Thermoplastic resin having a binaphthyl skeleton, and its production method and use

Abstract

To provide a thermoplastic resin having a low Abbe number and excellent heat resistance, a method for producing the same and a use thereof, and a monomer compound that can form the thermoplastic resin.SOLUTION: A thermoplastic resin has a dicarboxylic acid unit (A), the dicarboxylic acid unit (A) having at least a first dicarboxylic acid unit (A1) represented by the formula (1). In the formula (1), R1a and R1b may be alkoxy groups (where R1a and R1b independently represent a hydrogen atom or a substituent, R2a and R2b independently represent a substituent, k1 and k2 independently represent an integer of 0-5).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thermoplastic resin having a specific dicarboxylic acid component having a 1,1'-binaphthyl skeleton as a polymerization component, and to a production method and use thereof. [Background technology]

[0002] In recent years, the development of small devices or mobile devices such as smartphones and tablet PCs has been remarkable, and the development of devices with higher performance (higher functionality) is progressing. In addition, the spread of social networking services (SNS) has made it easy for individuals to disseminate information, and these devices are often equipped with optical functions such as camera functions as well as image display functions. Therefore, as the performance of devices improves, the requirements for optical components are also increasing. For the optical components of these devices, resin materials are often used, which have advantages over optical glass in terms of light weight, impact resistance (flexibility), moldability (productivity), etc., but existing resin materials may not be able to fully meet the increasing requirements, and there is a demand for the development of new resins with excellent optical properties and heat resistance.

[0003] In particular, imaging lens units mounted on small devices or mobile devices with camera functions are required to be miniaturized as the devices themselves become thinner and more multifunctional, while at the same time, high resolution is required as the imaging elements have a higher pixel count. For this reason, imaging lens units are designed in various ways to select the lens configuration, shape, and material, and are optically designed to be small and capable of correcting various aberrations with high imaging performance. In general, imaging lens units are composed of multiple lenses with different Abbe numbers and refractive indexes, and are usually composed of a combination of lenses with high Abbe numbers and lenses with low Abbe numbers. However, since the resin materials that can be used for optical lenses are limited, there is a limit to the design of various lens units with high effectiveness. Therefore, if resins with various Abbe numbers can be prepared, the range of material selection can be expanded, the degree of freedom in design can be improved, and optimization of imaging lens units can be expected. From this perspective, the development of new optical resin materials is also required.

[0004] On the other hand, polyester resins having a 1,1'-binaphthyl structure have been attracting attention as resin materials with excellent optical properties and heat resistance.

[0005] Japanese Patent Laid-Open Publication No. 2001-72872 (Patent Document 1) discloses a resin containing, as a monomer component, a biaryl compound bonded via a bond axis capable of imparting internal rotational isomerism, and in which at least one of the aryl groups has a π electron number of 4n+6 (n is a natural number) relative to the bond axis. It is described that a resin composition containing such a resin is useful as a resin for forming optical lenses, since it has excellent transparency, small optical anisotropy (birefringence), a high refractive index, and low moisture absorption.

[0006] In addition, JP 2017-171885 A (Patent Document 2) discloses a polyester resin containing 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).

[0007] [ka]

[0008] (In the formula, A 1 is a direct bond or an alkylene group, A 2 is an alkylene group, L1 is an alkylene group, R 1 and R 2 is a substituent, h is 0 or 1, n is an integer of 0 or more, m is an integer of 0 to 2, and k is an integer of 0 to 4.

[0009] [ka]

[0010] (In the formula, A 3 is an alkylene group, L2 is an alkylene group, R 3 and R 4is a substituent, j is 0 or 1, p is an integer of 0 or more, q is an integer of 0 to 2, and r is an integer of 0 to 4.

[0011] [ka]

[0012] (Wherein, ring Z is an arene ring, A 4 is an alkylene group, R 5 and R 6 is a substituent, 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. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] JP 2001-72872 A [Patent Document 2] JP 2017-171885 A Summary of the Invention [Problem to be solved by the invention]

[0014] In the examples of Patent Document 1, various biaryl compounds having a 1,1'-binaphthyl skeleton, for example, dicarboxylic acid components such as 2,2'-bis(chlorocarbonylmethoxy)-1,1'-binaphthyl [compound (1-21)], 2,2'-bis(methoxycarbonylmethoxy)-1,1'-binaphthyl [compound (1-23)], or 4,4'-bis(methoxycarbonylmethoxy)-1,1'-binaphthyl [compound (1-24)], are used as polymerization components (monomer components) to synthesize polyester-based resins, and the obtained resins are then injection molded to produce optical lenses.

[0015] However, the examples in Patent Document 1 do not specifically describe optical properties such as refractive index, birefringence, and Abbe number, and heat resistance.

[0016] Patent Document 2 describes that it is possible to achieve both a high refractive index and low birefringence, which are in a trade-off relationship, and further that it has a low Abbe number and is excellent in heat resistance, moldability, and mechanical properties. In addition, with regard to the formula (1), it is preferable that h is 1 from the viewpoint of reactivity, and further that it is preferable that the group -[O-(A 2 O) n -L1] h It is described that --CO-- is preferably located at the 2-position (or 2'-position) of the naphthalene ring.

[0017] In the examples of Patent Document 2, various polyester resins are prepared using 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl (or BNAC-E) as a polymerization component, and it is described that the obtained polyester resins can achieve both a high refractive index and low birefringence, and are also excellent in heat resistance, mechanical properties, and moldability. It is also described that the Abbe number of the polyester resins of Examples 1 to 9 containing BNAC-E as a polymerization component was 18.4 to 20.2, and the Tg was 132.5 to 161.1°C.

[0018] Although Patent Document 2 provides a polyester resin that exhibits relatively good properties, such as a low Abbe number, high heat resistance, a high refractive index, and low birefringence, it is desired to further improve these properties.

[0019] Therefore, an object of the present invention is to provide a thermoplastic resin having a low Abbe number and excellent heat resistance, a production method and uses thereof, and a monomer compound capable of forming the thermoplastic resin. [Means for solving the problem]

[0020] As a result of intensive research to achieve the above-mentioned object, the inventors have found that when a thermoplastic resin is prepared using a dicarboxylic acid or an ester-forming derivative thereof having a carboxyl group at a specific substitution position on a 1,1'-binaphthyl skeleton as a polymerization component, the resulting polyester resin exhibits a lower Abbe number and high heat resistance, and have completed the present invention.

[0021] That is, the thermoplastic resin of the present invention is a thermoplastic resin containing dicarboxylic acid units (A), and the dicarboxylic acid units (A) contain at least a first dicarboxylic acid unit (A1) represented by the following formula (1).

[0022] [ka]

[0023] (In the formula, R 1a and R 1b each independently represents a hydrogen atom or a substituent, R 2a and R 2b each independently represents a substituent, and k1 and k2 each independently represent an integer of 0 to 5).

[0024] In the formula (1), R 1a and R 1b may be an alkoxy group. The first dicarboxylic acid unit (A1) represented by the formula (1) may contain a dicarboxylic acid unit represented by the following formula (1a).

[0025] [ka]

[0026] (In the formula, R 1a and R 1b , R 2a and R 2b , k1 and k2 are the same as in equation (1).

[0027] The dicarboxylic acid unit (A) may contain a second dicarboxylic acid unit (A2) represented by the following formula (2a) or (2b).

[0028] [ka]

[0029] (In the formula, R 4a represents a substituent, m1 represents an integer of 0 to 8, A 1a and A 1b each independently represents a divalent hydrocarbon group which may have a substituent, R 4b represents a substituent, m2 represents an integer of 0 to 8, A 1c represents a divalent hydrocarbon group which may have a substituent, m3 represents an integer from 0 to 4).

[0030] The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) may be the former / latter (molar ratio) of about 30 / 70 to 95 / 5.

[0031] The thermoplastic resin may be a polyester resin further containing a diol unit (B). The diol unit (B) may contain at least one diol unit selected from a first diol unit (B1) represented by the following formula (3), a second diol unit (B2) represented by the following formula (4), and a third diol unit (B3) represented by the following formula (5).

[0032] [ka]

[0033] (In the formula, A 2 represents a linear or branched alkylene group, and n represents an integer of 1 or more.

[0034] [ka]

[0035] (In the formula, Z 1 and Z 2 each independently represents an aromatic hydrocarbon ring, R 5 represents a substituent, p represents an integer of 0 to 8, R 6a and R 6b each independently represents a substituent; q1 and q2 each independently represent an integer of 0 or 1 or more; A 3a and A 3b each independently represents a linear or branched alkylene group, and r1 and r2 each independently represent an integer of 0 or 1 or more.

[0036] [ka]

[0037] (In the formula, A 4 represents a direct bond or an alkylene group, A 5a and A 5b represents a linear or branched alkylene group; s1 and s2 each independently represent an integer of 0 or 1 or more; R 7a and R 7b each independently represents a substituent, and t1 and t2 each independently represent an integer of 0 to 6).

[0038] In the formula (3), A 2 is linear or branched C 2-6 It is an alkylene group, and n may be an integer of about 1 to 5. In the formula (4), Z 1 and Z 2 is a monocyclic aromatic hydrocarbon ring or a condensed polycyclic aromatic hydrocarbon ring, and A 3a and A 3b is linear or branched C 2-6 It is an alkylene group, and r1 and r2 may be integers of about 0 to 10. In the formula (5), A 4 is a direct bond or C 1-2 is an alkylene group, 5a and A 5b is linear or branched C 2-6 It is an alkylene group, and s1 and s2 may be integers of about 0 to 10.

[0039] The ratio of the first diol unit (B1) may be about 1 mol % or more based on the total diol unit (B). The ratio of the first diol unit (B1) to the second diol unit (B2) may be the former / latter (molar ratio)=about 1 / 99 to 50 / 50. The ratio of the first diol unit (B1) to the third diol unit (B3) may be the former / latter (molar ratio)=about 5 / 95 to 50 / 50.

[0040] The present invention encompasses a method for producing the thermoplastic resin by polymerizing polymerization components that contain at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1).

[0041] The present invention also includes a compound represented by the following formula (1A):

[0042] [ka]

[0043] (In the formula, R 1a and R 1b are each independently C 1-5 represents an alkoxy group, R 3a and R 3b are each independently C 1-5 represents an alkoxy group, R 2a and R 2b , k1 and k2 are the same as in formula (1) above).

[0044] Furthermore, the present invention includes an Abbe number reducer represented by the following formula (1B).

[0045] [ka]

[0046] (In the formula, R 3a and R 3beach independently represents a hydroxyl group, an alkoxy group, or a halogen atom, R 1a and R 1b , R 2a and R 2b , k1 and k2 are the same as in formula (1) above.)

[0047] The present invention also includes a resin composition containing a thermoplastic resin and the Abbe number reducing agent.

[0048] The present invention further includes a molded article comprising the thermoplastic resin or the resin composition. The molded article may be an optical member. The molded article may be an optical film or an optical lens.

[0049] In this specification and claims, a "diol unit" or a "structural unit derived from a diol component" refers to a unit (or a divalent group) obtained by removing hydrogen atoms from two hydroxyl groups of the corresponding diol component, and a "diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit." Similarly, a "dicarboxylic acid unit" or a "structural unit derived from a dicarboxylic acid component" refers to a unit (or a divalent group) obtained by removing OH (hydroxyl group) from two carboxyl groups of the corresponding dicarboxylic acid, and a "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid components) may be used synonymously with the corresponding "dicarboxylic acid unit."

[0050] In the present specification and claims, the term "dicarboxylic acid component" refers to a dicarboxylic acid and its ester-forming derivatives. Examples of the ester-forming derivatives include alkyl esters, acid halides, and acid anhydrides. Examples of the alkyl esters include lower alkyl esters, such as methyl esters, ethyl esters, and t-butyl esters. 1-4 Alkyl esters, etc. The ester-forming derivatives may be monoesters (half esters) or diesters.

[0051] In addition, the present invention may solve the following problems as a secondary object.

[0052] In other words, another object of the present invention is to provide a thermoplastic resin that can satisfy, at an even higher level and in a well-balanced manner, four properties that are difficult to achieve simultaneously, namely, a low Abbe number, a high refractive index, low birefringence, and high heat resistance, a production method and uses thereof, and a monomer compound capable of forming the thermoplastic resin.

[0053] Yet another object of the present invention is to provide a thermoplastic resin which can be efficiently polymerized to have a relatively high molecular weight and has excellent moldability (productivity) despite containing a 1,1'-binaphthyl skeleton which is rigid and bulky and is expected to have a reduced polymerization reactivity due to the influence of steric hindrance and the like, a production method and uses thereof, and a monomer compound capable of forming said thermoplastic resin.

[0054] Another object of the present invention is to provide an Abbe number reducer capable of reducing the Abbe number of a thermoplastic resin.

[0055] In this specification and claims, the number of carbon atoms of a substituent is represented as C1, C6, C 10 For example, an alkyl group with one carbon atom is represented as "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is represented as "C 6-10 It is indicated as "aryl".

[0056] In addition, in this specification and the claims, unless otherwise specified, the terms "low birefringence" and "low birefringence" mean that the absolute value of birefringence is low (that is, close to 0). Effect of the Invention

[0057] The thermoplastic resin of the present invention uses a dicarboxylic acid or its ester-forming derivative having a carboxyl group at a specific substitution position of the 1,1'-binaphthyl skeleton as a polymerization component, and therefore can greatly reduce the Abbe number and has excellent heat resistance. In addition, the four properties of low Abbe number, high refractive index, low birefringence, and high heat resistance, which are difficult to achieve simultaneously, can be satisfied at a higher level in a well-balanced manner. Furthermore, despite containing a 1,1'-binaphthyl skeleton which is rigid and bulky and is expected to have a reduced polymerization reactivity due to the influence of steric hindrance, etc., it can be efficiently polymerized to prepare a relatively high molecular weight, and moldability (productivity) can also be improved. In particular, by adjusting the composition ratio to a specific ratio, in addition to the four properties, high moldability (productivity) can also be satisfied (or heat resistance and moldability can be compatible). In addition, the dicarboxylic acid or its ester-forming derivative can also be used as an Abbe number reducer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0058] [Thermoplastic resin] The thermoplastic resin may contain at least the first dicarboxylic acid unit (A1) represented by the following formula (1) as the dicarboxylic acid unit (A). Examples of such thermoplastic resins include polyamide-based resins and polyester-based resins, and polyester-based resins are preferred because they have low water absorption and are easy to use as optical members. Examples of polyester-based resins include polyester resins and polyester carbonate resins, and polyester resins are preferred.

[0059] (Dicarboxylic acid unit (A)) First Dicarboxylic Acid Unit (A1)

[0060] [ka]

[0061] (In the formula, R 1a and R 1b each independently represents a hydrogen atom or a substituent, R 2a and R 2beach independently represents a substituent, and k1 and k2 each independently represent an integer of 0 to 5).

