JP6764353B2 - High refractive index resin and molded product - Google Patents

Description

The present invention relates to a novel polyester resin having a naphthalene skeleton and a fluorene skeleton, and a molded body (for example, an optical molded body such as an optical film or an optical lens) formed of the polyester resin.

There is a strong need for high refractive index resins for optical lenses, and thermoplastic resins with a refractive index of 1.66 are currently on the market. However, in response to the high demands of optical instruments in recent years, a higher refractive index (1.66 or more) is required. Among them, polyester resin is widely used as an optical lens because it has an excellent balance of optical properties and mechanical properties. On the other hand, as a high refractive index resin, a resin having a fluorene skeleton (9,9-bisarylfluorene skeleton) or a naphthalene skeleton introduced is known, and a polyester resin also has a high refractive index having a fluorene skeleton or a naphthalene skeleton introduced. Polyester resin has been proposed.

Japanese Patent Laying-Open No. 2001-72872 (Patent Document 1) states that a bond is formed on a bond axis capable of imparting internal rotational isomerism, and the number of π electrons of at least one aryl group is 4n + 6 (n is a natural number) with respect to this bond axis. A polyester resin containing a diol component having a biaryl compound and a dicarboxylic acid component is disclosed. In the examples of this document, polyesters obtained by polymerizing a diol component having a 1,1'-binaphthyl skeleton, ethylene glycol, and a dicarboxylic acid having a 1,1'-binaphthyl skeleton are described. ..

However, this polyester is also not sufficiently high in refractive index.

Japanese Unexamined Patent Publication No. 2011-168722 (Patent Document 2) contains a dicarboxylic acid component containing a polycyclic aromatic dicarboxylic acid component and a compound having a 9,9-bis (hydroxy (poly) alkoxyaryl) fluorene skeleton. A polyester resin containing a diol component as a polymerization component is disclosed.

However, although this polyester resin has a refractive index of more than 1.66, it also has a high birefringence.

The WO2015 / 170691 pamphlet (Patent Document 3) describes a structural unit derived from a diol component having a binaphthyl skeleton, a structural unit derived from a diol component having a 9,9-bisphenylfluorene skeleton, and a dicarboxylic acid or a derivative thereof. A polyester resin containing a unit derived from is disclosed. In the examples of this document, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 2,2'-bis (2-hydroxyethoxy) are 1,1'-binaphthalene and ethylene glycol. , Polyester obtained by polymerizing with dimethyl 2,6-naphthalenedicarboxylic acid and the like are described.

However, even with this polyester, the high refractive index is not sufficient, for example, the refractive index of the polyester of the example is less than 1.66.

That is, there is a trade-off relationship between high refractive index and low birefringence, and it has been difficult to achieve both characteristics with the conventional polyester resin.

JP 2001-72872 (Claims 1 and 5, Examples, Table 1) JP 2011-168722 (Claim 1, Example) WO2015 / 170691 Pamphlet (Claim 1, Example, Table 8)

Therefore, an object of the present invention is to provide a polyester resin capable of achieving both high refractive index and low birefringence, and a molded body (for example, an optical molded body such as an optical film or an optical lens) formed of the polyester resin. It is in.

Another object of the present invention is to provide a polyester resin having a low Abbe number and excellent heat resistance, moldability and mechanical properties, and a molded product formed of the polyester resin.

As a result of diligent studies to achieve the above problems, the present inventors have found that a novel polyester resin having a specific naphthalene skeleton and fluorene skeleton can achieve both high refractive index and low birefringence, which are contradictory characteristics. The invention was completed.

That is, the polyester resin of the present invention contains a structural unit represented by the following formula (1) and / or a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3). ..

(In the formula, A ¹ is a direct bond or an alkylene group, A ² is an alkylene group, L ₁ is an alkylene group, R ¹ and R ² are substituents, h is 0 or 1, n is an integer of 0 or more, and m is 0. An integer of ~ 2, k is an integer of 0-4).

(In the formula, A ³ is an alkylene group, L ₂ is an alkylene group, R ³ and R ⁴ are substituents, j is 0 or 1, p is an integer of 0 or more, q is an integer of 0 to 2, and r is 0 to 0. It is an integer of 4).

(In the formula, ring Z is an arene ring, 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 4, and u is an integer of 0 or more).

The structural unit represented by the formula (1) is a structural unit represented by the formula (1a), and the structural unit represented by the formula (2) is a structural unit represented by the formula (2a). There may be.

(In the formula, A ¹ is a direct bond or an alkylene group, A ² is an alkylene group, L ₁ is an alkylene group, R ¹ and R ² are substituents, h is 0 or 1, n is an integer of 0 or more, and m is 0. An integer of ~ 2, k is an integer of 0-4).

(In the formula, A ³ is an alkylene group, L ₂ is an alkylene group, R ³ and R ⁴ are substituents, j is 0 or 1, p is an integer of 0 or more, q is an integer of 0 to 2, and r is 0 to 0. It is an integer of 4).

In the formula (1) or (1a), A ¹ may be a direct bond or a methylene group, L ₁ may be a methylene group, h may be 1, and n may be 0. In the formula (2) or (2a), L ₂ may be a methylene group and j may be 0. In the above formula (3), Z may be a naphthalene ring.

The polyester resin of the present invention may further contain a structural unit represented by the following formula (4) and / or a structural unit represented by the following formula (5).

(In the formula, A ⁵ is an alkylene group, R ⁷ is a substituent, and v is an integer from 0 to 4).

(In the formula, A ⁶ is an alkylene group, R ⁸ is a substituent, and w and x are integers from 0 to 4).

The structural unit represented by the formula (1) and / or the structural unit represented by the formula (2), and the structural unit represented by the formula (4) and / or the structural unit represented by the formula (5). The molar ratio of the former / the latter is about 100/0 to 10/90.

The polyester resin of the present invention may further contain a structural unit represented by the following formula (6). The molar ratio of the structural unit represented by the formula (3) to the structural unit represented by the formula (6) is about 100/0 to 10/90 of the former / the latter.

(Wherein, ^{A 7} is an alkylene group).

The polyester resin of the present invention has a refractive index of 1.665 to 1.700 at 20 ° C. and a wavelength of 589 nm, an Abbe number of 15 to 25 at 20 ° C., and a temperature 10 ° C. higher than the glass transition point. The absolute value of birefringence at 20 ° C. and a wavelength of 600 nm in a three-fold stretched film may be 0.01 × 10 ^-4 to 75 × 10 ^-4 .

The present invention also includes a molded product containing the polyester resin. The molded product of the present invention may be an optical member such as an optical film, an optical sheet, or an optical lens.

The polyester resin of the present invention is a polyester resin (for example, a linear polyester resin) containing a unit derived from a specific dicarboxylic acid component (A) and a unit derived from a specific diol component (B) as constituent units.

