example, 50 mol% or less (for example, 0.1 to 50 mol%), preferably 30 mol% or less, based on the entire constituent unit of the polycarbonate resin. , More preferably 10 mol% or less (particularly 5 mol% or less).

[Manufacturing method of polycarbonate resin]
The polycarbonate resin of the present invention reacts (polymerizes or condenses) a diol component with a phosgene or a carbonic acid diester (diphenyl carbonate, etc.) by a conventional method, for example, a phosgene method (solvent method) or an ester exchange method (melting method). ) Can be manufactured. The diol component may contain at least the first diol component for forming the structural unit represented by the above formula (1), and further contains the second to fourth diol components, if necessary. You may be. Of these methods, the transesterification method is preferable because it does not require a solvent.

In the transesterification method, the ratio of the carbonic acid diester may be, for example, about 0.8 to 1.5 mol, preferably about 0.9 to 1.2 mol, with respect to 1 mol of the diol component.

The transesterification reaction may be carried out in the presence of a catalyst. Examples of the catalyst include various catalysts used in the transesterification reaction, for example, nitrogen-containing compounds and metal compounds.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides (eg, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; and trialkyls such as trimethylbenzylammonium hydroxide. -Aralkylammonium hydroxide and the like); Tertiary amines (trialkylamines such as trimethylamine and triethylamine; dimethyl-aralkylamines such as dimethylbenzylamine; triarylamines such as triphenylamine) and the like.

Examples of metal compounds include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, titanium, etc.), and periodic table group 13 metals. Metal compounds containing metals such as (aluminum, etc.), periodic table Group 14 metals (germanium, etc.), periodic table Group 15 metals (antimon, etc.) are used. More specifically, for example, the alkoxide of the metal, an organic acid salt (acetate, propionate, etc.), an inorganic acid salt (borate salt, carbonate, etc.), an oxide, a hydroxide, and the like can be mentioned.

These catalysts can be used alone or in combination of two or more. Among these catalysts, nitrogen-containing compounds such as quaternary ammonium hydroxide are preferable, and among them, tetraalkylammonium hydroxide such as tetramethylammonium hydroxide is preferable. The amount of the catalyst used is, for example, about 0.01 × 10 ^-4 to 100 × 10 ^-4 mol, preferably about 0.1 × 10 ^-4 to 40 × 10 ^-4 mol, per 1 mol of the diol component. May be good.

Further, the reaction may be carried out in the presence of additives such as stabilizers (antioxidants, heat stabilizers, etc.), if necessary.

The reaction can usually be carried out in an atmosphere of an inert gas (nitrogen; noble gas such as helium, argon, etc.). The reaction can also be carried out 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 250 to 300 ° C. In particular, when diphenyl carbonate is used as the carbonic acid diester, it is effective to carry out polycondensation while distilling off phenol under high temperature and reduced pressure.

[Characteristics of polycarbonate resin]
Since the polycarbonate resin of the present invention contains the first structural unit, it has high heat resistance and a refractive index. Further, by including the second structural unit in addition to the first structural unit, it is possible to achieve both high heat resistance and low birefringence, which are contradictory characteristics, and improve moldability and mechanical characteristics. Further, by including the third structural unit, it is possible to form a polycarbonate resin having a good balance between heat resistance and optical properties (high refractive index, low Abbe number, low birefringence, etc.).

The polycarbonate resin of the present invention has a high glass transition temperature (Tg) and is excellent in heat resistance. The Tg of the polycarbonate resin may be usually 130 ° C. or higher, for example, about 130 to 250 ° C. The preferred range may be 140 to 230 ° C., 150 to 220 ° C., 155 to 210 ° C., more preferably 160 to 200 ° C., and even more preferably 165 to 190 ° C. in a stepwise manner. ..