[0062] When the dicarboxylic acid unit (A) contains the first dicarboxylic acid unit (A1), the Abbe number can be significantly reduced and the heat resistance can be significantly improved. In addition, the first dicarboxylic acid unit (A1) can achieve both a high refractive index and a low birefringence, which are usually in a trade-off relationship, and therefore the above-mentioned heat resistance and optical properties (low Abbe number, high refractive index, low birefringence) can be satisfied in a well-balanced manner. Furthermore, despite containing a rigid and bulky binaphthyl skeleton, the first dicarboxylic acid unit (A1) unexpectedly has high polymerization reactivity, and can effectively improve the moldability, handling (productivity), mechanical strength, etc. of the thermoplastic resin.

[0063] In the formula (1), R 1a and R 1b The substituent represented by the following formula (I) is preferably a substituent which is inactive in the polymerization reaction.

[0064] In the present specification and claims, the term "substituent inactive to polymerization reaction" refers to a non-polymerizable group that does not include a polymerizable group that participates in the formation of a bond on the main chain of a thermoplastic resin, such as an ester bond or an amide bond. That is, it refers to a substituent (non-reactive substituent) excluding ester- or amide-forming substituents such as a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, a halocarbonyl group, an acid anhydride group, and an amino group, and substituents that contain these groups in their chemical structure, such as a hydroxy(poly)alkoxy group and a carboxy(poly)alkoxy group.

[0065] R 1a and R 1b The substituent represented by the following formula (I) is preferably an electron-donating group, since it is easy to form a 1,1'-binaphthyl skeleton and is excellent in productivity.

[0066] Examples of the electron-donating group include hydrocarbon groups such as alkyl groups and aryl groups, hydroxyl groups, alkoxy groups, acyloxy groups, and mono- or di-substituted amino groups, and the electron-donating group may not contain a hydroxyl group.

[0067] Examples of the alkyl group include C methyl and ethyl groups. 1-6 Examples of the aryl group include C phenyl groups. 6-12 An aryl group and the like can be given.

[0068] Examples of the alkoxy group include C alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, and t-butoxy groups. 1-6 Examples of the acyloxy group include C alkoxy groups, such as acetoxy groups (methylcarbonyloxy groups). 2-7 Examples include an acyloxy group.

[0069] Examples of the mono- or di-substituted amino group include mono- or di-alkylamino groups, specifically, mono- or di-C groups such as dimethylamino groups. 1-6 Alkylamino groups; mono- or di-acylamino groups, specifically, mono- or di-C such as monoacetylamino group (N-methylcarbonylamino group); 2-7 Examples include an acylamino group.

[0070] Preferred groups R 1a , R 1b The C is preferably a hydrogen atom or an alkoxy group, and is preferably a hydrogen atom from the viewpoint of improving the polymerization reactivity and suppressing the fluctuation in the refractive index and dimensions of the molded body due to water absorption (or improving the refractive index stability and dimensional stability). From the viewpoint of improving the refractive index stability and dimensional stability, and productivity in a well-balanced manner, a linear or branched C 1-5 Alkoxy groups such as alkoxy groups are particularly preferred. Among the alkoxy groups, linear or branched C 1-4 Alkoxy groups are preferred, and linear or branched C 1-3Alkoxy groups are more preferred, particularly C such as methoxy groups. 1-2 An alkoxy group is preferred. 1a and R 1b The types may be different from each other, but are usually the same.

[0071] R 2a and R 2b is preferably a substituent that is inactive in the polymerization reaction (non-polymerizable group), and examples thereof include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups (or groups R h ); a group -OR corresponding to the above-mentioned hydrocarbon group, such as an alkoxy group, a cycloalkyloxy group, an aryloxy group, or an aralkyloxy group; h (In the formula, R h represents the above-mentioned hydrocarbon group; a group -SR corresponding to the above-mentioned hydrocarbon group, such as an alkylthio group, a cycloalkylthio group, an arylthio group, or an aralkylthio group; h (In the formula, R h represents the above-mentioned hydrocarbon group); an acyl group; a nitro group; a cyano group; a substituted amino group, and the like.

[0072] R h Examples of the alkyl group represented by the formula (I) include linear or branched C alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, and t-butyl groups. 1-10 Alkyl groups, preferably linear or branched C 1-6 Alkyl groups, more preferably linear or branched C 1-4 Alkyl groups and the like.

[0073] R h Examples of the cycloalkyl group represented by the formula (I) include a cyclopentyl group, a cyclohexyl group, and the like. 5-10 cycloalkyl groups, etc.

[0074] R hExamples of the aryl group represented by the formula (I) include a phenyl group, an alkylphenyl group, a biphenylyl group, a naphthyl group, and the like. 6-12 Examples of the alkylphenyl group include a methylphenyl group (tolyl group) and a dimethylphenyl group (xylyl group).

[0075] R h Examples of the aralkyl group represented by the formula (I) include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Alkyl groups and the like.

[0076] Group -OR h The above-mentioned examples of the hydrocarbon group R h , including preferred embodiments thereof, for example, linear or branched C such as methoxy groups. 1-10 Alkoxy groups, cyclohexyloxy groups, etc. 5-10 Cycloalkyloxy group, phenoxy group, etc. 6-10 C such as aryloxy group, benzyloxy group 6-10 Aryl-C 1-4 Alkyloxy groups and the like.

[0077] Group -SR h The above-mentioned examples of the hydrocarbon group R h , including preferred embodiments thereof, for example, linear or branched C such as methylthio groups. 1-10 C such as alkylthio group and cyclohexylthio group 5-10 Cycloalkylthio group, thiophenoxy group (phenylthio group), etc. 6-10 C such as arylthio group, benzylthio group 6-10 Aryl-C 1-4 Examples of the alkyl group include an alkylthio group.

[0078] Examples of the acyl group include C 1-6 Examples include acyl groups.

[0079] Examples of the substituted amino group include mono- or di-alkylamino groups, mono- or bis(alkylcarbonyl)amino groups, etc. Examples of the mono- or di-alkylamino group include mono- or di-C groups such as dimethylamino group. 1-4 Examples of the mono- or bis(alkylcarbonyl)amino group include mono- or bis(C 1-4 alkyl-carbonyl)amino groups and the like.

[0080] Of these substituents, halogen atoms such as bromine atoms are preferred.

[0081] R 2a , R 2b The substitution numbers k1 and k2 of may be, for example, integers of about 0 to 4, and the preferred ranges are, in the following stepwise order, integers of 0 to 3, integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0. k1 and k2 may be different from each other, but are preferably the same. When k1 is 2, the two R 2a The types of R may be the same or different from each other. When k2 is 2, the two R 2b The types of R may be the same or different. 2a , R 2b The types may be the same or different from each other.

[0082] R 2a , R 2b The substitution position of is R of the 1,1'-binaphthyl skeleton. 1a ,R 1b (2,2'-positions) and a position other than the bonding position of the carbonyl group [-C(=O)-] that forms the main chain of the thermoplastic resin, i.e., any position selected from the 3-8 positions and the 3'-8' positions, and preferably any position selected from the 3-5 positions, the 7-8 positions, the 3'-5' positions, and the 7'-8' positions.

[0083] In formula (1), the bonding positions of the two carbonyl groups [-C(=O)-] forming the main chain of the thermoplastic resin may be any of the 5- to 8-positions and the 5'- to 8'-positions (i.e., the benzene ring opposite the benzene ring directly bonded at the 1,1'-position in the 1,1'-binaphthyl skeleton), but are preferably the 5,5'-positions, 6,6'-positions, or 7,7'-positions, and more preferably the 6,6'-positions as represented by the following formula (1a).

[0084] [ka]

[0085] (In the formula, R 1a and R 1b , R 2a and R 2b , k1 and k2 are the same as in formula (1) including preferred embodiments.

[0086] Representative first dicarboxylic acid components corresponding to the first dicarboxylic acid unit (A1) include R 1a and R 1b Dicarboxylic acid components corresponding to units in which is an alkoxy group, for example, 6,6'-dicarboxy-2,2'-dialkoxy-1,1'-binaphthyl, specifically, 6,6'-dicarboxy-2,2'-diC such as 6,6'-dicarboxy-2,2'-dimethoxy-1,1'-binaphthyl and 6,6'-dicarboxy-2,2'-diethoxy-1,1'-binaphthyl. 1-6 Examples include alkoxy-1,1'-binaphthyl and ester-forming derivatives thereof.

[0087] The first dicarboxylic acid unit (A1) may be contained alone or in combination of two or more kinds. Among the first dicarboxylic acid units (A1), 6,6'-dicarboxy-2,2'-dicarboxylate such as 6,6'-dicarboxy-2,2'-dimethoxy-1,1'-binaphthyl is preferred from the viewpoint of productivity. 1-4 A structural unit derived from alkoxy-1,1'-binaphthyl is preferred.

[0088] The ratio of the structural unit represented by the formula (1a), particularly the ratio of the dicarboxylic acid unit corresponding to 6,6'-dicarboxy-2,2'-dialkoxy-1,1'-binaphthyl, can be selected from the range of, for example, 1 mol% or more, specifically, about 10 to 100 mol% relative to the entire first dicarboxylic acid unit (A1), and the preferred ranges are 30 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and more preferably 100 mol% in the following stepwise manner. That is, it is preferable that the first dicarboxylic acid unit (A1) is substantially formed only by the structural unit represented by the formula (1a), particularly only by the dicarboxylic acid unit corresponding to 6,6'-dicarboxy-2,2'-dialkoxy-1,1'-binaphthyl.

[0089] Second Dicarboxylic Acid Unit (A2) The dicarboxylic acid unit (A) may or may not contain a second dicarboxylic acid unit (A2) represented by the following formula (2a) or (2b), as necessary.

[0090] [ka]

[0091] (In the formula, R 4a represents a substituent, m1 represents an integer of 0 to 8, A 1a and A 1b each independently represents a divalent hydrocarbon group which may have a substituent, R 4b represents a substituent, m2 represents an integer of 0 to 8, A 1c represents a divalent hydrocarbon group which may have a substituent, m3 represents an integer from 0 to 4).

[0092] When the second dicarboxylic acid unit (A2) is contained, birefringence is easily reduced while a relatively high refractive index is maintained, and polymerization reactivity tends to be easily improved even if the polymer has a rigid fluorene skeleton.

[0093] In the formula (2a) or (2b), R 4a and R 4b The substituent represented by the formula (I) is preferably a substituent that is inactive in a polymerization reaction (non-polymerizable group), and examples thereof include a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; and a hydrocarbon group such as an alkyl group or an aryl group.

[0094] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. 1-12 Examples of the aryl group include C alkyl groups such as phenyl and naphthyl groups. 6-10 An aryl group and the like can be given.

[0095] These substituents R 4a and R 4b Among these, when the number of substitutions m1 and m2 is 1 or more, a cyano group, a halogen atom, an alkyl group or an aryl group is preferable, an alkyl group or an aryl group is more preferable, and an aryl group is even more preferable. Preferred alkyl groups include linear or branched C 1-8 and preferably a linear or branched C alkyl group such as a methyl group. 1-4 Preferred aryl groups include C 6-10 An aryl group is preferable, and a naphthyl group is more preferable.

[0096] The substitution numbers m1 and m2 may each be, for example, an integer of about 0 to 6, and the preferred ranges are, in the following stepwise order, integers of 0 to 4, integers of 0 to 3, and integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0097] In addition, the group R 4a , R 4b When the number of substitutions m1 and m2 is 2 or more, two or more groups R 4a , R 4b The types of R may be the same or different from each other. 4a , R 4bThe bonding position (substitution position) of is not particularly limited, and examples thereof include the 2-position, 7-position, and 2,7-position of the fluorene ring.

[0098] In particular, the substituent R 4a and R 4b When the substituent R is an aryl group such as a naphthyl group, the Abbe number can be reduced. 4a and R 4b When m1 and m2 are each an aryl group such as a naphthyl group, m1 and m2 are each, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 3, and even more preferably 2. When m1 and m2 are each 2, the substituent R 4a and R 4b The substitution positions are preferably the 2- and 7-positions.

[0099] Base A 1a and A 1b And A 1c Examples of the hydrocarbon group represented by the formula (I) include linear or branched alkylene groups, such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl groups. 1-8 Preferred alkylene groups include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl groups. 1-6 An alkylene group is preferred, and a linear or branched C 1-4 It is an alkylene group.

[0100] The substituent that the hydrocarbon group may have is preferably a substituent that is inactive in the polymerization reaction (non-polymerizable group), and examples thereof include aryl groups such as a phenyl group, and cycloalkyl groups such as a cyclohexyl group. 1a and A 1b And A 1c Examples of the alkyl group include a 1-phenylethylene group and a 1-phenylpropane-1,2-diyl group.

[0101] Base A 1a and A1b is linear or branched C 2-4 It is preferably an alkylene group, and among them, a linear or branched C alkylene group such as an ethylene group or a propylene group is preferable. 2-3 It is preferably an alkylene group, particularly an ethylene group. 1c is a straight or branched chain C such as methylene or ethylene groups. 1-3 It is preferably an alkylene group. 1a and A 1b The types of may be different from each other, but are preferably the same.

[0102] In the formula (2b), the number of repeating methylene groups, m3, is, for example, an integer of about 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0103] Representative examples of the second dicarboxylic acid component corresponding to the constitutional unit represented by the formula (2a) include, for example, A 1a and A 1b is linear or branched C 2-6 Dicarboxylic acid components corresponding to the alkylene groups, such as 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene, 2-6 9,9-bis(carboxy)C such as 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene 2-6 Alkyl)-diC 6-10 Arylfluorenes and their ester-forming derivatives are included.

[0104] Representative examples of the second dicarboxylic acid component corresponding to the constitutional unit represented by the formula (2b) include 9-(dicarboxyphenyl)-1,2-dicarboxylic acid, 2-8 m3 is 0, A alkyl)fluorene and their ester forming derivatives, specifically, 9-(1,2-dicarboxyethyl)fluorene, 9-(1,2-dicarboxyethyl)-2,7-di(2-naphthyl)fluorene, etc. 1c is linear or branched C 1-6Dicarboxylic acid components corresponding to the alkylene groups; m3 is 1, such as 9-(2,3-dicarboxypropyl)fluorene, 9-(2,3-dicarboxypropyl)-2,7-di(2-naphthyl)fluorene, etc. 1c is linear or branched C 1-6 and a dicarboxylic acid component corresponding to the alkylene group.

[0105] The second dicarboxylic acid unit (A2) derived from these second dicarboxylic acid components (A2) may be contained alone or in combination of two or more. Among these second dicarboxylic acid units (A2), it is preferable to contain at least a dicarboxylic acid unit represented by the above formula (2a) in terms of ease of reducing birefringence, and 9,9-bis(carboxy C 2-6 More preferred are structural units derived from 9,9-bis(carboxyalkyl)fluorenes such as 9,9-bis(carboxyalkyl)fluorenes. 2-4 9,9-bis(carboxyalkyl)fluorene, more preferably 9,9-bis(carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, etc. 2-3 It is preferred that the compound contains a structural unit derived from 9,9-bis(2-carboxyethyl)fluorene, in particular 9,9-bis(2-carboxyethyl)fluorene.