[Unit derived from dicarboxylic acid component (A)]
(Constituent unit represented by equations (1) and (2))
In the present invention, the essential structural unit derived from the dicarboxylic acid component (A) includes the structural unit represented by the formula (1) and / or the structural unit represented by the formula (2). In the present invention, since the dicarboxylic acid component contains a structural unit having such a specific naphthalene skeleton, the expression of birefringence derived from the naphthalene ring is suppressed, and low birefringence can be realized.

In the above formula (1), examples of the alkylene group of group A ¹ include C _1-4 alkylene groups such as methylene group, ethylene group, propylene group, trimethylene group, 1,2-butandyl group and tetramethylene group. It can be exemplified. As the group A ¹ , a direct bond or a C _1-2 alkylene group is preferable, and a direct bond or a methylene group (particularly a direct bond) is particularly preferable from the viewpoint of optical characteristics.

The alkylene group of group A ² 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 ² on both sides may be the same alkylene group or different alkylene groups. When n is 2 or more polyoxyalkylene groups, the alkylene groups constituting the polyoxyalkylene group may be different alkylene groups, or may be usually the same alkylene group. As the group A ² , a C _2-3 alkylene group is preferable from the viewpoint of optical characteristics, and a C _2-3 alkylene group such as an ethylene group or a propylene group is particularly preferable.

Oxyalkylene group A ^{2 O} repetition number of a (addition molar number) n (number of repetition of each group A ^{2 O)} may but if an integer of 0 or more, from the viewpoint of optical properties, for example 0-3, It is preferably 0 to 2, more preferably 0 or 1 (particularly 0). h may be either 0 or 1, but 1 is preferable from the viewpoint of reactivity and the like. In many cases, n is 0 and h is 1.

Examples of the alkylene group of the group L ₁ include C _1-4 alkylene groups similar to the alkylene group of the group A ¹ . The group L _1, from the viewpoint of optical properties, C _1-2 alkylene group is preferred, usually often a methylene group.

The group- [O- (A ² O) _n- L ₁ ] _h- CO-, which is a carbonyl-containing group serving as a main chain for connecting the birefringence skeleton, is located at the 2-position, 3-position, 4-position (or) of the naphthalene ring. It may be in any position (2'position, 3'position, 4'position), but from the viewpoint of reducing birefringence, the 2nd position (or 2'position) which is the position represented by the above formula (1a). Is particularly preferable.

Examples of the substituent R ¹ include an alkyl group (for example, C _1-6 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group) and cycloalkyl group (C such as cyclohexyl group). _5-8 cycloalkyl group, etc.), aryl group (eg, C _6-10 aryl group such as phenyl group, tolyl group, xsilyl group), aralkyl group (C _6-10 aryl-C such as benzyl group, phenethyl group, etc.) Hydrocarbon groups such as _1-4 alkyl groups; alkoxy groups (such as C _1-6 alkoxy groups such as methoxy groups), cycloalkoxy groups (such as C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryl Oxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (C _6-10 aryl-C _1-4 alkyl group such as benzyloxy group); alkylthio group (C ₁ such as methylthio group) _-6 alkylthio groups, etc.); Acyl groups (C _1-6 acyl groups such as acetyl groups); Halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.); hydroxyl groups; nitro groups; cyano groups; dialkyl Amino groups (diC _1-4 alkylamino groups such as dimethylamino groups); dialkylcarbonylamino groups (diC _1-4 alkyl-carbonylamino groups such as diacetylamino groups) and the like can be exemplified.

These substituents R ¹ may be used singly or in combination. As the substituent R ¹ , 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 substitution number m of substituents R ¹ are each be selected from the integers from 0 to 2, preferably 0 or 1, more preferably may be 0. The number of substitutions m may be the same as or different from each other.

Even substituents R 2, can be exemplified such as exemplified substituents as the substituent R 1. The substituent R 2, C 1-6 alkyl, C 5-8 cycloalkyl group, a C 1-4 alkoxy group, and particularly preferably a C 1-4 alkyl group such as a methyl group.

The substitution number k of the substituent R ² 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 to 1 (particularly 0). The number of substitutions k may be the same as or different from each other.

In the formula (2), the alkylene group and the repeating number p that group A ³ constituting the oxyalkylene groups, including preferred embodiments, respectively group A ² and n in Formula (1) are identical. j may be either 0 or 1, but 1 is preferable from the viewpoint of reactivity. In many cases, p is 0 and j is 1.

The alkylene group of the group L ₂ is the same as the alkylene group of the group A ¹ in the above formula (1), including a preferable embodiment, and the group L ₂ is a C _1-2 alkylene group, usually a methylene group. There are many.

The group- [O- (A ³ O) _p- L ₂ ] _j- CO-, which is a carbonyl-containing group that serves as the main chain for connecting the naphthalene skeleton, has two groups at positions 1 to 4 of the naphthalene ring. 1st and 2nd, 1st and 3rd, 1st and 4th, 2nd and 4th may be used, but the above formula (2a) has a large effect of reducing birefringence. The 2nd and 3rd positions, which are the positions indicated by, are particularly preferable.

Examples of the substituent R 3 include the substituent exemplified as the substituent R 1 . The substituent R 3, C 1-6 alkyl, C 5-8 cycloalkyl group, a C 1-4 alkoxy group, and particularly preferably a C 1-4 alkyl group such as a methyl group.

The substitution number q of the substituent R ³ can be selected from an integer of 0 to 2, and may be preferably 0 or 1, and more preferably 0. The number of substitutions q may be the same as or different from each other.

Examples of the substituent R 4 include the substituent exemplified as the substituent R 1 . The substituent R 4, C 1-6 alkyl, C 5-8 cycloalkyl group, a C 1-4 alkoxy group, and particularly preferably a C 1-4 alkyl group such as a methyl group.

The substitution number r of substituents ^{R 4} each can be selected from the integers from 0 to 4, for example 0-3, preferably 0-2, more preferably may be a 0-1 (especially 0). The number of substitutions r may be the same as or different from each other.

(Constituent unit represented by equations (4) and (5))
The unit derived from the dicarboxylic acid component (A) is further represented by the formula (4) in addition to the structural unit represented by the formula (1) and / or the structural unit represented by the formula (2). The structural unit and / or the structural unit represented by the above formula (5) may be further included. By combining both units of the unit derived from the dicarboxylic acid component (A), birefringence can be further reduced and moldability can be improved.

In the formula (4), the alkylene group of group ^{A 5,} for example, methylene group, ethylene group, trimethylene group, propylene group, 2-ethyl ethylene group, a linear, such as 2-methylpropan-1,3-diyl Examples thereof _{include a} chain-like or branched chain-like C _1-8 alkylene group. Alkylene group A ⁵ represents, 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 5,} linear or branched _{C 1-6} alkylene group is preferred, a methylene group, an ethylene group, a trimethylene group, a propylene group, like a linear, such as 2-methylpropan-1,3-diyl Alternatively, a branched C _1-4 alkylene group is particularly preferable, and a linear or branched C _2-4 alkylene group such as an ethylene group or a propylene group is often used. The alkylene group having a substituent may be, for example, a 1-phenylethylene group, a 1-phenylpropane-1,2-diyl group, or the like.