From the viewpoint of ensuring not only high heat resistance but also good moldability, the Tg of the polycarbonate resin is, for example, 155 to 200 ° C, preferably 158 to 195 ° C, more preferably 160 to 190 ° C, still more preferably 162 to 185. The temperature is preferably about 165 to 180 ° C. In the polycarbonate resin of the present invention, the glass transition temperature can be easily adjusted within a range in which high heat resistance and good moldability can be compatible with each other by including the first structural unit and the like in the above range. Therefore, the polycarbonate resin of the present invention is suitable for applications that are expected to be exposed to a high temperature environment such as an in-vehicle optical lens.

The weight average molecular weight (Mw) of the polycarbonate resin of the present invention can be selected from the range of, for example, about 1.5 × 10 ⁴ to 50 × 10 ⁴ in terms of polystyrene in gel permeation chromatography (GPC). The preferred range is as follows, for example, 2 × 10 ⁴ to 30 × 10 ⁴ , 2 × 10 ⁴ to 20 × 10 ⁴ , 2 × 10 ⁴ to 15 × 10 ⁴ , 2 × 10 ⁴ to 10 × 10. ⁴ , 2.5 × 10 ⁴ to 8 × 10 ⁴ , more preferably 3 × 10 ⁴ to 8 × 10 ⁴ , still more preferably 3.5 × 10 ⁴ to 7.5 × 10 ⁴ Is.

The refractive index of the polycarbonate resin of the present invention at a temperature of 20 ° C. and a wavelength of 589 nm can be selected from, for example, in the range of about 1.63 to 1.75. The preferred range may be, for example, 1.64 to 1.7, 1.64 to 1.695, and more preferably 1.645 to 1.69 in a stepwise manner. In particular, the preferable range in the application where high refractive index is important is, for example, 1.65 to 1.75 and 1.66 to 1.72 in a stepwise manner, and more preferably 1.67 to 1. It may be about 0.7, more preferably about 1.68 to 1.695.

The Abbe number of the polycarbonate resin of the present invention at a temperature of 20 ° C. can be selected from the range of, for example, 23 or less (for example, about 17 to 23), for example, 22.5 or less (for example, about 17 to 21), preferably 20. It may be less than or equal to (for example, about 17 to 20), more preferably 19.5 or less (for example, about 17.5 to 19.5), and particularly preferably 19 or less (for example, about 18 to 19).

The absolute value of the birefringence of the polycarbonate resin of the present invention at a temperature of 20 ° C. and a wavelength of 600 nm (birefringence in a film uniaxially stretched three times at a temperature 10 ° C. higher than the glass transition point) is, for example, 100 × 10 ⁻ . It can be selected from the range of ⁴ or less (for example, about 0.001 × 10 ^-4 to 75 × 10 ^-4 ), and for example, 60 × 10 ^-4 or less (for example, 0.005 × 10 ^-4 to 50 × 10 ^-4 ). Approximately), preferably 40 × 10 ^-4 or less (for example, about 0.01 × 10 ^-4 to 30 × 10 ^-4 ), more preferably 20 × 10 ^-4 or less (for example, 0.1 × 10 ^-4 to about). 10 x 10 ^-4 or less), especially 8 x 10 ^-4 or less (for example, 0.5 x 10 ^-4 to 5 x 10 ^-4 ), especially 3 x 10 ^-4 or less (for example, 0.7 x 10). It may be about ^-4 to 2 × 10 ^-4 ). In the present specification and claims, this birefringence (triple birefringence) can be measured by the method described in Examples described later.

[Molded product]
Since the molded product of the present invention contains the polycarbonate resin and has excellent heat resistance and optical properties (high refraction rate, low birefringence, etc.), it is used for optics such as optical films, optical lenses, and optical sheets. It can be used as a member. The shape of the molded body is not particularly limited, and is, for example, a one-dimensional structure (for example, linear, thread-like, etc.), a two-dimensional structure (for example, film-like, sheet-like, plate-like, etc.), and a three-dimensional structure (for example, a film-like, sheet-like, plate-like, etc.). For example, a concave or convex lens shape, a rod shape, a hollow shape (tubular), etc.) can be mentioned.