[0106] The ratio of the structural unit represented by the formula (2a), particularly the ratio of the dicarboxylic acid unit corresponding to 9,9-bis(carboxyalkyl)fluorene, can be selected from the range of, for example, 1 mol% or more, specifically, about 10 to 100 mol%, based on the entire second dicarboxylic acid unit (A2), and the preferred range is 30 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and more preferably 100 mol%. That is, it is preferable that the second dicarboxylic acid unit (A2) is substantially formed only by the structural unit represented by the formula (2a), particularly only by the dicarboxylic acid unit corresponding to 9,9-bis(carboxyalkyl)fluorene.

[0107] Third Dicarboxylic Acid Unit (A3) In addition, the dicarboxylic acid unit (A) may or may not contain a third dicarboxylic acid unit (A3) different from the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2), as necessary.

[0108] Examples of the third dicarboxylic acid unit (A3) include structural units derived from an aromatic dicarboxylic acid component (excluding the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2)), an alicyclic dicarboxylic acid component, an aliphatic dicarboxylic acid component, and the like.

[0109] Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkyl benzene dicarboxylic acids, specifically, C 4-methylisophthalic acid and the like; 1-4 Alkyl-benzene dicarboxylic acids and the like.

[0110] Examples of polycyclic aromatic dicarboxylic acids include condensed polycyclic aromatic dicarboxylic acids, specifically, condensed polycyclic C dicarboxylic acids such as naphthalenedicarboxylic acid, anthracene dicarboxylic acid, and phenanthrene dicarboxylic acid. 10-24 Arene-dicarboxylic acids, preferably fused polycyclic C 10-14 arene-dicarboxylic acids, etc.; biaryl dicarboxylic acids, specifically, bi-C such as 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, and 3,3'-dicarboxy-1,1'-binaphthyl 6-10 Aryl-dicarboxylic acids, etc.; Bis(carboxyalkoxy)bis(C 6-10 Aryl, specifically, bis(carboxy C such as 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl 1-4 Alkoxy)BiC 6-10 Aryl, etc.; Bis[(carboxyalkoxy)-C 6-10aryl]alkanes, specifically bis[(carboxy C 1-4 Alkoxy)-C 6-10 Aryl)C 1-6 Alkanes, etc.; diarylalkane dicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethane dicarboxylic acid 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C 6-10 aryl) ketone-dicarboxylic acids; diaryl ether dicarboxylic acids, specifically, di(C aryl) ketone-dicarboxylic acids such as 4.4'-diphenyl ether dicarboxylic acid; 6-10 aryl) ether-dicarboxylic acids; diarylsulfone dicarboxylic acids, specifically, di(C aryl) ether-dicarboxylic acids such as 4.4'-diphenylsulfone dicarboxylic acid; 6-10 aryl)sulfone-dicarboxylic acids and the like.

[0111] Examples of the naphthalenedicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid is most often used.

[0112] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically, C 1,4-cyclohexane dicarboxylic acid. 5-10 Cycloalkane dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically, bi- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10Examples of the cycloalkene dicarboxylic acids include bridged cyclic cycloalkene dicarboxylic acids, specifically, bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid, and ester-forming derivatives thereof.

[0113] Examples of the aliphatic dicarboxylic acid component include alkanedicarboxylic acids, specifically, C carboxylic acids such as succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, and dodecanedicarboxylic acid. 2-18 Alkane-dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically, C such as maleic acid, fumaric acid, and itaconic acid 2-10 Alkene-dicarboxylic acids and their ester-forming derivatives are included.

[0114] These dicarboxylic acid components can be used alone or in combination of two or more. Among these, as the third dicarboxylic acid unit (A3), C dicarboxylic acids such as benzene dicarboxylic acid such as terephthalic acid and dodecane dicarboxylic acid are preferred because they can improve moldability. 2-12 Alkane-dicarboxylic acids are preferred.

[0115] The total proportion of the first dicarboxylic acid units (A1) and the second dicarboxylic acid units (A2) can be selected, for example, from 1 mol % or more, specifically from about 10 to 100 mol %, based on the entire dicarboxylic acid units (A). Preferred ranges are 30 mol % or more, 50 mol % or more, 60 mol % or more, 70 mol % or more, 80 mol % or more, 90 mol % or more, and 95 mol % or more in the following stepwise order. It is particularly preferred that the total proportion is 100 mol %, substantially free of the third dicarboxylic acid units (A3).

[0116] The ratio of the first dicarboxylic acid unit (A1) can be selected from, for example, 1 mol% or more, specifically, about 10 to 100 mol% relative to the total dicarboxylic acid unit (A), and the preferred ranges are 20 to 100 mol%, 30 to 100 mol%, 40 to 95 mol%, and 45 to 92 mol% or more in the following stepwise order, and from the viewpoint of improving excellent optical properties (low Abbe number, high refractive index, and low birefringence) and heat resistance in a more balanced manner, it is 40 to 80 mol%, preferably 45 to 75 mol%. If the ratio of the first dicarboxylic acid unit (A1) is too small, the Abbe number cannot be sufficiently reduced or the heat resistance cannot be sufficiently improved, so that it may be difficult to satisfy heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) in a balanced manner.

[0117] The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) (hereinafter simply referred to as A1 / A2) may be selected from the range of, for example, A1 / A2 (molar ratio) = about 1 / 99 to 100 / 0, and the preferred ranges are 10 / 90 to 99 / 1, 30 / 70 to 95 / 5, 40 / 60 to 93 / 7, 45 / 55 to 92 / 8, and 50 / 50 to 90 / 10 in the following stepwise manner. In applications where low birefringence is important, A1 / A2 (molar ratio) = 40 / 60 to 80 / 20, preferably 45 / 55 to 70 / 30 may be used. If the ratio of the first dicarboxylic acid unit (A1) is too low, the glass transition temperature may decrease, resulting in a decrease in heat resistance, or the Abbe number may not be sufficiently reduced, or the refractive index may decrease. On the other hand, if the proportion of the second dicarboxylic acid unit (A2) is too small, the birefringence may not be reduced sufficiently.

[0118] In addition, when the dicarboxylic acid unit (A) is combined with the first diol unit (B1) described later, the A1 / A2 (molar ratio) may be selected from the range of about 40 / 60 to 100 / 0, and the preferred ranges are 50 / 50 to 99 / 1, 60 / 40 to 98 / 2, 70 / 30 to 97 / 3, 80 / 20 to 96 / 4, and 85 / 15 to 95 / 5 in the following stepwise order. When the dicarboxylic acid unit (A) is combined with the first diol unit (B1) in such a ratio, the Abbe number can be further reduced and the heat resistance can be greatly improved.

[0119] When the dicarboxylic acid unit (A) is combined with the second diol unit (B2) described later, the A1 / A2 (molar ratio) may be selected from the range of about 10 / 90 to 100 / 0, and the preferred ranges are 20 / 90 to 95 / 5, 30 / 70 to 90 / 10, 35 / 65 to 85 / 15, 40 / 60 to 80 / 20, and 45 / 55 to 75 / 25 in the following stepwise order. When combined with the second diol unit (B2) in such a ratio, it appears that excellent optical properties (low Abbe number, high refractive index, and low birefringence) can be exhibited while the heat resistance can be greatly improved, making it suitable for applications requiring durability in high temperature environments such as vehicle-mounted lenses. In particular, Z in formula (4) 1 and Z 2 When A1 is combined with a second diol unit (B2) having a condensed polycyclic aromatic hydrocarbon ring such as a naphthalene ring, A1 / A2 (molar ratio) may be selected from a range of about 30 / 70 to 70 / 30, and preferred ranges are 35 / 65 to 65 / 35, 40 / 60 to 60 / 40, and 45 / 55 to 55 / 45 in the following stepwise order. When A1 is combined with the second diol unit (B2) in such a ratio, it appears that the refractive index and heat resistance in particular can be further improved while high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) are satisfied in a well-balanced manner. On the other hand, when Z in formula (4) is 1 and Z 2 When combined with the second diol unit (B2) having a benzene ring (monocyclic aromatic hydrocarbon ring), the A1 / A2 (molar ratio) may be selected from a range of about 50 / 50 to 90 / 10, and the preferred ranges are 55 / 45 to 85 / 15, 60 / 40 to 80 / 20, and 65 / 35 to 75 / 25 in the following stepwise order. When combined with the second diol unit (B2) in such a ratio, it appears that the birefringence in particular can be more effectively reduced and the heat resistance can be greatly improved while high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) are well balanced.

[0120] When the dicarboxylic acid unit (A) is combined with the third diol unit (B3) described later, the A1 / A2 (molar ratio) may be selected from the range of about 50 / 50 to 90 / 10, and the preferred ranges are 55 / 45 to 85 / 15, 60 / 40 to 80 / 20, and 65 / 35 to 75 / 25 in the following stepwise order. Combining with the third diol unit (B3) in such a ratio provides a particularly excellent balance of high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence), and also provides good moldability, which is most preferred.

[0121] [Diol unit (B)] The thermoplastic resin is preferably a polyester resin containing a diol unit (B) in addition to the dicarboxylic acid unit (A). The diol unit (B) is not particularly limited, but preferably contains at least one diol unit selected from a first diol unit (B1) represented by the following formula (3), a second diol unit (B2) represented by the following formula (4), and a third diol unit (B3) represented by the following formula (5), and more preferably contains at least the first diol unit (B1).

[0122] First Diol Unit (B1)

[0123] [ka]

[0124] (In the formula, A 2 represents a linear or branched alkylene group, and n represents an integer of 1 or more.

[0125] When the first diol unit (B1) is contained, the polymerization reactivity is increased, and the molecular weight is easily increased. At the same time, flexibility or toughness is imparted to the thermoplastic resin, and the moldability and handling properties are greatly improved.

[0126] In the formula (3), A 2Examples of the alkylene group represented by the formula (I) include linear or branched C alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetramethylene group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1,8-octanediyl group, and 1,10-decanediyl group. 2-12 Preferred alkylene groups A 2 The following are the linear or branched chain C 2-10 Alkylene group, linear or branched C 2-8 Alkylene group, linear or branched C 2-6 Alkylene group, linear or branched C 2-4 An alkylene group, more preferably a linear or branched C group such as an ethylene group or a propylene group. 2-3 An alkylene group is preferred, and an ethylene group is particularly preferred.

[0127] Alkyleneoxy group [-(A 2 The repeat number n of the alkyleneoxy group (-A)- can be selected, for example, from about 1 to 10, and preferred ranges are 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, with 1 being particularly preferred. The repeat number n may be an average value (arithmetic mean value or additive mean value), and preferred embodiments may be the same as those in the range of integers described above. When n is 2 or more, two or more alkyleneoxy groups (-A)- can be selected from the range of about 1 to 10, and preferred ranges are 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, with 1 being particularly preferred. 2 O-) may be different from each other, but are usually the same.

[0128] Examples of the first diol component corresponding to the first diol unit (B1) represented by the formula (3) include alkanediols (or alkylene glycols) and polyalkanediols (or polyalkylene glycols).

[0129] The alkylene glycol is, for example, the alkylene glycol represented by the formula (3) where n is 1 and A 2corresponding to the alkylene group exemplified above, specifically, linear or branched C alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol. 2-12 Alkylene glycol and the like are examples of the alkylene group A. 2 The same applies to the corresponding

[0130] The polyalkylene glycol is, for example, the polyalkylene glycol represented by the formula (3) in which n is 2 or more, preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4; 2 Compounds in which the alkylene group corresponds to the above-mentioned alkylene group, specifically, di- or deca-linear or branched C alkylenes such as diethylene glycol, dipropylene glycol, and triethylene glycol. 2-12 Alkylene glycols and the like are preferred, and di- or hexa-linear or branched C 2-6 Alkylene glycol, more preferably di- or tetra-linear or branched C 2-4 Alkylene glycols are included.

[0131] The first diol unit (B1) formed by these first diol components may be contained alone or in combination of two or more kinds. The first diol unit (B1) is preferably an alkylene glycol, more preferably a linear or branched C alkylene glycol, in terms of being easy to maintain high heat resistance. 2-6 Alkylene glycol, more preferably linear or branched C alkylene glycol, such as ethylene glycol, propylene glycol, 1,4-butanediol, etc. 2-4 Alkylene glycols, particularly linear or branched C alkylene glycols such as ethylene glycol and propylene glycol 2-3 It is preferred that the copolymer contains structural units derived from alkylene glycol, particularly ethylene glycol.

[0132] Second Diol Unit (B2) The diol unit (B) may or may not contain a second diol unit (B2) represented by the following formula (4) as necessary. When the second diol unit (B2) is contained, the optical properties (low Abbe number, high refractive index, and low birefringence) can be improved in a well-balanced manner while the heat resistance can be significantly improved, and the composition can be effectively used in applications requiring durability in high-temperature environments, such as vehicle-mounted lenses.

[0133] [ka]

[0134] (In the formula, Z 1 and Z 2 each independently represents an aromatic hydrocarbon ring, R 5 represents a substituent, p represents an integer of 0 to 8, R 6a and R 6b each independently represents a substituent; q1 and q2 each independently represent an integer of 0 or 1 or more; A 3a and A 3b each independently represents a linear or branched alkylene group, and r1 and r2 each independently represent an integer of 0 or 1 or more.

[0135] While exhibiting excellent optical properties (low Abbe number, high refractive index, and low birefringence), it appears possible to significantly improve heat resistance, making it suitable for applications that require durability in high-temperature environments, such as automotive lenses.

[0136] In the formula (4), Z 1 and Z 2 Examples of the aromatic hydrocarbon ring (arene ring) represented by the formula (I) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like. The polycyclic arene ring includes a fused polycyclic aromatic hydrocarbon ring (fused polycyclic arene ring), a ring-assembled aromatic hydrocarbon ring (ring-assembled arene ring), and the like.

[0137] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes, for example, fused bicyclic C rings such as naphthalene ring and indene ring. 10-16 Examples of the fused tricyclic arene ring include an anthracene ring and a phenanthrene ring. Examples of the preferred fused polycyclic arene ring include fused polycyclic C rings such as a naphthalene ring and an anthracene ring. 10-16 arene rings, and more preferably fused polycyclic C 10-14 An arene ring is exemplified, and a naphthalene ring is particularly preferred.

[0138] Examples of the ring assembly arene ring include biarene ring (or biaryl ring), terarene ring (or teraryl ring), etc. Examples of the biarene ring include biphenyl ring, binaphthyl ring, phenylnaphthalene ring, etc. 6-12 Examples of the phenylnaphthalene ring include a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring. Examples of the terarene ring include a terphenylene ring. 6-12 arene rings. Preferred ring-assembly arene rings include biC 6-10 An arene ring is exemplified, and a biphenyl ring is particularly preferred.