The substituent R ^7, such as exemplified substituents for the substituent R ¹ can be exemplified. The substituent R ⁷ 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (for example, C _1-8 alkyl group, particularly C such as methyl group). _(1-4 alkyl group) and the like can be exemplified.

When v is a plurality (2 or more), the group R ⁷ in the same benzene ring in the fluorene skeleton may be the same or different in each benzene ring. Further, the groups R ⁷ substituting for the two benzene rings constituting the fluorene skeleton may be the same or different from each other. The bond position (substitution position) of the group R ⁷ with respect to the two benzene rings constituting the fluorene skeleton is not particularly limited, and for example, the 2-position, 7-position, 2-position and 7-position of the fluorene skeleton and the like are not particularly limited. Can be exemplified. The preferred number of substitutions v is, for example, 0 to 1, especially 0. In the two benzene rings constituting the fluorene skeleton, the number of substitutions v may be the same as or different from each other.

In the formula (5), as the alkylene group for group A ^6, exemplified alkylene groups as the A ⁵ can be exemplified. As the group ^{A 6,} linear or branched _{C 1-6} alkylene group is preferred, a methylene group, an ethylene group, a trimethylene group, a propylene group, like a linear, such as 2-methylpropan-1,3-diyl Alternatively, a branched C _1-4 alkylene group is particularly preferable, and a linear or branched C _1-3 alkylene group such as a methylene group or an ethylene group is often used.

The number of repetitions of the methylene group, w, can be selected from an integer of 1 to 4, and is, for example, 0 to 2, preferably 0 or 1.

Substituents R ⁸ and number of the substituents x, including preferred embodiments, are respectively the same as the substituents R ⁷ and v in formula (4).

The structural unit represented by the formula (1) and / or the structural unit represented by the formula (2), and the structural unit represented by the formula (4) and / or the structural unit represented by the formula (5). The molar ratio is, 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 (particularly). It is about 60/40 to 40/60). If the proportion of the former constituent units is too small, the refractive index may be low, and if the proportion of the latter constituent units is too small, the birefringence may be high.

(Other building blocks)
The unit derived from the dicarboxylic acid component (A) may further contain a structural unit derived from another dicarboxylic acid. Other dicarboxylic acids include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acid components and the like.

Examples of the aromatic dicarboxylic acid component include a polycyclic aromatic dicarboxylic acid {for example, a condensed polycyclic aromatic dicarboxylic acid [for example, a naphthalenedicarboxylic acid having a carboxyl group on a different benzene ring (for example, 1,5-naphthalene). Dicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc.), anthracendicarboxylic acid, phenanthrene, etc. Condensed polycyclic C _10-24 allene-dicarboxylic acid such as dicarboxylic acid]; arylarene dicarboxylic acid [for example, biphenyldicarboxylic acid (eg, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.) ) Etc. C _6-10aryl- C _6-10 arene-dicarboxylic acid, etc.]; Diarylalcandicarboxylic acid [eg, diphenylalcandicarboxylic acid (eg, 4,4'-diphenylmethanedicarboxylic acid, etc.) and the like, diC _6- such as dicarboxylic acid] - ₁₀ aryl _{C 1-6} alkane; diaryl ketone dicarboxylic acid [for example, _{di-C 6-10} aryl ketones, such as diphenyl ketone dicarboxylic acid (e.g., 4,4'-diphenyl ketone dicarboxylic acid) - dicarboxylic acid ) Etc.}; C of monocyclic aromatic dicarboxylic acids [eg, phthalic acid, terephthalic acid, isophthalic acid, alkylisophthalic acid (eg, C _1-4 alkylisophthalic acid such as 4-methylisophthalic acid), etc.) _6-10 arene-dicarboxylic acid, etc.] and the like can be exemplified.

Examples of the alicyclic dicarboxylic acid component include cycloalcandicarboxylic acids (eg, C _{5-10 cycloalcan} -dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid); di or tricycloalkandicarboxylic acids (eg, decalin). Dicarboxylic acid, norbornandicarboxylic acid, adamantandicarboxylic acid, tricyclodecanedicarboxylic acid, etc.; cycloalkendicarboxylic acid (eg, C _5-10 cycloalkene-dicarboxylic acid, such as cyclohexendicarboxylic acid); di or tricycloalkenedicarboxylic acid (eg, cyclohexendicarboxylic acid) For example, norbornene dicarboxylic acid) and the like can be exemplified.

Examples of the aliphatic dicarboxylic acid component include an alkanedicarboxylic acid (for example, C _2-12 alkane-dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, and decandicarboxylic acid) and an unsaturated aliphatic dicarboxylic acid (for example, for example. Examples thereof include C _2-10 alkene-dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid).

The ratio of the other constituent units may be 30 mol% or less (for example, 0.01 to 30 mol%), preferably 20 mol% or less, more preferably 20 mol% or less, based on the total units derived from the dicarboxylic acid component (A). Is less than 10 mol%. If the proportion of other structural units is too large, the optical characteristics may deteriorate.

[Unit derived from diol component (B)]
(Constituent unit represented by equation (3))
In the present invention, the structural unit represented by the above formula (3) is included as an essential structural unit derived from the diol component (B). In the present invention, since the diol component contains a structural unit having such a 9,9-bisarylfluorene skeleton, birefringence can be suppressed even at a high refractive index.

In the above formula (3), examples of the arene ring represented by ring Z include a monocyclic arene ring such as a benzene ring and a polycyclic arene ring, and the polycyclic arene ring is a fused polycyclic arene ring. It includes an arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), and the like.

Examples of the fused polycyclic arene ring include a fused bicyclic arene ring (for example, a fused bicyclic C _10-16 arene ring such as a naphthalene ring) and a fused tricyclic arene ring (for example, anthracene ring and phenanthrene ring). Etc.), and the like can be exemplified as a fused bicyclic arene ring.

The ring-aggregated 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 bi-C _6-12 arene ring). For example, a Tel C _6-12 arene ring such as a terphenylene ring) can be exemplified.

Among these rings Z, a benzene ring, a naphthalene ring, an anthracene ring, and a biphenyl ring are preferable, and a biphenyl ring is particularly preferable because birefringence can be reduced, and a refractive index can be improved and mechanical properties can be improved. , Naphthalene ring is particularly preferable. The two rings Z substituted at the 9-position of fluorene may be the same or different rings, and usually may be the same ring.