The molded product of the present invention contains various additives [for example, fillers or reinforcing agents, coloring agents (for example, dyeing pigments, etc.), conductive agents, flame retardant agents, plasticizers, lubricants, stabilizers (for example, antioxidants, ultraviolet rays, etc.). Absorbents, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, defoaming agents, surface modifiers, low stress agents (eg, silicone oils, silicone rubbers, etc.) Plastic powder, various engineering plastic powder, etc.), carbon material, etc.] may be included. These additives may be used alone or in combination of two or more.

The molded body can be manufactured by 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, or the like.

In particular, the polycarbonate resin of the present invention is excellent in various optical properties, and is therefore useful for forming a film (particularly an optical film). 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) can be produced by forming (or molding) the polycarbonate resin by using a conventional film forming method, a casting method (solvent casting method), a melt extrusion method, a calendar method, or the like. ..

The film may be a stretched film. The film of the present invention can maintain low birefringence even if it is a stretched film. In addition, such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

The draw ratio may be about 1.1 to 10 times (preferably 1.2 to 8 times, more preferably 1.5 to 6 times) in the drawing direction in both uniaxial stretching and biaxial stretching. It may be usually about 1.1 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 if the stretching is equal (for example, 1.5 to 5 times in both the vertical and horizontal directions), the partial stretching (for example, 1.1 to 4 times in the vertical direction and 2 to 6 times in the horizontal direction). It may be double-stretched). Further, in the case of uniaxial stretching, it may be longitudinal stretching (for example, 2.5 to 8 times stretching in the longitudinal direction) or transverse stretching (for example, 1.2 to 5 times stretching in the transverse direction).

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

In addition, such a stretched film can be obtained by subjecting a film (or an unstretched film) after film formation to a stretching treatment. The stretching method is not particularly limited, and in the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used, and in the case of biaxial stretching, a tenter method (also referred to as a flat method) may be used by a tube method. Although it may be present, the tenter method having excellent 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 and the evaluation method of the obtained resin or film are shown below.

[material]
BPEF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, manufactured by Osaka Gas Chemical Co., Ltd. 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, manufactured by Osaka Gas Chemical Co., Ltd. BNF: 9,9-bis (6-hydroxy-2-naphthyl) fluorene, Osaka BINOL manufactured by Gas Chemical Co., Ltd .: 2,2'-dihydroxy-1,1'-binaphthalene, manufactured by Tokyo Kasei Kogyo Co., Ltd. BINOL-2EO: 2,2'-bis (2-hydroxyethoxy) -1,1' -Vinaphthalene (synthesized by Synthesis Example 2 described later)
DPC: Diphenyl carbonate.

[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 temperature (Tg)]
A sample was placed in an aluminum pan using a differential scanning calorimeter (“DSC 6220” manufactured by Seiko Instruments Co., Ltd.), and the glass transition temperature (Tg) was measured in the range of 30 to 200 ° C.

[Refractive index and Abbe number]
By hot pressing the sample at 200 to 240 ° C., a film having a thickness of 10 to 300 μm was formed. This film was cut into strips having a length of 20 to 30 mm and a width of 10 mm to obtain test pieces. For the obtained test piece, a multi-wavelength Abbe refractometer (“DR-M2 / 1550” manufactured by Atago Co., Ltd.) was used, and diiodomethane was used as the contact liquid, and the measurement temperature was 20 ° C. and the measurement wavelength was 486 nm (F line). ), Refractive indexes nF, nD, and nC at 589 nm (D line) and 656 nm (C line), respectively. The Abbe number was calculated by the following formula.

Abbe number = (nD-1) / (nF-nC).

[Birerefringence (or triple birefringence)]
By hot pressing the sample at 200 to 240 ° C., a film having a thickness of 200 to 600 μm was formed. This film was cut into strips of 10 mm × 50 mm and uniaxially stretched at 25 mm / min under a temperature condition of Tg + 10 ° C. so that the stretching ratio was 3 times to obtain a test piece. The stretched test piece is retarded by a rotary photon method using a retardation film / optical material inspection device (“RETS-100” manufactured by Otsuka Electronics Co., Ltd.) under the conditions of a measurement temperature of 20 ° C. and a measurement wavelength of 600 nm. Was measured, and the absolute value was divided by the thickness of the measurement site.