[0139] Z 1 and Z 2 The types of Z may be the same or different, and are preferably the same. 1 and Z 2 Among them, C rings such as benzene ring, naphthalene ring, and biphenyl ring 6-12 Arene rings are preferred, and C rings such as benzene rings and naphthalene rings are preferred. 6-10 Arene rings are more preferred. Z is particularly preferred in terms of being able to improve the refractive index and heat resistance even more significantly while providing a good balance between high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence). 1 and Z 2is more preferably a condensed polycyclic arene ring such as a naphthalene ring, and on the other hand, Z is more preferably a condensed polycyclic arene ring such as a naphthalene ring, from the viewpoints of being able to effectively reduce birefringence and greatly improve heat resistance while satisfying high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) in a well-balanced manner. 1 and Z 2 More preferably, is a benzene ring.

[0140] In addition, Z bonded to the 9-position of the fluorene ring 1 and Z 2 The substitution position of is not particularly limited, and for example, Z 1 , Z 2 When is a benzene ring, it may be at any position, and Z 1 , Z 2 is a naphthalene ring, it is either the 1-position or the 2-position, preferably the 2-position; Z 1 , Z 2 When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0141] R 5 The substituent represented by the formula (2a) or (2b) is preferably a substituent that is inactive in the polymerization reaction (non-polymerizable group), and examples of the substituent represented by the formula (2a) or (2b) are the groups R 4a and R 4b and the like, including preferred embodiments thereof.

[0142] Also, R 5 The number of substitutions p is the same as m1 and m2 described in the sections of formulae (2a) and (2b), including preferred embodiments, and is particularly preferably 0.

[0143] In addition, when the number of substitutions p is 2 or more, two or more groups R 5 The types of groups R may be the same or different from each other. 5 The bonding position (substitution position) of is not particularly limited, and examples thereof include the 2-position, 7-position, and 2,7-position of the fluorene ring.

[0144] R 6a and R6b The substituent represented by the formula (1) is preferably a substituent that is inactive in the polymerization reaction (non-polymerizable group), and examples of the substituent represented by the formula (1) include R 2a and R 2b Representative examples of the substituents include the same groups as those exemplified for R 6a and R 6b Examples of R include halogen atoms, hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. 6a and R 6b Examples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group, and more preferably a linear or branched C 1-6 C such as alkyl group and cyclohexyl group 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 Linear or branched C such as aryl and methoxy groups 1-4 Among these, alkyl groups and aryl groups are preferred, and in particular, linear or branched C aryl groups such as methyl groups are preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is preferred. 6a , R 6b is an aryl group, R 6a , R 6b are rings Z 1 , Z 2 may form the ring assembly arene ring.

[0145] R 6a , R 6b The numbers of substitutions q1 and q2 may be integers of 0 or more, and the ring Z 1 , Z 2The number of q1 and q2 may be appropriately selected depending on the type of R, and may be, for example, an integer of about 0 to 8. Preferred ranges are, in the following order, integers of 0 to 6, integers of 0 to 4, integers of 0 to 3, and integers of 0 to 2, with 0 or 1 being more preferred, and 0 being particularly preferred. q1 and q2 may be different from each other, but are preferably the same. When q1 and q2 are 2 or more, 2 or more R 6a , R 6b The types of R may be the same or different. 6a , R 6b The types of may be the same or different from each other. In particular, when q1 and q2 are 1, Z 1 , Z 2 is a benzene ring, a naphthalene ring or a biphenyl ring, R 6a , R 6b may be a methyl group. 6a , R 6b The substitution position of Z is not particularly limited. 1 , Z 2 The substitution may be made at any position other than the bonding position between the ether bond (-O-) forming the main chain and the 9-position of the fluorene ring. For example, Z 1 , Z 2 may be substituted at the ortho position (the carbon atom adjacent to the bonding position of the ether bond) relative to the ether bond (-O-).

[0146] Alkylene Group A 3a and A 3b Examples of the alkyl group include linear or branched C alkyl groups such as ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene groups. 2-6 Alkylene groups and the like are preferably linear or branched C 2-4 Alkylene groups, more preferably linear or branched C such as ethylene groups and propylene groups. 2-3 Alkylene groups, particularly ethylene groups, are preferred.

[0147] Alkyleneoxy group [-(A 3a O)-], [-(A 3bThe repeat numbers (number of added moles) r1 and r2 of the formula (O)-] may each be 0 or more, and may be selected from a range of about 0 to 15, for example, and the preferred ranges are 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1, in the following stepwise order. In addition, when the repeat numbers r1 and r2 are 1 or more, the polymerization reactivity is easily improved, and they may be selected from a range of about 1 to 15, and the preferred ranges are 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, and 1 is particularly preferred. In this specification and claims, the "repeat number (number of added moles)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of added moles, and the preferred embodiment may be the same as the preferred integer range described above. If r1 and r2 are too large, the heat resistance and refractive index may be reduced. In addition, r1 and r2 may be the same or different from each other. When r1 and r2 are 2 or more, they are each 2 or more alkyleneoxy groups [-(A 3a O)-], [-(A 3b O)-] may be different from each other, but are preferably the same. 3a and A 3b The types may be the same or different from each other.

[0148] The group [-O-(A 3a O) r1 -], [-O-(A 3b O) r2 -] (i.e., the ether bond forming the main chain) of ring Z 1 , Z 2 The substitution position for Z is not particularly limited. 1 , Z 2 The group [-O-(A 3a O) r1 -], [-O-(A 3b O) r2 -] Ring Z 1 , Z 2 The substitution position for Z 1 , Z 2When Z is a benzene ring, it is preferably substituted at any one of the 2-, 3-, or 4-positions, among which the 3- or 4-position, and particularly the 4-position, of the phenyl group bonded to the 9-position of the fluorene ring. 1 , Z 2 When Z is a naphthalene ring, it is often substituted at any one of the 5-8 positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted with respect to the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and it is preferred that the 1,5-position, 2,6-position, and especially 2,6-position are substituted with respect to this substitution position. 1 , Z 2 When is a ring assembly arene ring, the group [-O-(A 3a O) r1 -], [-O-(A 3b O) r2 The position of substitution of -] is not particularly limited, and may be, for example, substituted on the arene ring bonded to the 9-position of the fluorene or on the arene ring adjacent to this arene ring. For example, Z 1 , Z 2 is a biphenyl ring (or Z 1 , Z 2 is a benzene ring, q1 and q2 are 1, R 6a , R 6b is a phenyl group), the 3- or 4-position of the biphenyl ring, preferably the 3-position, may be bonded to the 9-position of the fluorene. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the group [-O-(A 3a O) r1 -], [-O-(A 3b O) r2 The substitution position of -] may be, for example, any of the 2-, 4-, 5-, 6-, 2'-, 3'-, or 4'-positions of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position.

[0149] Examples of the second diol component corresponding to the second diol unit (B2) include 9,9-bis(hydroxyaryl)fluorenes in which r1 and r2 are 0 in the formula (4) and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which r1 and r2 are 1 or more, for example, about 1 to 10. In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

[0150] Examples of 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene.

[0151] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0152] Examples of the 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[(mono or di)C]fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene and the like.

[0153] Examples of the 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene.

[0154] Examples of 9,9-bis(hydroxynaphthyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

[0155] Examples of 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes include 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene, 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene, and 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene.

[0156] Examples of the 9,9-bis[hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)phenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene and the like.

[0157] Examples of the 9,9-bis[alkyl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[(mono or di)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]fluorene. 1-4 Alkyl-hydroxy(mono or deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0158] Examples of the 9,9-bis[aryl-hydroxy(poly)alkoxyphenyl]fluorene include 9,9-bis[C such as 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis[4-(2-(2-hydroxyethoxy)ethoxy)-3-phenylphenyl]fluorene, and 9,9-bis(4-(2-hydroxypropoxy)-3-phenylphenyl)fluorene. 6-10 Aryl-hydroxy(mono to deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0159] Examples of the 9,9-bis[hydroxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[hydroxy(mono- to deca)C such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[6-(2-(2-hydroxyethoxy)ethoxy)-2-naphthyl]fluorene, and 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene. 2-4 alkoxy-naphthyl]fluorene and the like.

[0160] These second diol units (B2) may be contained alone or in combination of two or more. Preferred second diol units (B2) include 9,9-bis[hydroxy(mono- to penta)C 2-4 Alkoxy C 6-10 aryl]fluorene, more preferably 9,9-bis[hydroxy(poly)alkoxyaryl]fluorene 2-4 Alkoxy C 6-10 Among them, 9,9-bis[hydroxy C aryl]fluorene-derived structural units such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene are preferred because they can improve the refractive index and heat resistance even more while providing a good balance between heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence). 2-3A structural unit derived from a 9,9-bis[hydroxy C, alkoxy-phenyl]fluorene is more preferred, and a structural unit derived from a 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene is particularly preferred, since it can more effectively reduce birefringence and greatly improve heat resistance while satisfying high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) in a well-balanced manner. 2-3 Further preferred are structural units derived from alkoxy-naphthyl]fluorene.

[0161] The third diol unit (B3) The diol unit (B) may or may not contain a third diol unit (B3) represented by the following formula (5) as necessary. When the diol unit (B3) is contained, not only is the balance between high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) particularly excellent, but also an excessive increase in the glass transition temperature can be suppressed, making it possible to achieve both heat resistance and moldability, which is preferable.

[0162] [ka]

[0163] (In the formula, A 4 represents a direct bond (single bond) or an alkylene group, A 5a and A 5b represents a linear or branched alkylene group; s1 and s2 each independently represent an integer of 0 or 1 or more; R 7a and R 7b each independently represents a substituent, and t1 and t2 each independently represent an integer of 0 to 6).

[0164] In the formula (5), A 4 Examples of the alkylene group represented by the formula (I) include linear or branched C alkylene groups such as methylene, ethylene, propylene, trimethylene, 1,2-butanediyl, and tetramethylene groups. 1-4 An alkylene group is preferable. 4From the viewpoint of optical properties such as high refractive index, low Abbe number, and low birefringence, for example, C 1-2 An alkylene group is preferred, and a direct bond (single bond) is particularly preferred.

[0165] A 5a , A 5b Examples of the alkylene group represented by the formula (4) include the alkylene group A 3a , A 3b The same applies to the preferred embodiments.

[0166] Alkyleneoxy group [-(A 5a O)-], [-(A 5b The repeat numbers s1 and s2 of the formula [O)-] may be 0 or more, and may be selected from a range of, for example, about 0 to 15, and the preferred ranges are 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1, in the following stepwise order. The repeat numbers s1 and s2 are preferably 1 or more, in terms of high polymerization reactivity, excellent optical properties such as high refractive index, low Abbe number, and low birefringence, and heat resistance, and furthermore, suppression of coloring, and the preferred ranges are 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2, and particularly preferably 1. The repeat numbers s1 and s2 may be the average number of moles added, and the preferred embodiment is the same as the preferred integer range described above. If the repeat numbers s1 and s2 are too large, the heat resistance and the refractive index may be reduced. The repeat numbers s1 and s2 may be the same or different from each other. When s1 and s2 are 2 or more, two or more alkyleneoxy groups [-(A 5a O)-], [-(A 5b O)-] may be the same or different. 5a and A 5b The types of may be different from each other, but are preferably the same.

[0167] The (poly)oxyalkylene group [-O-(A 5a O) s1 -], [-O-(A 5b O) s2 The substitution position of -] is A4 The position may be any of the positions 2 to 4 relative to the position 1 of the two naphthalene ring skeletons bonded to A, and the position 2 is preferred in terms of reducing birefringence. 4 When is a direct bond (single bond), it may be any of the 2- to 4-positions or the 2'- to 4'-positions of the 1,1'-binaphthyl skeleton, and is preferably the 2,2'-positions in that birefringence can be reduced.

[0168] R 7a and R 7b is preferably a substituent that is inactive in the polymerization reaction (non-polymerizable group), and for example, the group R 2a and R 2b The same groups as those exemplified as above, including preferred embodiments thereof, are included.

[0169] R 7a , R 7b The numbers of substitutions t1 and t2 may be, for example, integers of about 0 to 5, and the preferred ranges are, in the following stepwise order, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, and integers of 0 to 1, and preferably 0. t1 and t2 may be the same or different. 7a and R 7b The types of R may be the same or different. When t1 and t2 are 2 or more, R 7a , R 7b The types may be the same or different from each other.

[0170] Also, R 7a , R 7b The substitution positions of are A in the two naphthalene ring skeletons. 4 and (poly)oxyalkylene groups [-O-(OA 5a ) s1 -], [-O-(OA 5b ) s2 -] is not particularly limited as long as it is a position other than the substitution position of 4 The 3- to 8-positions of the two naphthalene ring skeletons bonded to A are preferred relative to the 1-position. 4 When is a direct bond (single bond), it is preferably at the 3- to 8-positions or 3'- to 8'-positions of the 1,1'-binaphthyl skeleton.

[0171] As the third diol unit (B3), typically, 4 is a direct bond (single bond), and the like. Examples of the dihydroxy-1,1'-binaphthyls include dihydroxy-1,1'-binaphthyls such as 2,2'-dihydroxy-1,1'-binaphthyl; bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl; and the like.

[0172] Examples of bis[hydroxy(poly)alkoxy]-1,1'-binaphthyl include 2,2'-bis[hydroxy(mono- to deca)C such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-1,1'-binaphthyl, and 2,2'-bis[2-(2-hydroxyethoxy)ethoxy]-1,1'-binaphthyl. 2-4 Alkoxy]-1,1'-binaphthyl and the like.

[0173] These third diol units (B3) may be contained alone or in combination of two or more. Among these third diol units (B3), 2,2'-bis[hydroxy(mono- or deca)C] is particularly preferred from the viewpoints of not only polymerization reactivity but also excellent optical properties such as high refractive index, low Abbe number, and low birefringence, heat resistance, and suppression of coloration. 2-4 Alkoxy]-1,1'-binaphthyl, especially 2,2'-bis[hydroxy(mono to hexa)C 2-4 Alkoxy]-1,1'-binaphthyl is preferred, and 2,2'-bis[hydroxy(mono- or tri)C 2-3 alkoxy]-1,1'-binaphthyl, in particular 2,2'-bis[hydroxyC such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl. 2-3 A structural unit derived from [alkoxy]-1,1'-binaphthyl is preferred.

[0174] The fourth diol unit (B4) The diol unit (B) may or may not necessarily contain a fourth diol unit (B4) different from the first diol unit (B1), the second diol unit (B2) and the third diol unit (B3), if necessary.

[0175] Examples of the fourth diol unit (B4) include alicyclic diols, aromatic diols (excluding the second diol unit (B2) and the third diol unit (B3)), and structural units derived from alkylene oxide (or alkylene carbonate, haloalkanol) adducts of these diol components.

[0176] Examples of alicyclic diols include cycloalkane diols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; and hydrogenated aromatic diols exemplified below, such as hydrogenated bisphenol A.

[0177] Examples of aromatic diols include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; and biphenols such as p,p'-biphenol.

[0178] Examples of the alkylene oxide (or corresponding alkylene carbonate, haloalkanol) adducts of these diol components include, for example, 2-4 Alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, and the like 2-3 Examples of the alkylene oxide adduct include an alkylene oxide adduct, and the number of moles of the adduct is not particularly limited. Specifically, examples of the alkylene oxide adduct include an adduct in which about 2 to 10 moles of ethylene oxide are added to 1 mole of bisphenol A.