In the ring Z, the positions of the two bonds forming the main clavicle are not particularly limited, and when Z is a benzene ring, the other bond position is, for example, o with respect to the bond position with the 9-position of fluorene. It may be in the − position or the p − position, and the p- position is widely used. In the case of a naphthalene ring, the other bonding position with respect to the naphthalene ring in which fluorene is bonded to the 1-position may be, for example, 2-position, 4-position, 5-position or 7-position, and the 5-position may be used. Is generalized. The other bonding position with respect to the naphthalene ring in which fluorene is bonded to the 2-position may be, for example, the 1-position, 3-position, 6-position or 8-position, and the 6-position is generally used. When Z is a biphenyl ring, the two bonding positions may be the same or different rings, for example, the other bonding position with respect to the biphenyl ring in which fluorene is bonded at the 3-position is the 5-position or 6-position. , 2'-position, 3'-position, 4'-position, 5'-position, 6'-position, etc. may be used, and the 6-position is generally used.

In the formula (3), alkylene groups of group A ⁴ constituting the oxyalkylene groups, including preferred embodiments, is the same as group A ² in Formula (1). Oxyalkylene group A ^{4 O} is a number of repetitions (number of moles) s is sufficient if an integer of 0 or more, from the viewpoint of optical properties, for example 0-3, preferably 0-2, more preferably 0 Or 1 (especially 1).

The substituent R 5, can be exemplified such as exemplified substituents as R 1 in Formula (1). The substituent R 5, C 1-6 alkyl, C 5-8 cycloalkyl group, a C 1-4 alkoxy group, and particularly preferably a C 1-4 alkyl group such as a methyl group.

Substitution number t of the substituents ^{R 5} may be selected from the integers from 0 to 4, for example 0-3, preferably 0-2, more preferably may be a 0-1 (especially 0). The number of substitutions t may be the same as or different from each other.

As the substituent R 6 , among the substituents exemplified as R 1 in the above formula (1), a substituent other than the aryl group can be exemplified. The substituent R 5, C 1-6 alkyl, C 5-8 cycloalkyl group, a C 1-4 alkoxy group, and particularly preferably a C 1-4 alkyl group such as a methyl group. The number of substitutions u may be an integer of 0 or more, and can be appropriately selected depending on the type of ring Z. For example, it may be an integer of about 0 to 8, preferably 0 to 4 (for example, 0 to 3), more preferably 0 to 2 (for example, 0 or 1), and particularly 0. The number of substitutions u may be the same or different from each other. Further, when the substitution number u is 2 or more, two or more kinds of groups R 6 to be substituted with the same ring Z may be the same or different. In particular, when u is 1, the ring Z may be a benzene ring, a naphthalene ring or a biphenyl ring, and the group R 6 may be a methyl group. The substitution position of the group R 6 is not particularly limited, and may be substituted at a position other than the bond position of the ring Z with the ether bond (-O-) and the 9-position of fluorene.

(Constituent unit represented by equation (6))
The unit derived from the diol component (B) may further include the structural unit represented by the formula (6) in addition to the structural unit represented by the formula (3). By including the structural unit represented by the formula (6) as the unit (B) derived from the diol component, the polymerization reactivity (molecular weight of the polyester resin), the moldability of the polyester resin, and the like can be improved.

In the formula (6), the alkylene group of group ^{A 7,} for example, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, tetramethylene group, 1,5-butanediyl group, 1,6 Examples thereof include a C _2-10 alkylene group such as a diyl group. These alkylene groups can be used alone or in combination of two or more. Among these alkylene groups include ethylene group, C _2-4 alkylene group such as propylene group are preferred, C _2-3 alkylene group (particularly an ethylene group) is particularly preferred.

The molar ratio of the structural unit represented by the formula (3) to the structural unit represented by the formula (6) is the former / the latter = 100/0 to 10/90, preferably 99/1 to 30 /. It is about 70 (for example, 95/5 to 50/50), more preferably about 92/8 to 70/30 (particularly 90/10 to 75/25). If the proportion of the structural unit represented by the formula (6) is too large, the optical characteristics may deteriorate.

(Other building blocks)
The unit derived from the diol component (B) may further contain a structural unit derived from another diol. Other diols include polyalkane diols, alicyclic diols, aromatic diols and the like.

Examples of the polyalkadiol include diethylene glycol, dipropylene glycol, triethylene glycol and the like, or tri-C _2-4 alkane diol. Examples of the alicyclic diol include cycloalkanediol (for example, C _5-8 cycloalkanediol such as cyclohexanediol) and di (hydroxyalkyl) cycloalkane (for example, di (hydroxy C _1-4 ) such as cyclohexanedimethanol). Alkyl) C _5-8 cycloalkane etc.), isosorbide and the like can be exemplified. Examples of the aromatic diol include dihydroxyarene (hydroquinone, resorcinol, etc.) and aromatic aliphatic diols (eg, di (hydroxy C _1-4 alkyl) such as 1,3-benzenedimethanol and 1,4-benzenedimethanol). Examples thereof include C _6-10 arene), bisphenols [for example, biphenol, bis (hydroxyphenyl) C _1-10 alkane such as bisphenol A], and alkylene oxide adducts of bisphenol.

The ratio of the other constituent units may be 30 mol% or less (for example, 0.01 to 30 mol%), preferably 20 mol% or less, more preferably 20 mol% or less, based on the total units derived from the diol component (B). It is 10 mol% or less. If the proportion of other structural units is too large, the optical characteristics may deteriorate.

[Characteristics of polyester resin]
The polyester resin of the present invention is a resin containing the dicarboxylic acid component (A) and the diolic acid component (B) as a polymerization component, and has various properties (for example, optical properties, mechanical properties, thermal properties, etc.). , Especially in optical and mechanical properties). For example, the polyester resin of the present invention has a specific dicarboxylic acid component (derived skeleton) and a specific diol component (derived skeleton) in combination, and has both high refractive index and low birefringence.

The refractive index of the polyester resin of the present invention at 20 ° C. and a wavelength of 589 nm can be selected from the range of, for example, 1.655 or more (for example, about 1.655 to 1.750), for example, 1.665 or more (for example, 1.665 to 1.650). 1.700 or more (for example, about 1.670 to 1.679), more preferably 1.675 or more (for example, about 1.675 to 1.695), particularly high refractive index is required. It may be 1.680 or more (for example, about 1.680 to 1.690).

The Abbe number of the polyester resin of the present invention at 20 ° C. can be selected from the range of, for example, 23.0 or less (for example, about 17.0 to 23.0), for example, 22.0 or less (for example, 17.0 to 22.0). Degree), preferably 21.0 or less (for example, about 17.0 to 21.0), more preferably 20.0 or less (for example, about 17.0 to 20.0), especially 19.0 or less (for example, 17.0). ~ 19.0) may be used.