[Synthesis Example 1] Synthesis of BNEF In a 1 L separable flask, 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 After adding 1 g of 3-mercaptopropionic acid, the mixture was heated to 60 ° C. and completely dissolved. After that, 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 rate of 9-fluorenone was 99% or more. did it. After neutralizing by adding a 48 wt% sodium hydroxide aqueous solution to the obtained reaction solution, 400 g of xylene was added, the mixture was washed with distilled water several times, and cooled to precipitate crystals. Further, it was filtered and dried to obtain the desired 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF) as crystals of 87 g (yield 67%). The HPLC purity of the obtained crystals was measured and found to be 98.3%. The obtained crystal was confirmed to be 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF) by ¹ H-NMR and mass spectrum.

[Synthesis Example 2] Synthesis of BINOL-2EO 89 g (0.31 mol) of BINOL, 86 g (0.62 mol) of potassium carbonate, and 295 g of N, N-dimethylformamide (DMF) were put into a 1 L separable flask. After heating to 100 ° C., a solution in which 110 g of ethylene carbonate was dissolved 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 that the conversion rate of BINOL was 99% or more. 800 g of distilled water and 900 g of ethyl acetate were added to the obtained reaction solution, washed several times with distilled water, concentrated under reduced pressure, and then recrystallized from a mixed solvent of ethyl acetate / ethanol. When the precipitate was filtered and dried, 67 g (yield 58%) of crystals was obtained. As a result of analyzing the obtained crystals, the purity by HPLC was 94.8%, and ¹ H-NMR and mass spectrum showed that the target compound was 2,2'-bis (2-hydroxyethoxy) -1,1'-. It was confirmed that it was binaftalene (BINOL-2EO).

[Example 1]
0.10 mol of BNF and 0.90 mol of BPEF as diol components, 1.05 mol of DPC, and 2 × 10 ^-4 mol of tetramethylammonium hydroxide as a transesterification catalyst were added and gradually heated and melted with stirring. After raising the temperature to 250 ° C., the pressure was gradually reduced to 10,000 Pa. Phenol was removed by gradually raising the temperature and reducing the pressure until the temperature reached 270 ° C. and 0.13 kPa or less. After reaching the predetermined stirring torque, the contents were taken out from the reactor to obtain pellets of polycarbonate resin. When the obtained pellets were analyzed by ¹ H-NMR, 90 mol% of the constituent units of the polycarbonate resin were derived from BPEF and 10 mol% were derived from BNF.

[Example 2]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.15 mol of BNF and 0.85 mol of BPEF were used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 15 mol% of the constituent units of the polycarbonate resin were derived from BNF, and 85 mol% were derived from BPEF.

[Example 3]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.2 mol of BNF and 0.8 mol of BPEF were used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 20 mol% of the constituent units of the polycarbonate resin were derived from BNF and 80 mol% were derived from BPEF.

[Example 4]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.25 mol of BNF and 0.75 mol of BPEF were used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 25 mol% of the constituent units of the polycarbonate resin were derived from BNF, and 75 mol% were derived from BPEF.

[Comparative Example 1]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 1 mol of BPEF was used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. When the obtained pellets were analyzed by ¹ H-NMR, 100 mol% of the constituent units of the polycarbonate resin were derived from BPEF.

[Example 5]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.3 mol of BNEF and 0.6 mol of BINOL were used instead of 0.90 mol of BPEF as a diol component. When the obtained pellets were analyzed by ¹ H-NMR, 10 mol% of the constituent units of the polycarbonate resin were derived from BNF, 30 mol% were derived from BNEF, and 60 mol% were derived from BINOL.