[0179] The diol unit (B) may contain these fourth diol units (B4) either alone or in combination of two or more kinds.

[0180] The total proportion of the first diol unit (B1), the second diol unit (B2) and the third diol unit (B3) can be selected, for example, from 1 mol% or more, specifically from about 10 to 100 mol%, based on the entire diol unit (B). Preferred ranges are 30 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more in the following stepwise order, and it is particularly preferred that the total proportion is 100 mol%, substantially free of the fourth diol unit (B4).

[0181] The ratio of the first diol unit (B1) is, for example, about 1 mol% or more, preferably 5 to 100 mol%, based on the entire diol unit (B). In order to lower the Abbe number and greatly improve the heat resistance, it may be about 50 to 100 mol%, and the preferred ranges are 70 to 100 mol%, 90 to 100 mol%, 95 to 100 mol%, and particularly 100 mol%, in the following stepwise order. On the other hand, in order to further improve high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) while maintaining them in a well-balanced manner by combining with the second diol unit (B2) and / or the third diol unit (B3), the ratio of the first diol unit (B1) may be, for example, 1 to 50 mol%, based on the entire diol unit (B), and the preferred ranges are 3 to 45 mol%, 5 to 40 mol%, 8 to 35 mol%, and 10 to 30 mol%, in the following stepwise order.

[0182] The ratio of the first diol unit (B1) to the second diol unit (B2) (hereinafter also referred to as B1 / B2) may be selected, for example, from a range of about B1 / B2 (molar ratio) = 1 / 99 to 100 / 0, and preferred ranges are 5 / 95 to 50 / 50, 8 / 92 to 40 / 60, and 10 / 90 to 35 / 65 in the following stepwise order. If the ratio of the first diol unit (B1) is too low, the polymerization reactivity and moldability (productivity) may decrease, while if the ratio of the second diol unit (B2) is too low, the heat resistance may not be sufficiently improved, and the composition may not be usable in applications requiring durability in high-temperature environments, such as vehicle-mounted lenses. In particular, Z in the formula (4) 1 and Z 2 When the second diol unit (B2) is a condensed polycyclic aromatic hydrocarbon ring such as a naphthalene ring, the molar ratio of B1 / B2 may be selected from a range of about 1 / 99 to 30 / 70, and preferred ranges are 5 / 95 to 25 / 75, 8 / 92 to 20 / 80, and 10 / 90 to 15 / 85 in the following stepwise order. With such a ratio, it appears that the refractive index and heat resistance in particular can be further improved while high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) are satisfied in a well-balanced manner. On the other hand, Z in the formula (4) 1 and Z 2 When the second diol unit (B2) is a benzene ring (monocyclic aromatic hydrocarbon ring), the molar ratio of B1 / B2 may be selected from a range of about 5 / 95 to 50 / 50, and the preferred ranges are 10 / 90 to 45 / 55, 20 / 80 to 40 / 60, and 25 / 75 to 35 / 65 in the following stepwise order, and in applications where low birefringence is important, the preferred range is 10 / 90 to 40 / 60, and more preferably 15 / 85 to 35 / 75. With such a ratio, it appears that birefringence can be reduced more effectively and heat resistance can be greatly improved while maintaining high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) in a well-balanced manner.

[0183] The ratio of the first diol unit (B1) to the third diol unit (B3) (hereinafter also referred to as B1 / B3) may be selected from a range of, for example, B1 / B3 (molar ratio) = about 1 / 99 to 100 / 0, and the preferred ranges are 5 / 95 to 50 / 50, 10 / 90 to 40 / 60, 15 / 85 to 35 / 65, and 20 / 80 to 30 / 70 in the following stepwise order. If the ratio of the first diol unit (B1) is too low, the polymerization reactivity and moldability (productivity) may decrease, while if the ratio of the third diol unit (B3) is too low, not only is it difficult to improve high heat resistance and optical properties (low Abbe number, high refractive index, and low birefringence) in a balanced manner, but it may also be difficult to suppress an excessive increase in the glass transition temperature to achieve both heat resistance and moldability.

[0184] The thermoplastic resin may or may not contain other structural units (C) different from the dicarboxylic acid units (A) and the diol units (B) as necessary, within the scope of not impairing the effects of the present invention. Examples of the other structural units (C) include structural units derived from hydroxyalkanoic acids and lactones, polyfunctional polymerization components having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups), carbonate bond-forming components, etc.

[0185] Examples of hydroxyalkanoic acids include lactic acid, 3-hydroxybutyric acid, 6-hydroxyhexanoic acid, and the like, and examples of lactones include lactones corresponding to hydroxyalkanoic acids, such as ε-caprolactone.

[0186] Examples of polyfunctional polymerization components having a total of three or more polymerizable groups (carboxyl groups and / or hydroxyl groups) include trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; trivalent or higher polyhydric alcohols such as glycerin and pentaerythritol; and the like.

[0187] The carbonate bond forming component may be any compound capable of forming a carbonate bond by reacting with two diol components. That is, the constituent unit derived from the carbonate bond forming component means a carbonyl group [-C(=O)-], and forms a carbonate bond together with the terminal oxygen atoms of the two diol units bonded adjacent to this carbonyl group. Representative carbonate bond forming components include, for example, phosgenes such as phosgene and triphosgene, and carbonate diesters such as diphenyl carbonate.

[0188] The proportion of such other structural units (C) relative to all structural units (the total amount of dicarboxylic acid units (A), diol units (B) and other structural units (C)) is, for example, 50 mol % or less, and preferred ranges are 0 to 30 mol %, 0 to 15 mol %, 0 to 10 mol %, and 0.01 to 1 mol %, respectively, and it is preferable that the other structural units (C) are not substantially contained.

[0189] [Manufacturing method] (Method for Producing First Dicarboxylic Acid Component) The first dicarboxylic acid component may be a commercially available product, but the first dicarboxylic acid component represented by the following formula (1A) is a novel compound and may be prepared, for example, according to the following reaction scheme.

[0190] [ka]

[0191] (In the formula, R 1a and R 1b are each independently C 1-5 represents an alkoxy group, R 3a and R 3b are each independently C 1-5 represents an alkoxy group, R 2a and R 2b , k1 and k2 are the same as in the above formula (1), including preferred embodiments.

[0192] In the above reaction scheme, 6-hydroxy-2-naphthoic acids (or 2-hydroxy-6-naphthoic acids) are subjected to an esterification reaction, a coupling reaction (oxidative coupling reaction), and an etherification reaction in this order, to prepare a dicarboxylic acid component represented by formula (1A).

[0193] (i) Esterification of 6-hydroxy-2-naphthoic acids In the esterification reaction, 6-hydroxy-2-naphthoic acids are 3a , R 3b This is reacted with an alcohol corresponding to the alkoxy group represented by the formula:

[0194] As the 6-hydroxy-2-naphthoic acid, R 2a , R 2b Examples of the 6-hydroxy-2-naphthoic acid include 6-hydroxy-2-naphthoic acid which may have a substituent represented by the formula: 2a and R 2b It is also preferred that k1 and k2 are the same as each other, that is, one kind of 6-hydroxy-2-naphthoic acid is used.

[0195] Alkoxy group R 3a , R 3b Examples of the corresponding alcohols include linear or branched C alcohols such as methanol, ethanol, and isopropanol. 1-5 Alcohols, preferably linear or branched C 1-3 C such as alcohol, more preferably methanol 1-2 It is an alcohol. 3a and R 3b are preferably the same as each other, i.e., one type of alcohol is preferably used.

[0196] The proportion of the alcohols used is, for example, 50 to 500 parts by mass, preferably 100 to 400 parts by mass, and more preferably 200 to 300 parts by mass, relative to 100 parts by mass of 6-hydroxy-2-naphthoic acids.

[0197] The esterification reaction may be carried out in the presence of a conventional esterification catalyst. Examples of the esterification catalyst include acid catalysts, base catalysts, and metal catalysts such as metal alkoxides, specifically titanium(IV) alkoxides such as titanium(IV) tetraisopropoxide. Among these catalysts, acid catalysts are preferably used.

[0198] The acid catalyst is not particularly limited, and examples thereof include inorganic acids, organic acids, Lewis acids such as boron trifluoride etherate and tin tetrachloride, and solid acid catalysts such as cation exchange resins. These acid catalysts may be used alone or in combination of two or more. These acid catalysts may also be hydrates.

[0199] Examples of the inorganic acid include strong acids, specifically, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.; and homo- or heteropoly acids, specifically, tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid, etc.

[0200] Examples of the organic acid include sulfonic acids, specifically, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, fluorinated alkanesulfonic acids such as trifluoromethanesulfonic acid, arenesulfonic acids such as p-toluenesulfonic acid, etc. As the acid catalyst, inorganic acids, for example, sulfuric acid such as concentrated sulfuric acid, etc. are often used.

[0201] The proportion of the esterification catalyst used is, for example, 5 to 50 parts by mass, preferably 10 to 40 parts by mass, and more preferably 20 to 30 parts by mass, relative to 100 parts by mass of 6-hydroxy-2-naphthoic acids.

[0202] The reaction temperature is, for example, 50 to 150° C., and preferably 60 to 100° C. The reaction may be carried out at the reflux temperature. The reaction time may be, for example, about 1 to 24 hours.

[0203] The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or a rare gas with stirring, and may be carried out under normal pressure, elevated pressure or reduced pressure.

[0204] After completion of the reaction, the produced 6-hydroxy-2-naphthoic acid esters may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, reprecipitation, centrifugation, column chromatography, or a combination of these means.

[0205] (ii) Oxidative coupling reaction of 6-hydroxy-2-naphthoic acid esters In the coupling reaction, the 6-hydroxy-2-naphthoic acid esters obtained in the above-mentioned esterification reaction are used to synthesize 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyls.

[0206] As mentioned above, R 2a and R 2b , k1 and k2 and R 3a and R 3b are preferably the same as each other, and the 6-hydroxy-2-naphthoic acid esters used in the coupling reaction are preferably one type of compound (the same compound).

[0207] The coupling reaction is often carried out in the presence of a catalyst, and examples of the catalyst include copper salts. Examples of the copper salt include copper halides such as copper chloride (I), copper chloride (II), copper bromide (I), copper bromide (II), and copper iodide (I); and copper carboxylates such as copper formate (II) and copper acetate (II). These catalysts can be used alone or in combination of two or more. Among these catalysts, copper halides are preferred, copper halides (I) are more preferred, and copper chloride (I) is particularly preferred.

[0208] The ratio of the catalyst may be, for example, about 0.005 to 1 mol relative to 1 mol of the 6-hydroxy-2-naphthoic acid esters, and preferred ranges are 0.01 to 0.8 mol, 0.05 to 0.6 mol, 0.1 to 0.5 mol, 0.2 to 0.4 mol, 0.25 to 0.35 mol, and 0.27 to 0.33 mol in the following stepwise manner.

[0209] The reaction may be carried out in the presence of a solvent, which is preferably a polar solvent having a nitrogen atom, such as amides, ureas, anilines, morpholines, and pyridines.

[0210] Examples of the amides include N,N-substituted amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylpropioamide, N-methylacetanilide, and N-methyl-2-pyrrolidone.

[0211] Examples of the ureas include tetraalkylureas such as tetramethylurea and tetraethylurea.

[0212] Examples of the anilines include N,N-substituted anilines such as N,N-dimethylaniline and N,N-dimethyl-methoxyaniline.

[0213] Examples of morpholines include morpholine, N-methylmorpholine, and the like.

[0214] Examples of pyridines include pyridine and 2-methylpyridine.

[0215] These solvents may be used alone or in combination of two or more. Among these solvents, amides such as N,N-dimethylformamide are preferred in terms of solubility.

[0216] The proportion of the solvent used is not particularly limited and may be, for example, about 10 to 5,000 parts by mass relative to 100 parts by mass of the 6-hydroxy-2-naphthoic acid esters, and preferred ranges are 15 to 3,000 parts by mass, 20 to 1,000 parts by mass, 30 to 500 parts by mass, 50 to 150 parts by mass, 70 to 130 parts by mass, 80 to 120 parts by mass, and 90 to 110 parts by mass, in the following stepwise order.

[0217] The reaction temperature is, for example, 40 to 120° C., and preferably 60 to 80° C. The reaction time may be, for example, about 1 to 48 hours, and preferably 12 to 36 hours.

[0218] The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or rare gas with stirring, and may be carried out under normal pressure, pressure, or reduced pressure. When copper(I) chloride is used as a catalyst, it is preferable to carry out the reaction while bubbling air or oxygen gas at, for example, 1 to 20 L / min, preferably 2 to 10 L / min, since the catalytic activity is regenerated by oxygen and the amount of catalyst can be reduced.

[0219] After completion of the reaction, the produced 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyls may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, reprecipitation, centrifugation, column chromatography, or a combination of these means.

[0220] (iii) 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1 Etherification of '-binaphthyls In the etherification reaction, 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyls are reacted with the alkoxy group R 1a , R 1b This is reacted with a corresponding etherifying agent to etherify the hydroxyl groups at the 2,2' positions of the 1,1'-binaphthyl skeleton.

[0221] The alkoxy group R 1a , R1b Examples of the corresponding etherification agent include alkyl halides, dialkyl sulfates, etc. Examples of the alkyl halides include alkyl iodides, alkyl bromides, alkyl chlorides, etc., and preferably iodides such as methyl iodide. 1-5 The dialkyl sulfate ester is, for example, dimethyl sulfate or other sulfate C 1-5 Alkyl and the like.

[0222] These etherification agents can be used alone or in combination of two or more. Among these alkylation agents, alkyl halides are preferred, and alkyl iodides such as methyl iodide are more preferred. 1-5 The alkoxy group R 1a , R 1b are preferably the same, and therefore the corresponding etherification agents are also preferably one type of compound (the same compound).

[0223] The proportion of the etherification agent used may be, for example, about 2 to 10 moles per mole of the 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyls, and preferred ranges are 2.1 to 8 moles, 2.2 to 5 moles, 2.3 to 4 moles, 2.5 to 3.5 moles, 2.7 to 3.3 moles, and 2.8 to 3.2 moles, in the following stepwise manner.

[0224] The etherification reaction may be carried out in the presence of a base, and examples of the base include metal hydroxides, metal carbonates, and metal hydrogen carbonates. Examples of the metal hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the metal carbonates include alkali metal carbonates such as sodium carbonate and potassium carbonate. Examples of the metal hydrogen carbonates include alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate.

[0225] These bases may be used alone or in combination of two or more. Among these bases, metal carbonates are preferred, and alkali metal carbonates such as potassium carbonate are more preferred.

[0226] The ratio of the base may be, for example, about 2 to 10 moles per mole of the 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyl compound, and preferred ranges are 2.1 to 8 moles, 2.2 to 6 moles, 2.3 to 5 moles, 2.5 to 4 moles, 2.7 to 3.8 moles, 3 to 3.6 moles, and 3.2 to 3.4 moles, in the following stepwise order.