The absolute value of the birefringence of the polyester resin of the present invention at 20 ° C. and a wavelength of 600 nm (birefringence in a film stretched three times at a temperature 10 ° C. higher than the glass transition point) is, for example, 75 × 10 ^-4 or less (for example). It can be selected from the range of 0.001 × 10 ^-4 to 75 × 10 ^-4 ), for example, 60 × 10 ^-4 or less (for example, 0.005 × 10 ^{-4 to} 60 × 10 ^-4 ), preferably 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, about 0.1 × 10 ^-4 to 40 × 10 ^-4 ), In particular, it may be 30 × 10 ^-4 or less (for example, about 1 × 10 ^-4 to 30 × 10 ^-4 ), and when lower birefringence is required, for example, 25 × 10 ^-4 or less (for example, 5 ×). It may be about 10 ^{-4 to} 25 × 10 ^-4 ), preferably 20 × 10 ^-4 or less (for example, about 10 × 10 ^{-4 to} 20 × 10 ^-4 ). In addition, within the scope of this specification and claims, this birefringence can be measured by the method (measurement condition B) described in Examples described later. The birefringence depends on the unique birefringence derived from the molecular structure and the degree of orientation of the polymer chain after being molded under specific conditions, but the measurement condition B is higher than the measurement condition A described later. The degree of orientation of the molecular chain is high, that is, the absolute value is large.

The glass transition temperature (Tg) of the polyester resin of the present invention is relatively high and can be selected from the range of, for example, about 120 to 200 ° C., for example, 130 ° C. or higher (for example, about 130 to 190 ° C.), preferably 140 ° C. or higher (for example, 140). ~ 180 ° C.), more preferably 150 ° C. or higher (for example, about 150 to 170 ° C.), particularly 155 ° C. or higher (for example, about 155 to 165 ° C.).

The weight average molecular weight of the polyester 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), for example, 2 × 10 ⁴ to 2. 40 × 10 ^4, preferably ^{2.5 × 10 4 ~30 × 10 4} , more preferably 3 × ^{10 4} ~20 × ¹⁰ 4 nm, even particularly 3.5 × ¹⁰ 4 ~15 × ¹⁰ about ⁴ Good.

[Manufacturing method of polyester resin]
The polyester resin of the present invention can be produced by reacting (polymerizing or condensing) the dicarboxylic acid component (A) and the diol component (B). Examples of the polymerization method (manufacturing method) include a conventional method, a melt polymerization method (a method of polymerizing a dicarboxylic acid component and a diol component under melt mixing), a solution polymerization method, and an interfacial polymerization method. A preferred method is a melt polymerization method.

Further, in the reaction, the amount (usage ratio) of the dicarboxylic acid component (A) and the diol component (B) used can be selected from the same range as that of the constituent unit, but each component or the like is excessively used as necessary. You may react. For example, the diol component such as ethylene glycol distillable from the reaction system (raw material of the structural unit represented by the above formula (6)) is excessive more than the proportion of the skeleton derived from other diol components introduced into the polyester resin. May be used for. Further, the reaction may be carried out in the presence or absence of a solvent, depending on the polymerization method.

The reaction may be carried out in the presence of a catalyst. As the catalyst, various catalysts used in the production of polyester resin, for example, metal catalysts can be used. Examples of metal catalysts include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, titanium, etc.), and metals of Group 13 of the periodic table. Metal compounds containing (such as aluminum), metals of Group 14 of the periodic table (such as germanium), and metals of Group 15 of the periodic table (such as Antimon) are used. Examples of the metal compound include alkoxides, organic acid salts (acetate, propionate, etc.), inorganic acid salts (borate salt, carbonate, etc.), metal oxides, and the like. These catalysts can be used alone or in combination of two or more. 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 dicarboxylic acid component. You may.

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, helium, 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 melt polymerization method may be 150 to 300 ° C., preferably 180 to 290 ° C., more preferably 200 to 280 ° C. The polyester resin of the present invention has a relatively low viscosity and is easily produced by melt polymerization, probably because it uses a specific dicarboxylic acid component including a dicarboxylic acid component having a fluorene skeleton as a raw material.

Among the dicarboxylic acid components (A), the dicarboxylic acid which is a typical raw material (monomer or monomer) for forming the structural unit represented by the formula (1) is, for example, 2,2'. Dicarboxybinaphthyls such as −dicarboxybinaphthyl, 3,3′-dicarboxybinaphthyl, 4,4′-dicarboxybinaphthyl; bis (carboxyalkoxy) binaphthyl, eg, 2,2′-bis (carboxymethoxy) -1, Bis (carboxy C _1-4 alkoxy) such as 1'-binaphthyl, 3,3'-bis (carboxymethoxy) -1,1'-binaphthyl, 4,4'-bis (carboxymethoxy) -1,1'-binaphthyl ) Binaphthyl (eg, bis (carboxymethoxy) binaphthyl); bis (carboxyalkoxyalkoxy) binaphthyl, eg, 2,2'-bis (carboxymethoxyethoxy) -1,1'-binaphthyl, 3,3'-bis (carboxy) Bis (carboxy C _1-3 alkoxy C _2-4 alkoxy) binaphthyl (eg, bis) such as methoxyethoxy) -1,1'-binaphthyl, 4,4'-bis (carboxymethoxyethoxy) -1,1'-binaphthyl (Carboxymethoxy C _2-4 alkoxy) binaphthyl) and the like can be exemplified.

Typical dicarboxylic acids for forming the structural unit represented by (2) above include, for example, 1,2-naphthalene carboxylic acid, 1,3-naphthalene carboxylic acid, 1,4-naphthalene carboxylic acid, and 2 Naphthalene dicarboxylic acids such as 3-naphthalenedicarboxylic acid and 2,4-naphthalenedicarboxylic acid; bis (carboxyalkoxy) naphthalene, for example, 1,2-bis (carboxymethoxy) naphthalene, 1,3-bis (carboxymethoxy) naphthalene. , 1,4-Bis (carboxymethoxy) naphthalene, 2,3-bis (carboxymethoxy) naphthalene, 2,4-bis (carboxymethoxy) naphthalene and other bis (carboxyC _1-4 alkoxy) naphthalene (for example, bis (eg (Carboxymethoxy) naphthalene); bis (carboxyalkoxyalkoxy) naphthalene, for example 1,2-bis (carboxymethoxyethoxy) naphthalene, 1,3-bis (carboxymethoxyethoxy) naphthalene, 1,4-bis (carboxymethoxyethoxy) Bis (carboxy C _1-3 alkoxy C _2-4 alkoxy) naphthalene such as naphthalene, 2,3-bis (carboxymethoxyethoxy) naphthalene, 2,4-bis (carboxymethoxyethoxy) naphthalene (for example, bis (carboxymethoxy C) _2-4 alkoxy) naphthalene) and the like can be exemplified.

As a typical dicarboxylic acid for forming the structural unit represented by the formula (4), 9,9-bis (carboxyalkyl) fluorene, for example, 9,9-bis (2-carboxyethyl) fluorene, is used. Examples thereof include 9,9-bis (carboxyC _2-6 alkyl) fluorene such as 9,9-bis (2-carboxypropyl) fluorene.

Typical dicarboxylic acids for forming the structural unit represented by the above formula (5) include 9- (carboxy-carboxyalkyl) fluorene, for example, 9- (1-carboxy-2-carboxyethyl) fluorene. Examples thereof include 9- (carboxy-carboxy C _2-6 alkyl) fluorene such as 9- (2-carboxy-3-carboxypropyl) fluorene.