[Example 6]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.35 mol of BNEF and 0.55 mol of BINOL were used instead of 0.90 mol of BPEF as a diol component. When the obtained pellets were analyzed by ¹ H-NMR, 10 mol% of the constituent units of the polycarbonate resin were derived from BNF, 35 mol% were derived from BNEF, and 55 mol% were derived from BINOL.

[Example 7]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.45 mol of BNEF and 0.45 mol of BINOL were used instead of 0.90 mol of BPEF as a diol component. When the obtained pellets were analyzed by ¹ H-NMR, 10 mol% of the constituent units of the polycarbonate resin were derived from BNF, 45 mol% were derived from BNEF, and 45 mol% were derived from BINOL.

[Example 8]
Polycarbonate as in Example 1 except that 0.2 mol of BNF, 0.4 mol of BNEF and 0.4 mol of BINOL are used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. Resin pellets were obtained. When the obtained pellets were analyzed by ¹ H-NMR, 20 mol% of the constituent units of the polycarbonate resin were derived from BNF, 40 mol% were derived from BNEF, and 40 mol% were derived from BINOL.

[Comparative Example 2]
Polycarbonate resin 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 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 55 mol% of the constituent units of the polycarbonate resin were derived from BNEF, and 45 mol% were derived from BINOL.

[Comparative Example 3]
Polycarbonate resin 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 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 45 mol% of the constituent units of the polycarbonate resin was derived from BNEF, and 55 mol% was derived from BINOL.

[Comparative Example 4]
Polycarbonate resin 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 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 40 mol% of the constituent units of the polycarbonate resin were derived from BNEF, and 60 mol% were derived from BINOL.

[Example 9]
Same as Example 1 except that 0.2 mol of BNF, 0.3 mol of BNEF and 0.5 mol of BINOL-2EO are used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. Obtained pellets of polycarbonate resin. When the obtained pellets were analyzed by ¹ H-NMR, 20 mol% of the constituent units of the polycarbonate resin were derived from BNF, 30 mol% were derived from BNEF, and 50 mol% were derived from BINOL-2EO.

[Comparative Example 5]
Polycarbonate resin pellets were prepared in the same manner as in Example 1 except that 0.5 mol of BNEF and 0.5 mol of BINOL-2EO were used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. Obtained. When the obtained pellets were analyzed by ¹ H-NMR, 50 mol% of the constituent units of the polycarbonate resin were derived from BNEF, and 50 mol% were derived from BINOL-2EO.

[Comparative Example 6]
Polycarbonate resin pellets were prepared 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 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. Obtained. When the obtained pellets were analyzed by ¹ H-NMR, 55 mol% of the constituent units of the polycarbonate resin were derived from BNEF, and 45 mol% were derived from BINOL-2EO.

[Comparative Example 7]
Polycarbonate resin pellets were prepared 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 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. Obtained. When the obtained pellets were analyzed by ¹ H-NMR, 70 mol% of the constituent units of the polycarbonate resin were derived from BNEF, and 30 mol% were derived from BINOL-2EO.

[Comparative Example 8]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.5 mol of BPEF and 0.5 mol of BNEF were used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 50 mol% of the constituent units of the polycarbonate resin were derived from BPEF, and 50 mol% were derived from BNEF.

[Comparative Example 9]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.5 mol of BOPPEF and 0.5 mol of BNEF were used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 50 mol% of the constituent units of the polycarbonate resin were derived from BOPPEF, and 50 mol% were derived from BNEF.

[Comparative Example 10]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 0.5 mol of BPEF and 0.5 mol of BOPPEF were used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. .. When the obtained pellets were analyzed by ¹ H-NMR, 50 mol% of the constituent units of the polycarbonate resin were derived from BPEF, and 50 mol% were derived from BOPPEF.

[Comparative Example 11]
Polycarbonate resin pellets were obtained in the same manner as in Example 1 except that 1 mol of BOPPEF was used instead of 0.10 mol of BNF and 0.90 mol of BPEF as the diol component. When the obtained pellets were analyzed by ¹ H-NMR, 100 mol% of the constituent units of the polycarbonate resin were derived from BOPPEF.