[0227] The reaction may be carried out in the presence of a solvent. Examples of the solvent include nitriles such as acetonitrile; amides such as N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; and hydrocarbons, specifically, aliphatic or alicyclic hydrocarbons such as hexane, and aromatic hydrocarbons such as benzene and toluene.

[0228] These solvents can be used alone or in combination of two or more. Among these solvents, amides such as N,N-dimethylformamide are preferred. The ratio of the solvent used is not particularly limited, and may be, for example, about 10 to 5000 parts by mass relative to 100 parts by mass of 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyls, and the preferred ranges are 50 to 3000 parts by mass, 80 to 2000 parts by mass, 100 to 1000 parts by mass, 200 to 800 parts by mass, 300 to 700 parts by mass, 400 to 600 parts by mass, and 450 to 550 parts by mass in the following stepwise manner.

[0229] The reaction temperature is, for example, 40 to 120° C., and preferably 60 to 80° C. The reaction time may be, for example, about 1 to 48 hours, and preferably 12 to 36 hours.

[0230] The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or rare gas with stirring, and may be carried out under normal pressure, pressure, or reduced pressure. When copper(I) chloride is used as a catalyst, it is preferable to carry out the reaction while bubbling air or oxygen gas at, for example, 1 to 20 L / min, preferably 2 to 10 L / min, since the catalytic activity is regenerated by oxygen and the amount of catalyst can be reduced.

[0231] After completion of the reaction, the produced 6,6'-bis(alkoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyls may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, reprecipitation, centrifugation, column chromatography, or a combination of these means.

[0232] (Polycondensation of thermoplastic resin) The method for producing the thermoplastic resin is not particularly limited except that the dicarboxylic acid component (A) containing the first dicarboxylic acid component (A1) is used as a polymerization component, and a conventional method can be used depending on the type of resin and other polymerization components (copolymerization components). For example, in the case of a polyester-based resin such as a polyester resin, it is sufficient to produce it by reacting a dicarboxylic acid component (A) corresponding to each of the above-mentioned dicarboxylic acid units with a diol component (B) corresponding to the above-mentioned diol units, and it can be prepared by a conventional method, specifically, a melt polymerization method such as an ester exchange method or a direct polymerization method, a solution polymerization method, or an interfacial polymerization method, and the melt polymerization method is preferred. The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method.

[0233] The ratio of the dicarboxylic acid component (A) to the diol component (B) used (or the ratio of the diol component (B) charged) is usually, for example, 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9 (molar ratio), but it is not necessarily required to be within this range, and at least one component selected from each dicarboxylic acid component (A) and each diol component (B) may be used in excess of the expected ratio of introduction. For example, the first diol component (B1) such as ethylene glycol that can be distilled from the reaction system may be used in excess of the ratio of introduction (or the ratio of introduction) into the polyester resin.

[0234] The reaction may be carried out in the presence of a catalyst. As the catalyst, a conventional esterification catalyst, for example, a metal catalyst, etc., can be used. As the metal catalyst, for example, a metal compound containing an alkali metal such as sodium; an alkaline earth metal such as magnesium, calcium, barium, etc.; a transition metal such as titanium, manganese, cobalt, etc.; a metal of Group 12 of the periodic table such as zinc, cadmium, etc.; a metal of Group 13 of the periodic table such as aluminum, etc.; a metal of Group 14 of the periodic table such as germanium, lead, etc.; a metal of Group 15 of the periodic table such as antimony, etc., can be used. As the metal compound, for example, alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; metal oxides, etc., or hydrates thereof can be used. Representative metal compounds include germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, and antimony ethylene glycolate; titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0235] These catalysts can be used alone or in combination of two or more. When using multiple catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, titanium (IV) tetrabutoxide, etc. are preferred. The amount of catalyst used is, for example, 0.01 x 10 per mole of the dicarboxylic acid component (A). -4 ~100×10 -4 Molar, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0236] The reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. Usually, a heat stabilizer is often used, and examples of the heat stabilizer include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (dibutyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite. Of these, dibutyl phosphate is often used. The amount of the heat stabilizer used is, for example, 0.01×10 per mole of the dicarboxylic acid component (A). -4 ~100×10 -4 Molar, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0237] The reaction is usually carried out in an atmosphere of an inert gas, such as nitrogen gas, or a rare gas such as helium or argon. The reaction is also carried out under reduced pressure, for example, at a pressure of 1×10 2 ~1×10 4 The reaction temperature can be selected according to the polymerization method, and for example, the reaction temperature in the melt polymerization method is 150 to 320°C, preferably 250 to 310°C, and more preferably 280 to 300°C.

[0238] [Characteristics and applications of thermoplastic resins] (characteristic) Since the thermoplastic resin contains the first dicarboxylic acid unit (A1), the refractive index can be improved without excessively increasing the low birefringence, and in particular, the Abbe number can be significantly reduced and the heat resistance is excellent, compared to a thermoplastic resin formed using a dicarboxylic acid component having a conventional 1,1'-binaphthyl skeleton, for example, a dicarboxylic acid component having a carboxyl group at the 2,2'-position via a methoxy group or the like. That is, a high refractive index and a low birefringence, which are usually in a trade-off relationship, can be simultaneously achieved, and the optical properties (low Abbe number, high refractive index, low birefringence) and heat resistance can be improved in a well-balanced manner.

[0239] The refractive index nD of the thermoplastic resin can be selected, for example, from the range of about 1.6 to 1.75 at a temperature of 20° C. and a wavelength of 589 nm, and is preferably 1.64 to 1.72, 1.66 to 1.71, 1.665 to 1.7, 1.67 to 1.695, 1.675 to 1.69, and more preferably 1.68 to 1.685 in the following stepwise manner.

[0240] The Abbe number of the thermoplastic resin is, for example, 19 or less at a temperature of 20°C, and the preferred ranges are 18.5 or less, 18 or less, 17.5 or less, and 17 or less in the following stepwise order. As described above, the thermoplastic resin can effectively reduce the Abbe number, and therefore can be effectively used in applications requiring a low Abbe number, such as optical components in various cameras, such as camera lenses using a combination of concave and convex lenses. In the optical systems of various cameras, a concave lens with a low Abbe number is used to reduce (or cancel) the chromatic aberration (blurring) that occurs in the convex lens, and is usually composed of a combination of multiple concave and convex lenses, and the thermoplastic resin can fully meet the low Abbe number required for the concave lens. The lower limit of the Abbe number may be, for example, 15 or more, 15.5 or more, 16 or more, or 16.5 or more.

[0241] The birefringence of a thermoplastic resin may be evaluated by measuring the birefringence (triple birefringence) of a stretched film obtained by uniaxially stretching a film made of only a thermoplastic resin at a stretching temperature of glass transition temperature Tg+10° C., a stretching speed of 25 mm / min, and a stretching ratio of 3. The absolute value of the triple birefringence of the stretched film is, for example, 75×10 at a measurement temperature of 20° C. and a wavelength of 600 nm. -4 The following ranges can be selected, with the preferred range being as follows: 60×10 -4 Below, 50 x 10 -4 Below, 40 x 10 -4 Below, 30 x 10 -4 Below, 25 x 10 -4 Below, 20 x 10 -4 Below, 15 x 10 -4 The following is 10 x 10 -4 The lower limit of the absolute value of the triple birefringence is, for example, 0 or more and 0.1×10 or less. -4 It may be more than that.

[0242] The glass transition temperature Tg of the thermoplastic resin can be selected, for example, from a range of about 120 to 280°C, and the preferred ranges are 150 to 250°C, 160 to 240°C, 170 to 230°C, 180 to 220°C, 185 to 215°C, and 190 to 210°C in the following stepwise order, and more preferably 195 to 205°C. If the glass transition temperature Tg is too low, the heat resistance decreases, and the resin may be easily discolored (or colored) during production and / or use, or may deform in a high-temperature environment after being molded into a predetermined shape. Therefore, the resin may not be usable in applications requiring high heat resistance or thermal stability, such as optical lenses for vehicles. If the glass transition temperature Tg is too high, the moldability decreases, and it may be difficult to form a smooth surface of a molded body such as an optical lens by a method such as injection molding. Therefore, from the viewpoint of achieving high heat resistance and high moldability at the same time, the glass transition temperature Tg is preferably 150 to 170°C, and more preferably 160 to 170°C.

[0243] Although the thermoplastic resin has a rigid and bulky binaphthyl skeleton, it has surprisingly high polymerization reactivity and is therefore excellent in moldability (productivity). The weight-average molecular weight Mw of the polyester resin can be measured by gel permeation chromatography (GPC) or the like, and can be selected from a range of, for example, about 10,000 to 1,000,000 in terms of polystyrene, with the preferred ranges being 15,000 to 150,000, 20,000 to 100,000, preferably 25,000 to 80,000, 30,000 to 70,000, 40,000 to 65,000, and 50,000 to 60,000, in the following stepwise order. If the weight-average molecular weight Mw is too low, the moldability (productivity) may be easily reduced.

[0244] In this specification and claims, the refractive index nD, Abbe number, triple birefringence, glass transition temperature Tg, and weight average molecular weight Mw can be measured by the method described in the examples below.

[0245] (Molded body) The molded article contains at least the thermoplastic resin and has excellent optical properties (low Abbe number, high refractive index, low birefringence, etc.) and heat resistance, and can be used as an optical member such as an optical film (optical sheet) or an optical lens. Such a molded article may contain conventional additives. Examples of the additives include fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, release agents, antistatic agents, dispersants, flow control agents, leveling agents, defoamers, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress reducing agents. Examples of the stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. Examples of the stress reducing agents include silicone oils, silicone rubbers, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination of two or more.

[0246] The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, or the like.

[0247] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous, and thread-like structures, two-dimensional structures such as film-like, sheet-like, and plate-like structures, and three-dimensional structures such as concave or convex lens-like, rod-like, and hollow (tubular) structures.

[0248] In particular, thermoplastic resins are useful for forming optical films because of their excellent optical properties, and therefore the present invention also includes films (optical films or optical sheets) formed from the thermoplastic resins.

[0249] The average thickness of such a film can be selected from the range of about 1 to 1000 μm depending on the application, and is, for example, 1 to 200 μm, preferably 5 to 150 μm, and more preferably 10 to 120 μm.

[0250] Such a film (optical film) can be produced by forming (or molding) the thermoplastic resin into a film using a conventional film-forming method such as a casting method (solvent casting method), a melt extrusion method, or a calendar method.

[0251] The film may be an unstretched or stretched film, and even if it is a stretched film, low birefringence can be maintained. Note that such a stretched film may be either a uniaxially stretched film or a biaxially stretched film.

[0252] The stretching ratio in each direction in uniaxial or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, and more preferably 1.5 to 6 times. In the case of biaxial stretching, it may be equal stretching, for example, 1.5 to 5 times stretching in both the longitudinal and transverse directions, or uneven stretching, for example, 1.1 to 4 times stretching in the longitudinal direction and 2 to 6 times stretching in the transverse direction. In the case of uniaxial stretching, it may be longitudinal stretching, for example, 2.5 to 8 times stretching in the longitudinal direction, and transverse stretching, for example, 1.2 to 5 times stretching in the transverse direction.

[0253] The average thickness of the stretched film is, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably 5 to 100 μm.

[0254] Such a stretched film can be obtained by stretching the film (or unstretched film) after film formation. 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, either a tenter method (flat method) or a tube method may be used, but the tenter method, which has excellent uniformity in the stretched thickness, is preferred.

[0255] [Abbe number reducer] The Abbe number reducing agent is represented by the following formula (1B).

[0256] [ka]

[0257] (In the formula, R 3a and R 3b each independently represents a hydroxyl group, an alkoxy group, or a halogen atom, R 1a and R 1b , R 2a and R 2b , k1 and k2 are the same as in formula (1), including preferred embodiments.

[0258] R 3a and R 3b The alkoxy group is a C group such as a methoxy group, an ethoxy group, or a t-butoxy group. 1―5 Examples of the halogen atom include chlorine and bromine. 3a ] and the radical [-C(=O)-R 3b The bonding positions of the two carbonyl groups [-C(=O)-] in the above formula (1), including preferred embodiments, are the same as the bonding positions of the two carbonyl groups [-C(=O)-] in the above formula (1).

[0259] The Abbe number reducer is suitable as an Abbe number reducer for resins, particularly thermoplastic resins, and when blended with a thermoplastic resin, it can not only reduce the Abbe number of the thermoplastic resin, but also improve the refractive index and moldability of the thermoplastic resin.

[0260] Examples of thermoplastic resins include polyolefin-based resins such as chain olefin-based resins and cyclic olefin-based resins (or cycloolefin-based resins); (meth)acrylic resins; styrene-based resins; polyester-based resins such as polyalkylene arylate resins, polyarylate resins, and polycarbonate resins; and polyamide-based resins.

[0261] These thermoplastic resins may be used alone or in combination of two or more kinds. Among these, cyclic olefin resins, polymethyl methacrylate resins, polyester resins, and polycarbonate resins are preferred, and cyclic olefin resins are particularly preferred.

[0262] The proportion of the Abbe number reducer is, for example, 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, further preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

[0263] The molded article formed from the resin composition containing the Abbe number reducer and the thermoplastic resin is similar to the molded article formed from the thermoplastic resin containing the dicarboxylic acid unit (A) in terms of conventional additives contained in the molded article, molding method, and shape, including preferred embodiments. EXAMPLES

[0264] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Details of evaluation items and raw materials are shown below.

[0265] [Evaluation method] (HPLC) The HPLC (high performance or high performance liquid chromatograph) was performed using a Shimadzu Corporation "LC-2010CHT" and a Tosoh Corporation "ODS-80TM" column. The sample was dissolved in acetonitrile and measured, and the HPLC purity [area %] was calculated. The detailed measurement conditions are shown in Table 1.

[0266] [Table 1]

[0267] ( 1 H-NMR) The sample was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard, and the results were analyzed using a nuclear magnetic resonance spectrometer (BRUKER's "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0268] For the resin samples, the integral values ​​of the peaks derived from each monomer used in the polymerization were determined based on the obtained spectrum, and the proportion of each monomer component (structural unit) introduced into the polymer (polymer composition ratio) was calculated.

[0269] (glass transition temperature Tg) The measurements were carried out using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII NanoTechnology Inc.) in a nitrogen atmosphere at a temperature rise rate of 10° C. / min.

[0270] (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-8320GPC" manufactured by Tosoh Corporation).

[0271] (Refractive index nD) The sample was heat pressed at 200-240°C to form a film with a thickness of 200-300 μm. This film was cut into a rectangular shape with a length of 20-30 mm and a width of 10 mm to obtain a test piece. The refractive index nD of the obtained test piece at 589 nm (D line) was measured using a multi-wavelength Abbe refractometer (Atago Co., Ltd.'s "DR-M4 (circulating thermostatic bath 60-C3)") at a measurement temperature of 20°C and diiodomethane as a contact liquid.

[0272] (Abbe number) Using the test piece for measuring the refractive index nD at 589 nm (D line), the refractive indexes nF and nC were measured in the same manner as for the refractive index nD, except that the measurement wavelengths were changed to 486 nm (F line) and 656 nm (C line). The Abbe number was calculated from the refractive indexes nF, nD, and nC at each wavelength obtained using the following formula.