These dicarboxylic acid components (A) may be ester-forming derivatives. Examples of the ester-forming derivative include esters [eg, alkyl esters [eg, lower alkyl esters such as methyl esters and ethyl esters (eg, C _1-4 alkyl esters, especially C _1-2 alkyl esters)] and the like]. , Acid halides (eg, acid chlorides, etc.), acid anhydrides, and the like can be exemplified. The ester-forming derivative may be a monoester (half ester) or a diester. In particular, the dicarboxylic acid for forming the structural unit represented by the formulas (1) and (2) may be an ethyl ester.

Among the diol components (B), typical diols for forming the structural unit represented by the formula (3) include, for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl]. 9,9-bis (hydroxy C _2-4 alkoxyphenyl) fluorene such as fluorene; 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- ( 2-Hydroxypropoxy) -3-phenylphenyl] 9,9-bis (hydroxy C _2-4 alkoxy-C _6-10 aryl-phenyl) fluorene, etc.}; 9,9-bis [6- (2- (2-) Hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] Examples thereof include 9,9-bis (hydroxy C _2-4 alkoxynaphthyl) fluorene such as fluorene.

Typical diols represented by the formula (6) include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1 , 4-Butanediol, 1,3-Pentanediol, 1,4-Pentanediol, 1,5-Pentanediol, C _2-10 alkanediol such as neopentyl glycol and the like can be exemplified.

[Molded product]
Since the molded product of the present invention contains the polyester and has excellent optical properties (high refractive index, low birefringence, etc.), mechanical properties, and high heat resistance, an optical film, an optical lens, and an optical sheet It can be used as an optical member such as. The shape of the feature is not particularly limited, and may include, 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 tubular shape, a rod shape, a tubular shape, a hollow shape, etc.). Can be mentioned.

The molded product of the present invention has various additives [for example, filler or reinforcing agent, colorant (for example, dye pigment, etc.), conductive agent, flame retardant, plasticizer, lubricant, stabilizer (for example, antioxidant, ultraviolet ray, etc.). Absorbents, heat stabilizers, hydrolysis inhibitors, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents (eg silicone oils) , Silicone rubber, various plastic powders, various engineering plastic powders, etc.), carbon materials, 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 polyester 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 polyester 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 polyester resin 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 each direction in uniaxial stretching or biaxial stretching, and is usually 1 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 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 about 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 the wet stretching method or the dry stretching method may be used, and in the case of biaxial stretching, the tenter method (also referred to as the flat method) may be used by the 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 characteristics of the resin or film were measured and evaluated by the following methods.

[Polymer composition]
The sample was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard substance, and the spectrum of ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (“AVANCE III HD” manufactured by BRUKER). For the spectrum, the integrated value of the peak derived from each monomer used for the polymerization was obtained, and the ratio of each monomer component (constituent unit) introduced into the polymer was calculated.

[Molecular weight]
The sample was dissolved in chloroform, and the polystyrene-equivalent weight average molecular weight (Mw) was determined using gel permeation chromatography (“HLC-8320GPC” manufactured by Tosoh Corporation).

[Glass transition temperature (Tg)]
Using a differential scanning calorimeter (“EXSTAR6000 DSC6220 ASD-2” manufactured by SII Nanotechnology Co., Ltd.), the measurement was performed at a heating rate of 10 ° C./min under a nitrogen atmosphere.

[Refractive index (nD)]
The sample was heat pressed at 200-240 ° C. to form a film having a thickness of 200-300 μm. 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, diiodomethane was used as the contact liquid at a measurement temperature of 20 ° C. using a multi-wavelength Abbe refractometer (“DR-M4 (circulation type constant temperature water tank 60-C3)” manufactured by Atago Co., Ltd.). The refractive index nD of 589 nm (D line) was measured.

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

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

[Birerefringence]
<Measurement condition A>
The sample was hot pressed at 200-240 ° C. to form a film with a thickness of 200-600 μm. This film was cut into strips having a length of 10 mm and a width of 50 mm, and uniaxially stretched at 25 mm / min under a temperature condition of Tg + 30 ° C. so that the stretching ratio was 1.7 times to obtain a test piece. The stretched test piece is retarded by the parallel Nicol rotation method under the conditions of a measurement temperature of 20 ° C. and a measurement wavelength of 600 nm using a retardation film / optical material inspection device (“RETS-100” manufactured by Otsuka Electronics Co., Ltd.). Was measured, and the value was calculated by dividing the value by the thickness of the measurement site.

<Measurement condition B>
The sample was hot pressed at 200-240 ° C. to form a film with a thickness of 200-600 μm. 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 subjected to retardation by the parallel Nicol rotation method under the conditions of a measurement temperature of 20 ° C. and a measurement wavelength of 600 nm using a retardation film / optical material inspection device (RETS-100), and the value is measured. It was calculated by dividing by the thickness of the part.

[Reference example 1]
In the reactor, 2,2'-bis (ethoxycarbonylmethoxy) -1,1'-binaphthyl (hereinafter referred to as "BNAC-E") (91.69 g (0.20 mol)), diol component as a dicarboxylic acid component. As a catalyst for ethylene glycol (hereinafter, EG) (37.28 g (0.60 mol)), transesterification reaction, and polycondensation reaction, titanium tetrabutoxide (13.6 mg (40 μmol)), and as a heat stabilizer, phosphorus. Dibutyl acid (42.0 mg (200 μmol)) was charged, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component generated by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 270 ° C. and 300 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin. However, since this polyester resin was brittle and colored red and black, it was difficult to form a film, and it was difficult to measure the Abbe number and birefringence.

[Reference example 2]
Melt polymerization was carried out in the same manner as in Example 1 of JP-A-2001-72872. That is, in the reactor, BNAC-E (55.04 g (0.12 mol)) as the dicarboxylic acid component and 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl (hereinafter) as the diol component. , BINOL-EO) (26.97 g (0.072 mol)), EG (17.88 g (0.288 mol)), calcium acetate monohydrate (33.8 mg (192 μmol)) as a catalyst for transesterification reaction. ) Was charged, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, trimethyl phosphate (44.1 mg (210 μmol)) was added as a heat stabilizer, and germanium oxide (15.0 mg (144 μmol)) was added as a catalyst for the polycondensation reaction, and gradually added. The transesterification reaction was carried out while removing ethylene glycol by reducing the pressure while raising the temperature to 285 ° C. and 200 Pa. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin. However, since this polyester resin was brittle and colored red and black, it was difficult to form a film, and it was difficult to measure the Abbe number and birefringence.