Table 1 shows the glass transition temperature Tg, weight average molecular weight Mw, refractive index, Abbe number, and triple refraction of the polycarbonate resins obtained in Examples and Comparative Examples.

As is clear from Table 1, according to Examples 1 to 4 using the polycarbonate resin containing the structural unit (BNF as the diol component) represented by the above formula (1), the diol component is only BPEF. Compared with Comparative Example 1, the glass transition temperature Tg of the polycarbonate resin could be remarkably increased. Although the proportion of BNF-derived units in the examples is as low as 10 to 25 mol% with respect to the entire constituent units, it is possible to improve Tg by about 14 to 29 ° C. with respect to Comparative Example 1. It was a surprising result.

Further, in the polycarbonate resins of Examples 1 to 4, the refractive index could be improved as compared with Comparative Example 1. Moreover, the triple birefringence, which indicates the degree of birefringence, was about the same as or even smaller than that of Comparative Example 1, and was an excellent value.

On the other hand, Comparative Examples 2 to 4 and 8 to 10 are examples in which BNEF having a naphthalene skeleton and an ethylene oxide skeleton and BINOL or BINOL-2EO having a binaftyl skeleton are used in combination as a diol component. With these polycarbonate resins, the glass transition temperature Tg could be increased, but the birefringence was increased.

Further, in Examples 1 to 4 (particularly, Example 1), the triple birefringence was particularly low, and the balance between high refractive index and heat resistance and low birefringence was excellent.

The polycarbonate resin of the present invention has high heat resistance and excellent optical properties (high refractive index, low birefringence, high transparency, etc.), and is also excellent in various properties such as mechanical properties. Therefore, the polycarbonate 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. Further, the polycarbonate resin (or resin composition thereof) of the present invention is a paint, an antioxidant, an ink, an adhesive, an adhesive, a resin filler, a charging tray, a conductive sheet, a protective film (for example, an electronic device, a liquid crystal member). Protective films such as), electrical / electronic materials (eg, carrier transport agents, light emitters, organic photoconductors, heat sensitive recording materials, hologram recording materials, etc.), electrical / electronic parts or equipment (eg, optical disks, inkjet printers, digital). Resins, mechanical parts or equipment (eg, automobiles, aeronautical / space materials, sensors, sliding) for papers, organic semiconductor lasers, dye-sensitized solar cells, EMI shield films, photochromic materials, organic EL elements, color filters, etc. It can be suitably used as a resin for (members, etc.).

In particular, since the polycarbonate resin of the present invention has excellent optical properties, it is useful for forming a molded product (optical molded product) for optical use. Examples of the optical molded body made of such a polycarbonate resin include an optical film, an optical sheet, and an optical lens.

Optical films include polarizing films (and the polarizing elements and polarizing plate protective films that compose them), retardation films, alignment films (alignment films), viewing angle expansion (compensation) films, diffuser plates (films), prism sheets, etc. Light guide plate, brightness improving film, near infrared absorption film, reflective film, antireflection (AR) film, antireflection (LR) film, antiglare (AG) film, transparent conductive (ITO) film, idiosyncratic conductive film (ACF) ), Electromagnetic wave shielding (EMI) film, electrode substrate film, color filter substrate film, barrier film, color filter layer, black matrix layer, adhesive layer between optical films, or release layer. In particular, the film of the present invention is useful as an optical film used for a display of an apparatus. Specific examples of the display member (or display) provided with 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.). , Game machines, car navigation systems, FPD devices such as touch panels (for example, LCD, PDP, etc.) and the like.

As the optical lens, for example, a lens that requires a low number of cameras, such as a camera lens [for example, a lens mounted on a small device having a camera function (or a mobile device, for example, a mobile phone, a digital camera, etc.)]. And so on. In particular, since the polycarbonate resin of the present invention has high heat resistance, it can be suitably used even in applications that are expected to be used in a high temperature environment such as an in-vehicle optical lens.