[0273] (Abbe number)=(nD-1) / (nF-nC).

[0274] (Birefringence (stretched 3 times)) The sample was heat pressed at 200-240°C to form a film with a thickness of 200-600μm. This film was cut into a rectangular shape of 10mm x 50mm, and uniaxially stretched at a stretch ratio of 3 times at 25mm / min under a temperature condition of glass transition temperature Tg+10°C to obtain a test piece. The retardation of the obtained test piece was measured by the parallel Nicol rotation method under conditions of a measurement temperature of 20°C and a measurement wavelength of 600nm using a retardation film / optical material inspection device (Otsuka Electronics Co., Ltd., "RETS-100"), and the value was divided by the thickness of the measurement site to calculate the birefringence (or triple birefringence).

[0275] (Melt Flow Rate MFR) In accordance with JIS K7210, the measurements were performed at a temperature of 280° C. and a load of 16 kg in Comparative Example 1. In Comparative Example 2 and Example 17, the measurements were performed at a temperature of 280° C. and a load of 2.16 kg.

[0276] [Raw materials] (Dicarboxylic acid component) BNAC-E: 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl, synthesized according to Synthesis Example 4 described in JP2018-59074A 2,3-BMN-m: 3,3'-bis(methoxycarbonyl)-2,2'-dimethoxy-1,1'-binaphthyl, synthesized according to Synthesis Example 1 described below. 2,6-BMN-m: 6,6'-bis(methoxycarbonyl)-2,2'-dimethoxy-1,1'-binaphthyl, synthesized according to Example 1 described below. FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene [or 9,9-bis(2-carboxyethyl)fluorene or dimethyl ester of fluorene-9,9-dipropionic acid], synthesized in the same manner as in Example 1 of JP-A-2005-89422, except that methyl acrylate [37.9 g (0.44 mol)] was used instead of t-butyl acrylate. 2-DNFDP-m: 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene, synthesized according to Example 1B in WO2020-213470. DDA-m: 1,12-dodecanedioic acid dimethyl ester DMT: Dimethyl terephthalate

[0277] (Carbonate bond forming component) DPC: Diphenyl carbonate

[0278] (Diol component) BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, synthesized according to Synthesis Example 1 described in JP2018-59074A BINOL-2EO: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, synthesized according to Synthesis Example 2 described in JP-A-2018-59074 EG: Ethylene glycol 1,5-PDO: 1,5-pentanediol

[0279] [Synthesis Example 1] Preparation of 2,3-BMN-m While mixing and stirring 3-hydroxy-2-naphthoic acid (14.0 kg, 74.4 mol) and methanol (36.3 kg), concentrated sulfuric acid (3.65 kg, 36.5 mol) was added dropwise so that the temperature of the reaction solution (mixture) was 20°C or less, and the mixture was reacted while refluxing and dehydrating for 21 hours, and then methanol was distilled off under reduced pressure. Methyl isobutyl ketone (hereinafter also referred to as MIBK; 37.0 kg) and ion-exchanged water (14.0 kg) were added (added) to dissolve the reaction mixture, and after performing an analysis operation, the organic layer was washed with water until the pH became 7. After concentrating the obtained organic layer, methanol (42.0 kg) was added so that the temperature of the reaction solution (concentrated organic layer) was 50°C or less, and cooling crystallization was performed. After crystals were precipitated at 45°C, the mixture was gradually cooled and held at 10°C or less for 1 hour, and the precipitated crystals were filtered. The filtered crystals were rinsed with methanol and then dried under reduced pressure to obtain 12.7 kg of methyl 3-hydroxy-2-naphthoate (yield 84%, HPLC purity 99.6% area%).

[0280] Next, the obtained methyl 3-hydroxy-2-naphthoate (12.5 kg, 61.8 mol), N,N-dimethylformamide (12.5 kg), and copper(I) chloride (1.32 kg, 13.3 mol) were dissolved (mixed) at 70°C, and the reaction was carried out at 70°C for 20 hours while bubbling air at a rate of 5 L / min. After confirming the disappearance of the raw materials by HPLC, ion-exchanged water (25.0 kg) was added, and the precipitated crystals were filtered. The filtered crystals were rinsed with ion-exchanged water and methanol in that order, and then dried under reduced pressure to obtain 12.4 kg of 3,3'-bis(methoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyl (yield 99%, HPLC purity 99.6 area%).

[0281] Next, 12.4 kg of the obtained 3,3'-bis(methoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyl, potassium carbonate (14.1 kg, 102 mol), and N,N-dimethylformamide (26.0 kg) were mixed and stirred, while methyl iodide (13.2 kg, 93.0 mol) was added dropwise so that the temperature of the reaction solution was 20° C. or less. After that, the mixture was stirred at 40° C. for 12 hours, and after confirming the disappearance of the raw materials by HPLC, MIBK (25.8 kg) and ion-exchanged water (12.9 kg) were charged (added), and unnecessary substances (insoluble substances) were appropriately filtered and washed with water. The organic layer was washed with 1N hydrochloric acid (25.8 kg), ion-exchanged water (12.9 kg), and 0.5% by mass sodium hydroxide aqueous solution (12.9 kg) in that order, and then washed twice with ion-exchanged water (12.9 kg) until the pH of the aqueous layer became 7. The obtained organic layer was concentrated, and 2-propanol (19.0 kg) was added so that the temperature of the reaction solution (concentrated organic layer) was 80 ° C or less, and then cooling crystallization was performed. After confirming crystal precipitation at around 45 ° C, it was gradually cooled and held at 10 ° C or less for 1 hour. The precipitated crystals were filtered, rinsed twice with 2-propanol cooled to 10 ° C or less, and then dried under reduced pressure to obtain 11.8 kg of crystals of 2,3-BMN-m represented by the following formula (yield 89%, HPLC purity 99.7% area%).

[0282] [ka]

[0283] [Example 1] Preparation of 2,6-BMN-m 6-Hydroxy-2-naphthoic acid (10.0 kg, 53.1 mol) and dehydrated methanol (26.0 kg) were mixed and stirred, and 98% by mass concentrated sulfuric acid (2.6 kg) was dropped so that the temperature of the reaction solution (mixture) was 25 ° C or less. The mixture was reacted while refluxing and dehydrating for 10.5 hours, and then methanol was distilled off under reduced pressure. MIBK (42.0 kg) was added thereto to dissolve the reaction mixture, and the organic layer was washed with water until the pH became 7. The obtained organic layer was concentrated, and then methanol (30.0 kg) was added and dissolved at 75 ° C., followed by cooling and crystallization. After crystals were precipitated at 45 ° C., the mixture was gradually cooled and held at 10 ° C. or less for 1 hour, and the precipitated crystals were filtered. The filtered crystals were rinsed by pouring cold methanol into them, and then dried under reduced pressure at 60°C to obtain 8.47 kg of methyl 6-hydroxy-2-naphthoate (yield 78.8%, HPLC purity 98.5 area%).

[0284] Subsequently, the obtained 6-hydroxy-2-naphthoic acid methyl ester (4.0 kg, 19.8 mol), N,N-dimethylformamide (4.0 kg), and copper (I) chloride (588.0 g, 5.9 mol, added in three portions) were dissolved (mixed) at 70 ° C., and the reaction was carried out at 70 ° C. for 23.5 hours while bubbling air at a rate of 2 to 10 L / min. After confirming the disappearance of the raw material by HPLC, ion-exchanged water (4.0 kg) was added, and the precipitated crystals were filtered. The filtered crystals were rinsed (rinsed) at room temperature with ion-exchanged water and methanol in that order, and the crystals were taken out. Thereafter, a series of operations, that is, a series of operations in which methanol was added to the taken out crystals, heated and stirred at 50 ° C., filtered, and rinsed with 50 ° C. methanol, was carried out multiple times. Thereafter, 1N hydrochloric acid (12.0 kg) was added, the mixture was stirred at room temperature, and filtered. The obtained crystals were rinsed with ion-exchanged water and then with methanol, and then dried under reduced pressure at 60°C to obtain 2.83 kg of 6,6'-bis(methoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyl (yield 71.1%, HPLC purity 98.1% area%).

[0285] Next, the obtained 6,6'-bis(methoxycarbonyl)-2,2'-dihydroxy-1,1'-binaphthyl (1.4 kg, 3.5 mol), potassium carbonate (1.6 kg, 11.5 mol), and dehydrated N,N-dimethylformamide (7.0 kg, added in two portions) were mixed and stirred, while methyl iodide (1.5 kg, 10.4 mol) was added dropwise. After that, the mixture was stirred at 40°C for 6 hours, and the disappearance of the raw material was confirmed by HPLC, and then MIBK (25.8 kg) and ion-exchanged water (7.0 kg) were charged (added), and the precipitated crystals were filtered and rinsed with ion-exchanged water. Next, a series of operations, that is, the crystals were dispersed and washed in 1N hydrochloric acid (4.9 kg) and ion-exchanged water (4.9 kg) at 50°C, filtered, and rinsed with ion-exchanged water at 50°C, were carried out twice. The crystals were washed by dispersing them in ion-exchanged water (10.0 kg) at 50°C, filtered, rinsed several times with a mixture of ion-exchanged water and methanol (volume ratio 50 / 50), and then rinsed several times with methanol. The obtained crystals were dried under reduced pressure at 60°C to obtain 1.44 kg (yield 96%, HPLC purity 99.0 area%) of 6,6'-bis(methoxycarbonyl)-2,2'-dimethoxy-1,1'-binaphthyl (crude 2,6-BMN-m) as a crude product.

[0286] Next, the obtained crude 2,6-BMN-m (700 g) was dissolved in tetrahydrofuran (THF, 8.9 kg) by heating at about 65° C., concentrated and adsorbed onto silica gel (2.1 kg), and column purified by developing with a solvent obtained by mixing solvent A and solvent B in the solvent ratio (volume ratio) shown in Table 2 in accordance with the addition order, addition amount, and number of times shown in Table 2 below.

[0287] [Table 2]

[0288] The resulting solution was then concentrated, dispersed in methanol (2.1 kg) at room temperature and washed, and then dried under reduced pressure at 60°C to obtain 650 g (yield 93%, HPLC purity 99.8% by area) of crystals of 2,6-BMN-m represented by the following formula. 1The H-NMR results are shown below.

[0289] [ka]

[0290] 1 H-NMR (CDCl3, 300MHz): δ(ppm)3.8(s,6H),3.9(s,6H),7.1(d,2H),7.5(d,2H),7.8(dd,2H),8.1(d,2H),8.6(s,2H).

[0291] <Preparation of Thermoplastic Resin> [Comparative Example 1] A polyester resin was prepared in accordance with Example 5 of JP 2017-171885 A (Patent Document 2).

[0292] [Reference example 1] In a reactor, 2,3-BMN-m (10.76g (25mmol)), FDP-m (8.46g (25mmol)), BNEF (24.24g (45mmol)), EG (6.51g (105mmol)), titanium(IV) tetrabutoxide (5.1mg (15μmol)), calcium acetate monohydrate (4.4mg (25μmol)) were charged as catalysts for transesterification and polycondensation in a nitrogen atmosphere. The mixture was gradually heated to 250℃ and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (15.8mg (75μmol)) was added as a thermal stabilizer, and the temperature was gradually raised to 285℃ and 150Pa, the pressure was reduced, and the polycondensation reaction was carried out while removing EG until the specified stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0293] [Example 2] In the reactor, 2,6-BMN-m (8.61 g (20 mmol)) and FDP-m (6.77 g (20 mmol)) were charged as dicarboxylic acid components, BNEF (19.38 g (36 mmol)) and EG (5.22 g (84 mmol)) were charged as diol components, and titanium (IV) tetrabutoxide (2.7 mg (8 μmol)) was charged as a catalyst for transesterification and polycondensation reactions. The mixture was gradually heated to 250 ° C. under a nitrogen atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 285 ° C. and 120 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0294] [Example 3] In the reactor, 2,6-BMN-m (46.49 g (108 mmol)) and FDP-m (4.07 g (12 mmol)) were charged as dicarboxylic acid components, EG (22.36 g (360 mmol)) was charged as a diol component, and titanium (IV) tetrabutoxide (10.2 mg (30 μmol)) was charged as a catalyst for the transesterification and polycondensation reactions. The mixture was gradually heated to 240 ° C. under a nitrogen atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 295 ° C. and 170 Pa, the pressure was reduced, and the polycondensation reaction was carried out while removing EG until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0295] [Example 4] In the reactor, 2,6-BMN-m (36.16 g (84 mmol)) and FDP-m (12.18 g (36 mmol)) were charged as dicarboxylic acid components, EG (22.36 g (360 mmol)) as a diol component, and titanium (IV) tetrabutoxide (6.8 mg (20 μmol)) was charged as a catalyst for transesterification and polycondensation reactions, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (4.2 mg (20 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 290 ° C. and 170 Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0296] [Example 5] In the reactor, 2,6-BMN-m (25.83 g (60 mmol)) and FDP-m (20.29 g (60 mmol)) were charged as dicarboxylic acid components, EG (22.36 g (360 mmol)) was charged as a diol component, and titanium (IV) tetrabutoxide (4.1 mg (12 μmol)) was charged as a catalyst for transesterification and polycondensation reactions. The mixture was gradually heated to 240 ° C. under a nitrogen atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (4.2 mg (20 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 284 ° C. and 140 Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0297] [Example 6] In the reactor, 2,6-BMN-m (24.11 g (56 mmol)) and FDP-m (8.13 g (24 mmol)) were charged as dicarboxylic acid components, BINOL-2EO (20.97 g (56 mmol)) and EG (16.41 g (264 mmol)) were charged as diol components, and titanium (IV) tetrabutoxide (6.8 mg (20 μmol)) was charged as a catalyst for transesterification and polycondensation reactions. The mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification was carried out. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (4.2 mg (20 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 290 ° C. and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0298] [Example 7] In the reactor, 2,6-BMN-m (24.11 g (56 mmol)) and FDP-m (8.13 g (24 mmol)) were charged as dicarboxylic acid components, BPEF (24.56 g (56 mmol)) and EG (16.40 g (264 mmol)) were charged as diol components, and titanium (IV) tetrabutoxide (3.4 mg (10 μmol)) was charged as a catalyst for transesterification and polycondensation reactions. The mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (6.7 mg (32 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 286 ° C. and 170 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0299] [Example 8] In the reactor, 2,6-BMN-m (21.52 g (50 mmol)) and 2-DNFDP-m (29.54 g (50 mmol)) were charged as dicarboxylic acid components, EG (18.62 g (300 mmol)) was charged as a diol component, and titanium (IV) tetrabutoxide (6.8 mg (20 μmol)) was charged as a catalyst for transesterification and polycondensation reactions, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (5.3 mg (25 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 279 ° C. and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0300] [Example 9] In the reactor, 2,6-BMN-m (12.91 g (30 mmol)) and 2-DNFDP-m (41.35 g (70 mmol)) were charged as dicarboxylic acid components, EG (18.62 g (300 mmol)) was charged as a diol component, and titanium (IV) tetrabutoxide (6.8 mg (20 μmol)) was charged as a catalyst for transesterification and polycondensation reactions, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere and stirred to carry out the transesterification reaction. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (5.3 mg (25 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 279 ° C. and 130 Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0301] [Example 10] In the reactor, 2,6-BMN-m (21.52 g (50 mmol)), FDP-m (10.15 g (30 mmol)), DDA-m (5.17 g (20 mmol)) as dicarboxylic acid components, BPEF (30.7 g (70 mmol)) as diol components, EG (14.28 g (230 mmol)), titanium (IV) tetrabutoxide (4.3 mg (12.5 μmol)) as a catalyst for transesterification and polycondensation reaction were charged, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification reaction was performed. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (12.6 mg (60 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 278 ° C. and 220 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0302] [Example 11] In the reactor, 2,6-BMN-m (24.11 g (56 mmol)), FDP-m (8.12 g (24 mmol)) as dicarboxylic acid components, BPEF (10.52 g (24 mmol)), 1,5-PDO (2.50 g (24 mmol)), EG (11.92 g (192 mmol)) as diol components, titanium (IV) tetrabutoxide (2.7 mg (8 μmol)) as a catalyst for transesterification and polycondensation reactions were charged, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (8.4 mg (40 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 282 ° C. and 150 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0303] [Example 12] In the reactor, 2,6-BMN-m (25.83 g (60 mmol)), FDP-m (13.54 g (40 mmol)) as dicarboxylic acid components, BPEF (17.54 g (40 mmol)) as diol components, EG (16.14 g (260 mmol)), titanium (IV) tetrabutoxide (3.4 mg (10 μmol)) as a catalyst for transesterification and polycondensation reactions were charged, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (10.5 mg (50 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 282 ° C. and 170 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0304] [Example 13] In the reactor, 2,6-BMN-m (19.37g (45mmol)), FDP-m (18.61g (55mmol)) as dicarboxylic acid components, BPEF (36.40g (83mmol)) as diol components, EG (13.47g (217mmol)), titanium (IV) tetrabutoxide (3.4mg (10μmol)) as a catalyst for transesterification and polycondensation reactions were charged, and the mixture was gradually heated to 240°C under a nitrogen atmosphere, stirred, and transesterification was carried out. After removing the alcohol component produced by the transesterification reaction, dibutyl phosphate (10.5mg (50μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 278°C and 140Pa, the pressure was reduced, and the polycondensation reaction was carried out until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0305] [Example 14] In the reactor, 2,6-BMN-m (10.76 g (25 mmol)), FDP-m (25.38 g (75 mmol)) as dicarboxylic acid components, BPEF (6.58 g (15 mmol)), BNEF (37.70 g (70 mmol)), EG (13.35 g (215 mmol)) as diol components, titanium (IV) tetrabutoxide (3.4 mg (10 μmol)) as a catalyst for transesterification and polycondensation reactions were charged, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (8.4 mg (40 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 276 ° C. and 120 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0306] [Example 15] In the reactor, 2,6-BMN-m (8.61 g (20 mmol)), FDP-m (3.38 g (10 mmol)), DMT (13.59 g (70 mmol)) as dicarboxylic acid components, BPEF (39.47 g (90 mmol)) as diol components, EG (13.03 g (210 mmol)), calcium acetate dihydrate (14.1 mg (80 μmol)) titanium (IV) tetrabutoxide (5.1 mg (15 μmol)) as catalysts for transesterification and polycondensation reactions were charged, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, dibutyl phosphate (9.5 mg (45 μmol)) was added as a heat stabilizer, and the temperature was gradually raised to 269 ° C. and 130 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached while removing EG. After the reaction was completed, the contents were removed from the reactor to obtain a polyester resin.