[Example 1]
In the reactor, BNAC-E (68.75 g (0.15 mol)) as the dicarboxylic acid component and 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene as the diol component (hereinafter (Referred to as "BOPPEF") (35.44 g (0.06 mol)), EG (24.25 g (0.39 mol)), manganese acetate tetrahydrate (24.5 mg (100 μmol)) as a catalyst for transesterification reaction ) Was charged, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, trimethyl phosphate (31.5 mg (150 μmol)) was added as a heat stabilizer, and germanium oxide (41.8 mg (400 μmol)) was added as a catalyst for the polycondensation reaction. The pressure was gradually increased to 280 ° C. and 200 Pa, and the pressure was reduced. While removing ethylene glycol, a transesterification reaction was carried out until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 2]
In the reactor, BNAC-E (45.86 g (0.10 mol)) as a dicarboxylic acid component, BOPPEF (47.28 g (0.08 mol)) and EG (11.17 g (0.12 mol)) as a diol component. , Titanium tetrabutoxide (4.3 mg (12.5 μmol)) as a catalyst for transesterification reaction and polycondensation reaction, and dibutyl phosphate (31.5 mg (150 μmol)) as a heat stabilizer, gradually up to 230 ° C. Was heated and stirred, and a transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 255 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 3]
In the reactor, BNAC-E (55.04 g (0.12 mol)) as the dicarboxylic acid component and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (hereinafter referred to as "BPEF") as the diol component. (No.) (26.29 g (0.06 mol)), BOPPEF (28.36 g (0.048 mol)), EG (11.95 g (0.192 mol)), manganese acetate as a catalyst for transesterification reaction. A product (19.6 mg (80 μmol)) was charged, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, trimethyl phosphate (25.2 mg (120 μmol)) was added as a heat stabilizer, and germanium oxide (33.5 mg (320 μmol)) was added as a catalyst for the polycondensation reaction. The pressure was gradually increased to 275 ° C. and 300 Pa, and the pressure was reduced. While removing ethylene glycol, a transesterification reaction was carried out until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin. The polymer composition could not be calculated due to the overlap of peaks in the ¹ H-NMR spectrum. In addition, the obtained polyester resin was brittle, and it was difficult to prepare a film of a size used for measuring birefringence.

[Example 4]
In the reactor, BNAC-E (45.88 g (0.10 mol)) as a dicarboxylic acid component and 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene as a diol component (hereinafter, "" BNEF ”(40.4 g (0.075 mol)), EG (13.92 g (0.225 mol)), Titanium tetrabutoxide (8.5 mg (25 μmol)) as a catalyst for transesterification and polycondensation reactions. )), Dibutyl phosphate (31.5 mg (150 μmol)) was charged as a heat stabilizer, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 275 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 5]
In the reactor, as the dicarboxylic acid component, BNAC-E (27.51 g (0.06 mol)), 9,9-bis (2-methoxycarbonylethyl) fluorene (hereinafter referred to as "FDP-m") (20.29 g). (0.06 mol)), as a diol component, BNEF (58.18 g (0.108 mol)), EG (15.62 g (0.252 mol)), as a catalyst for transesterification reaction and polycondensation reaction, titanium tetra. Butoxide (3.4 mg (10 μmol)) and dibutyl phosphate (35.7 mg (170 μmol)) as a heat stabilizer were charged, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 280 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 6]
In the reactor, BNAC-E (48.15 g (0.105 mol)) and FDP-m (11.85 g (0.035 mol)) as the dicarboxylic acid component and BNEF (56.54 g (0.105 mol)) as the diol component. )), EG (19.64 g (0.317 mol)), titanium tetrabutoxide (4.1 mg (12 μmol)) as a catalyst for transesterification reaction and polycondensation reaction, and dibutyl phosphate (37) as a heat stabilizer. 8.8 mg (180 μmol)) was charged, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 275 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 7]
A polyester resin was obtained in the same manner as in Example 6 except that BNAC-E was changed to 0.070 mol and FDP-m was changed to 0.070 mol.

[Example 8]
A polyester resin was obtained in the same manner as in Example 6 except that BNAC-E was changed to 0.035 mol, FDP-m was changed to 0.105 mol, BNEF was changed to 0.119 mol, and EG was changed to 0.300 mol.

[Example 9]
In the reactor, BNAC-E (27.50 g (0.06 mol)) and FDP-m (20.31 g (0.06 mol)) as the dicarboxylic acid component and BNEF (38.79 g (0.072 mol)) as the diol component. )), EG (17.92 g (0.289 mol)), manganese acetate tetrahydrate (22.1 mg (90 μmol)) as a catalyst for the transesterification reaction, gradually heated to 240 ° C. and stirred. A transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, trimethyl phosphate (47.3 mg (225 μmol)) was added as a heat stabilizer, and germanium oxide (37.7 mg (360 μmol)) was added as a catalyst for the polycondensation reaction. The pressure was gradually increased to 280 ° C. and 200 Pa, and the pressure was reduced. While removing ethylene glycol, a transesterification reaction was carried out until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 10]
In the reactor, dimethyl 2,3-naphthalenedicarboxylic acid (hereinafter referred to as "2,3-DMN") (24.43 g (0.10 mol)) as a dicarboxylic acid component and BNEF (21.56 g) as a diol component. 0.04 mol)), EG (16.15 g (0.26 mol)), transesterification reaction, and titanium tetrabutoxide (6.8 mg (20 μmol)) as a catalyst for the polycondensation reaction were charged and gradually increased to 245 ° C. The ester exchange reaction was carried out by heating and stirring. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 280 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 11]
In the reactor, 2,3-DMN (24.44 g (0.10 mol)) as a dicarboxylic acid component, BNEF (40.42 g (0.075 mol)) as a diol component, and EG (13.99 g (0.225 mol)). )), Titanium tetrabutoxide (6.8 mg (20 μmol)) was charged as a catalyst for the transesterification reaction and the transesterification reaction, and the mixture was gradually heated to 240 ° C. and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually increased to 310 ° C. and 200 Pa, and the pressure was reduced. While removing ethylene glycol, a polycondensation reaction was carried out until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 12]
In the reactor, 2,3-DMN (17.11 g (0.070 mol)), FDP-m (23.69 g (0.070 mol)) as the dicarboxylic acid component, and BNEF (56.57 g (0)) as the diol component. .105 mol)), EG (19.58 g (0.315 mol)), transesterification reaction, and titanium tetrabutoxide (10.2 mg (30 μmol)) as a catalyst for the polycondensation reaction, and gradually heated to 240 ° C. , Stirred and transesterified. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 295 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 13]
In the reactor, 2,3-DMN (9.76 g (0.040 mol)), FDP-m (20.32 g (0.060 mol)) as the dicarboxylic acid component, and BNEF (40.42 g (0)) as the diol component. .075 mol)), EG (13.95 g (0.225 mol)), transesterification reaction, and titanium tetrabutoxide (6.1 mg (18 μmol)) as a catalyst for the polycondensation reaction, and gradually heated to 240 ° C. , Stirred and transesterified. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 285 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 14]
In the reactor, 2,3-DMN (21.99 g (0.090 mol)) as a dicarboxylic acid component, BOPPEF (21.26 g (0.036 mol)) as a diol component, and EG (14.55 g (0.234 mol)). )), Titanium tetrabutoxide (15.3 mg (45 μmol)) was charged as a catalyst for the transesterification reaction and the transesterification reaction, and the mixture was gradually heated to 240 ° C. and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 290 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 15]
In the reactor, 2,3-DMN (24.44 g (0.100 mol)) as the dicarboxylic acid component, BPEF (30.69 g (0.070 mol)) and EG (14.30 g (0.230 mol)) as the diol component. )), Titanium tetrabutoxide (17.0 mg (50 μmol)) was charged as a catalyst for the transesterification reaction and the transesterification reaction, and the mixture was gradually heated to 240 ° C. and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 295 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Example 16]
In the reactor, bis [2- (methoxycarbonylmethoxy) -1-naphthyl] methane (hereinafter referred to as "MBNAC-M") (3.56 g (0.008 mol)) as a dicarboxylic acid component, and BNEF as a diol component. (3.23 g (0.006 mol)), EG (1.62 g (0.026 mol)), transesterification reaction, and titanium tetrabutoxide (0.7 mg (2 μmol)) as a catalyst for the polycondensation reaction were charged. The ester exchange reaction was carried out by gradually heating and stirring to 240 ° C. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 275 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin. In addition, the obtained polyester resin was brittle, and it was difficult to prepare a film of a size used for measuring birefringence.