Claims (10)

The following formula (1)

(In the formula, ring Z ¹ is a condensed polycyclic arene ring, R ¹ is a substituent, and k is an integer of 0 or more.)
The structural unit represented by and the following formula (2)

(In the formula, ring Z ² is a benzene ring, R ³ and R ⁴ are substituents, n and p are integers of 0 or more, respectively, A ¹ is a linear or branched C _2-4 alkylene group, and q is. Indicates an integer of 1 or more.)
It is a polycarbonate resin containing
The ratio of the constituent unit represented by the formula (1) is 5 to 30 mol% with respect to the entire constituent unit of the polycarbonate resin [however, the following formula (4)

(In the formula, ring Z ³ is a naphthalene ring, A ³ is an alkylene group, R ⁷ is the same or different, an alkyl group, a cyano group, a halogen atom, and R ⁸ is the same or different, an alkyl group or a cycloalkyl group. , W is an integer of 0 to 3, u is an integer of 0 to 4, and v is an integer of 0 to 6.)
The structural unit represented by
The following formula (5)

( ^In the formula, A4 is an alkylene group, R9 is the same or different, an alkyl group, a cyano group, a halogen atom, x is an integer of ⁰ to 4, and rings Z3 ^, A3 ^, w, ^R7 , u, R8 and v are the ^same as the above formula (4).
The structural unit represented by and / or the following formula (6)

(In the formula, A ⁵ is an alkylene group, R ¹⁰ is the same or different, an alkyl group, a cyano group, a halogen atom, y and z are integers of 0 to 4, and rings Z ³ , A ³ , w, R. ⁷ , u, R8 and v are the ^same as the above formula (4).
Including the structural unit represented by, the refractive index at 20 ° C. and a wavelength of 589 nm is 1.660 to 1.700, and 20 ° C. in a film stretched three times at a temperature 10 ° C. higher than the glass transition point. Excludes polycarbonate resins whose absolute value of birefringence at a wavelength of 600 nm is 75 × 10 ^-4 or less. ]. The polycarbonate resin according to claim ¹ , wherein the ring Z1 is a naphthalene ring in the formula (1). Furthermore, the following formula ( 3 )

(In the formula, X is a direct bond or an alkylene group, R ⁵ and R ⁶ are substituents, A ² is an alkylene group, r is an integer of 0 to 4, s is an integer of 0 to 2, and t is an integer of 0 or more. Shows.)
The polycarbonate resin according to claim 1 or 2, which comprises a structural unit represented by. In formula (2) , R ⁴ is a C _1-6 alkyl group or C _6-12 aryl group, p is an integer of 0 to 2, and q is an integer of 1 to 10.
In formula (3), X is a direct bond or alkylene group, R ⁵ and R ⁶ are C _1-6 alkyl groups or C _6-12 aryl groups, respectively, and A ² is a linear or branched C _2-6 alkylene. The polycarbonate resin according to claim 3, wherein r is an integer of 0 to 2, s is an integer of 0 or 1, and t is an integer of 0 to 10. The ratio of the constituent unit represented by the formula (1) to the total amount of the constituent units represented by the formulas (2) and (3) is the former / the latter (molar ratio) = 5/95 to 25/75. The polycarbonate resin according to claim 3 or 4. Claims 3 to 5 in which the ratio of the structural unit represented by the formula (2) to the structural unit represented by the formula (3) is the former / the latter (molar ratio) = 20/80 to 70/30. The polycarbonate resin described in any of them. A diol component containing a first diol component for forming the structural unit represented by the formula (1) and a second diol component for forming the structural unit represented by the formula (2), and a carbonic acid diester. The method for producing the polycarbonate resin according to any one of claims 1 to 6. A molded product containing the polycarbonate resin according to any one of claims 1 to 6. The molded body according to claim 8, which is an optical member. The molded body according to claim 8 or 9, which is an in-vehicle optical lens.