[0307] [Example 16] Polyester carbonate In the reactor, 2,6-BMN-m (15.5 g (36 mmol)) as a dicarboxylic acid component, DPC (18.77 g (87.6 mmol)) as a carbonate bond forming component, BPEF (31.57 g (72 mmol)), BINOL-2EO (13.48 g (36 mmol)), 1,5-PDO (1.25 g (12 mmol)) as a diol component, titanium (IV) tetrabutoxide (6.1 mg (18 μmol)) as a catalyst for transesterification and polycondensation reaction were charged, and the mixture was gradually heated to 240 ° C. under a nitrogen atmosphere, stirred, and transesterification reaction was performed. After removing the alcohol component and phenol component generated by the transesterification reaction, the temperature was gradually raised to 269 ° C. and 130 Pa, the pressure was reduced, and the polycondensation reaction was performed until a predetermined stirring torque was reached. After the reaction was completed, the contents were removed from the reactor to obtain a polyester carbonate resin.

[0308] The charging ratios of the comparative examples, reference examples and examples are shown in Table 3, and the evaluation results of each obtained polyester resin, i.e., the polymer composition ratio (the ratio of structural units derived from each polymerization component used in the preparation) and each physical property value, are shown in Tables 4 and 5.

[0309] [Table 3]

[0310] [Table 4]

[0311] [Table 5]

[0312] As is clear from Tables 3 to 5, compared to the comparative examples, the polyester resins obtained in the examples exhibited high refractive indices and low Abbe numbers without excessively increasing birefringence, and also exhibited relatively high Tgs.

[0313] Comparative Example 1, Reference Example 1, and Example 2 are examples prepared by varying the type of dicarboxylic acid component having a binaphthyl skeleton, but compared to Comparative Example 1 (BNAC-E) and Reference Example 1 (2,3-BMN-m), which form the main chain at the 2,2' or 3,3' positions of the binaphthyl skeleton, Example 2 (2,6-BMN-m), which forms the main chain at the 6,6' positions, is able to achieve a high refractive index, a low Abbe number, and a high Tg while maintaining a low birefringence, and it was found that 2,6-BMN-m is a particularly effective dicarboxylic acid component for achieving a good balance between these four properties. It was an unexpected result that each property could be greatly improved by changing the substitution position on the binaphthyl skeleton.

[0314] The polyester resin of the embodiment satisfies the four characteristics (high refractive index, low Abbe number, low birefringence, and high Tg) in a relatively well-balanced manner, and can be effectively used as an optical lens, since it is possible to prepare a resin with a low Abbe number. In other words, it is possible to expand the options for optical lens materials with a low Abbe number, and to improve the design freedom of a lens unit formed of multiple lenses.

[0315] Among these Examples, Examples 2, 3, and 7 have particularly high Tg and are preferred as highly heat-resistant lenses for vehicle use, with Example 2 being preferred in terms of high refractive index and low birefringence, and Example 7 being more preferred in terms of extremely low birefringence. Example 6 is even more preferred in terms of a particularly excellent balance of the four properties and excellent moldability (or productivity). Examples 12 to 14 are preferred, with Example 13 being particularly preferred, in terms of a particularly excellent balance of the four properties and low birefringence.

[0316] [Reference example 2] The physical and optical properties of ARTON F4520 (manufactured by JSR Corporation) as a cyclic olefin resin were measured.

[0317] [Reference example 3] The procedure was carried out in accordance with Example 13 described in WO2016-147847. That is, 450 g of ARTON F4520 pellets and 50 g of BNEF as a fluorene compound were kneaded using a twin-screw extruder to obtain a resin composition.

[0318] [Example 17] 90 g of ARTON F4520 pellets and 10 g of 2,6-BMN-m were kneaded using a twin-screw extruder to obtain a resin composition.

[0319] [Table 6]

[0320] As is clear from the results in Table 6, the resin composition of Example 17 had higher fluidity and a reduced Abbe number than the Reference Example. [Industrial Applicability]

[0321] The thermoplastic resin and resin composition of the present invention exhibit high heat resistance, and therefore can be suitably used as heat-resistant members and the like, as well as in various applications requiring heat resistance. For example, they may be used in coating agents or coating films, specifically, paints, inks, protective films for electronic devices and liquid crystal members, adhesives, pressure sensitive adhesives, resin fillers, electric and electronic materials or electric and electronic parts (electric and electronic devices), specifically, antistatic agents, carrier transport agents, light emitting bodies, organic photoreceptors, heat sensitive recording materials, photochromic materials, hologram recording materials, charging trays, conductive sheets, optical disks, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, and the like; mechanical materials or mechanical parts (equipment), specifically, automotive materials or parts, aerospace-related materials or parts, sliding members, and the like.

[0322] Furthermore, thermoplastic resins and resin compositions have a good balance of optical properties such as high refractive index, low Abbe number, and low birefringence as well as high heat resistance, and therefore can be effectively used as optical members.

[0323] Representative optical members include optical films (optical sheets) such as films for liquid crystals and films for organic electroluminescence (EL); optical lenses such as lenses for glasses and lenses for cameras; prisms, holograms, optical fibers, and the like.

[0324] Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films that constitute polarizing films, phase difference films, alignment films (alignment films), viewing angle widening (compensation) films, diffusion plates (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorbing films, reflective films, anti-reflection (AR) films, reflection reducing (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, and adhesive layers or release layers between optical films. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic light-emitting diode displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper. Specific devices or apparatuses that can be used for these optical films include televisions; personal computers (PCs) such as desktop PCs, notebook PCs, and tablet PCs; smartphones, mobile phones; car navigation systems; and devices or apparatuses equipped with flat panel displays (FPDs) such as touch panels.

[0325] Examples of optical lenses include glasses lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar condensing lenses, objective lenses, and rod lens arrays. Thermoplastic resins can effectively reduce the Abbe number, and are therefore suitable for use in lenses that require a low Abbe number, such as camera lenses. Typical examples of devices or equipment that can be equipped with such optical lenses include small or mobile devices with camera functions, such as smartphones, mobile phones, and digital cameras; and in-vehicle cameras, such as drive recorders and back cameras (rear cameras). Thermoplastic resins in particular have high heat resistance, and can therefore be suitable for use in applications where use in high-temperature environments, such as in-vehicle optical lenses, is expected.

Claims

1. A thermoplastic resin containing a dicarboxylic acid unit (A), wherein the dicarboxylic acid unit (A) is at least one selected from the group consisting of a carboxylic acid unit represented by the following formula (1): 【Chemistry 1】 (In the formula, R １ａ and R １ｂ each independently represents a hydrogen atom or a substituent, R ２ａ and R ２ｂ each independently represents a substituent, and k1 and k2 each independently represent an integer of 0 to 5. The first dicarboxylic acid unit (A1) is represented by the following formula (1a): 【Chemistry 2】 (In the formula, R 1a and R 1b , R 2a and R 2b , k1 and k2 are the same as in formula (1).) A thermoplastic resin containing a dicarboxylic acid unit represented by the formula:

2. In formula (1), R １ａ and R １ｂ 2. The thermoplastic resin according to claim 1, wherein is an alkoxy group.

3. The dicarboxylic acid unit (A) is represented by the following formula (2a) or (2b): 【Chemistry 3】 (In the formula, R ４ａ represents a substituent; m1 represents an integer of 0 to 8; A １ａ and A １ｂ each independently represents a divalent hydrocarbon group which may have a substituent, R ４ｂ represents a substituent, m2 represents an integer of 0 to 8, A １ｃ represents a divalent hydrocarbon group which may have a substituent, m3 represents an integer of 0 to 4. The thermoplastic resin according to claim 1 or 2, which contains a second dicarboxylic acid unit (A2) represented by the following formula:

4. 4. The thermoplastic resin according to claim 3, wherein the ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) is the former / the latter (molar ratio)=30 / 70 to 95 / 5.

5. the thermoplastic resin is a polyester resin further containing a diol unit (B); The diol unit (B) is represented by the following formula (3): 【Chemistry 4】 (In the formula, A ２ represents a linear or branched alkylene group, and n represents an integer of 1 or more. 【Chemistry 5】 (In the formula, Z １ and Z ２ each independently represents an aromatic hydrocarbon ring, R ５ represents a substituent, p represents an integer of 0 to 8, R ６ａ and R ６ｂ each independently represents a substituent; q1 and q2 each independently represent 0 or an integer of 1 or more; A ３ａ and A ３ｂ each independently represents a linear or branched alkylene group, and r1 and r2 each independently represent an integer of 0 or 1 or more. and a second diol unit (B2) represented by the following formula (5): 【Chemistry 6】 (In the formula, A ４ represents a direct bond or an alkylene group, A ５ａ and A ５ｂ represents a linear or branched alkylene group; s1 and s2 each independently represent 0 or an integer of 1 or more; R ７ａ and R ７ｂ each independently represents a substituent, and t1 and t2 each independently represent an integer of 0 to 6. The thermoplastic resin according to any one of claims 1 to 4, further comprising at least one diol unit selected from the third diol units (B3) represented by:

6. In formula (3), A ２ is linear or branched C ２－６ an alkylene group, n being an integer from 1 to 5; In formula (4), Z １ and Z ２ is a monocyclic aromatic hydrocarbon ring or a condensed polycyclic aromatic hydrocarbon ring, ３ａ and A ３ｂ is linear or branched C ２－６ an alkylene group, r1 and r2 being integers from 0 to 10; In formula (5), A ４ is a direct bond or C １－２ is an alkylene group, ５ａ and A ５ｂ is linear or branched C ２－６ The thermoplastic resin according to claim 5, which is an alkylene group, and s1 and s2 are integers of 0 to 10.

7. 7. The thermoplastic resin according to claim 5, wherein the proportion of the first diol units (B1) is 1 mol % or more based on the total diol units (B).

8. The thermoplastic resin according to any one of claims 5 to 7, wherein the ratio of the first diol unit (B1) to the second diol unit (B2) is the former / the latter (molar ratio) = 1 / 99 to 50 / 50.

9. The thermoplastic resin according to any one of claims 5 to 8, wherein the ratio of the first diol unit (B1) to the third diol unit (B3) is the former / the latter (molar ratio) = 5 / 95 to 50 / 50.

10. A method for producing the thermoplastic resin according to any one of claims 1 to 9, comprising polymerizing a polymerization component containing at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1).

11. The following formula (1A) 【Chemistry 7】 (In the formula, R １ａ and R １ｂ are each independently C １－５ represents an alkoxy group, R 2a and R 2b each independently represent a substituent; k1 and k2 each independently represent an integer of 0 to 5; R ３ａ and R ３ｂ are each independently C １－５ It represents an alkoxy group. A compound represented by the formula:

12. The following formula (1B) 【Chemistry 8】 (In the formula, R 1a and R 1b each independently represent a hydrogen atom or a substituent, R 2a and R 2b each independently represent a substituent; k1 and k2 each independently represent an integer of 0 to 5; R ３ａ and R ３ｂ each independently represents a hydroxyl group, an alkoxy group, or a halogen atom. An Abbe number reducer represented by the formula:

13. A resin composition comprising a thermoplastic resin and the Abbe number reducing agent according to claim 12.

14. A molded article comprising the thermoplastic resin according to any one of claims 1 to 9 or the resin composition according to claim 13.

15. The molded article according to claim 14, which is an optical member.

16. The molded article according to claim 14 or 15, which is an optical film or an optical lens.

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