[Example 17]
In the reactor, MBNAC-M (26.67 g (0.06 mol)), FDP-m (20.32 g (0.06 mol)) as the dicarboxylic acid component, and BNEF (54.95 g (0.102 mol)) as the diol component. )), EG (16.05 g (0.258 mol)), titanium tetrabutoxide (3.4 mg (10 μmol)) as a catalyst for transesterification reaction and polycondensation reaction, and dibutyl phosphate (31) as a heat stabilizer. .5 mg (150 μmol)) was charged, and the mixture was gradually heated to 240 ° C. and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the pressure was gradually reduced while raising the temperature to 270 ° C. and 200 Pa, and the polycondensation reaction was carried out while removing ethylene glycol until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

[Comparative Example 1]
In the reactor, dimethyl isophthalate (DMI) (38.8 g (0.20 mol)) as a diester component, BNEF (86.2 g (0.16 mol)) and EG (27.2 g (0.44 mol)) as a diol component. )), Calcium acetate monohydrate (28.2 mg (160 μmol)) and manganese acetate tetrahydrate (9.8 mg (40 μmol)) were charged as catalysts for the transesterification reaction, and gradually heated to 240 ° C. and stirred. Then, a transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, trimethyl phosphate (39.2 mg (280 μmol)) was added as a heat stabilizer, and germanium oxide (41.8 mg (400 μmol)) was added as a catalyst for the polycondensation reaction. The pressure was gradually increased to 298 ° C. and 200 Pa, and the pressure was reduced. While removing ethylene glycol, a transesterification reaction was carried out until a predetermined stirring torque was reached. After completion of the reaction, the contents were taken out from the reactor to obtain a polyester resin.

Table 1 summarizes the charging ratios for producing the polyester resin in Examples and Comparative Examples. Further, Table 2 shows the polymer composition and various properties of the obtained polyester resin.

As is clear from Table 2, in the examples, both a high refractive index and a low birefringence could be achieved as compared with the comparative example. In particular, in the examples, heat resistance, mechanical properties, and moldability were also excellent.

The polyester 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 polyester resin (or its resin composition) 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. The polyester 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 for papers, 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 members, etc.) Etc.) can be suitably used for resins and the like.

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

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, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, heteroconductive film (ACF) ), Electromagnetic wave shielding (EMI) film, electrode substrate film, color filter substrate film, barrier film, color filter layer, black matrix layer, adhesive layer or release layer between optical films, and the like. 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 FPD devices (for example, personal computer monitors, televisions, mobile phones, car navigation systems, touch panels, etc.). LCD, PDP, etc.) and the like.

Claims (11)

The structural unit represented by the following formula (1) and / or the structural unit represented by the following formula (2 a ), the structural unit represented by the following formula (3), and the structural unit represented by the following formula (4). A polyester resin containing a structural unit and / or a structural unit represented by the following formula (5) .

(In the formula, A ¹ is a direct bond or an alkylene group, A ² is an alkylene group, L ₁ is an alkylene group, R ¹ and R ² are substituents, h is 0 or 1, n is an integer of 0 or more, and m is 0. ~ 2 integer, k is an integer 0-4)

(In the formula, A ³ is an alkylene group, L ₂ is an alkylene group, R ³ and R ⁴ are substituents, j is 0 or 1, p is an integer of 0 or more, q is an integer of 0 to 2, and r is 0 to 0. (An integer of 4)

(In the formula, ring Z is an arene ring, 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 4, and u is an integer of 0 or more.)

(In the formula, A ⁵ is an alkylene group, R ⁷ is a substituent, and v is an integer from 0 to 4).

(In the formula, A ⁶ is an alkylene group, R ⁸ is a substituent, and w and x are integers from 0 to 4). Claim 1, wherein the polyester resin structural unit represented by the formula (1) is a structural unit represented by the formula (1a).

(In the formula, A ¹ is a direct bond or an alkylene group, A ² is an alkylene group, L ₁ is an alkylene group, R ¹ and R ² are substituents, h is 0 or 1, n is an integer of 0 or more, and m is 0. ~ 2 integer, k is an integer 0-4 ) The polyester resin according to claim 1 or 2, wherein in the formula (1) or (1a), A ¹ is a direct bond or a methylene group, L ₁ is a methylene group, h is 1, and n is 0. The polyester resin according to any one of claims 1 to 3, wherein L ₂ is a methylene group and j is 0 in the formula ( 2a). The polyester resin according to any one of claims 1 to 4, wherein in the formula (3), Z is a naphthalene ring. The structural unit represented by the formula (1) and / or the structural unit represented by the formula (2 a ), and the structural unit represented by the formula (4) and / or the structural unit represented by the formula (5). The polyester resin according to any one of claims 1 to 5 , wherein the molar ratio of the former / the latter = 90/10 to 10/90. The molar ratio of the structural unit represented by the following formula (6) and the structural unit represented by the formula (3) to the structural unit represented by the formula (6) is the former / the latter = 100 /. The polyester resin according to any one of claims 1 to 6 , which is 0 to 10/90.

(Wherein, ^{A 7} is an alkylene group) In a film stretched three times at a temperature 10 ° C. higher than the glass transition point, the refractive index at 20 ° C. and a wavelength of 589 nm is 1.665 to 1.700, and the Abbe number at 20 ° C. is 15 to 25. The polyester resin according to any one of claims 1 to 7 , wherein the absolute value of birefringence at 20 ° C. and a wavelength of 600 nm is 0.01 × 10 ^-4 to 75 × 10 ^-4 . A molded product containing the polyester resin according to any one of claims 1 to 8 . The molded product according to claim 9, which is an optical member. The molded product according to claim 9 or 10, which is an optical film, an optical sheet, or an optical lens.