Dicarboxylic acid and derivative of the same, and production method and use of the same

Abstract

To provide a dicarboxylic acid or a derivative of the same which enables formation of a resin exhibiting abnormal dispersion characteristics (partial dispersion ratio θgF) which is not too high and adequate, even if a refractive index is high or Abbe number is low, and a production method and use of the same.SOLUTION: A dicarboxylic acid represented by the following formula (1) or a derivative of the same is prepared. In the formula, Z1 represents an arene ring, R1 represents a substituent, m1 represents an integer of 0 or more, k represents an integer of 1 to 4, R2a and R2b independently represent a non-aromatic substituent, m2a represents an integer of 0 to 3, m2b represents an integer of 0 to 4, k+m2a is 4 or less, and A1a and A1b independently represent an alkylene group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to specific dicarboxylic acids and derivatives thereof, as well as production methods and uses thereof, such as resins having dicarboxylic acid units derived from the dicarboxylic acids or derivatives thereof. [Background technology]

[0002] Many small or mobile devices such as smartphones and tablet PCs are equipped with optical functions such as cameras as well as image display functions, and the requirements for optical components are increasing as the performance of these devices improves. Optical components often use resin materials that have advantages over optical glass in terms of light weight, impact resistance (flexibility), moldability (productivity), etc., but there are cases where existing resin materials are unable to fully meet the increasing requirements.

[0003] For example, imaging lens units mounted on devices with camera functions are required to be miniaturized as the devices themselves become thinner and more multifunctional, while at the same time, higher resolution is required as the imaging elements have higher pixel counts. For this reason, imaging lens units are optically designed to be small and capable of correcting various aberrations with high imaging performance, with various ingenuity being applied to the lens configuration, shape, and material selection. In general, imaging lens units are composed of multiple lenses with different Abbe numbers and refractive indexes, and are often composed of a combination of lenses with high Abbe numbers and lenses with low Abbe numbers, but there is a limit to the types of resin materials that can be used for optical lenses, and there is a limit to the design of lens units that are highly effective. For this reason, from the viewpoint of high functionality or high performance, it is important to widen the range of material selection in order to increase the degree of design freedom and enable the design of various lens units, and there is a demand for the development of various optical resin materials with different optical properties such as Abbe numbers.

[0004] For example, International Publication No. 2020 / 213470 (Patent Document 1) describes that a resin having a specific dicarboxylic acid unit exhibits a high refractive index and a low Abbe number.

[0005] On the other hand, the partial dispersion ratio θgF is known as an index that represents wavelength dispersion characteristics other than the Abbe number, and materials with a high partial dispersion ratio θgF (which shows large anomalous dispersion characteristics) can effectively correct or reduce chromatic aberration (shift in the imaging position due to wavelength).

[0006] For example, International Publication No. 2017 / 146022 (Patent Document 2) proposes a resin that has a sufficiently low Abbe number and a high partial dispersion ratio θgF. In addition, Japanese Patent Application Laid-Open No. 2023-152924 (Patent Document 3) proposes a thermoplastic resin that exhibits a high partial dispersion ratio θgF even in a region where the Abbe number is high. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2020 / 213470 [Patent Document 2] International Publication No. 2017 / 146022 [Patent Document 3] JP 2023-152924 A Summary of the Invention [Problem to be solved by the invention]

[0008] In the examples of Patent Document 1, a resin containing a specific dicarboxylic acid unit in which naphthyl groups are substituted on both sides (2,7-positions) of a fluorene skeleton is prepared, but nothing is described or suggested about the anomalous dispersion characteristics (partial dispersion ratio θgF) of the obtained resin.

[0009] Patent Document 2 discloses a polycarbonate resin that exhibits a low Abbe number and high anomalous dispersion as a material in which the resin itself exhibits high anomalous dispersion without the addition of an anomalous dispersion compound (low molecular weight compound). In the examples of this document, it is stated that a specific polycarbonate resin exhibited a low Abbe number and high anomalous dispersion, but no specific numerical values ​​are given, except that the θgF value is 0.600 or more. It is also stated that comparative examples with a lower refractive index or a higher Abbe number than the examples had low anomalous dispersion.

[0010] Patent Document 3 discloses a thermoplastic resin containing a specific dicarboxylic acid unit and a constituent unit derived from an alicyclic monomer component, and in the examples, it describes that a polyester-based resin containing a specific dicarboxylic acid unit in which a naphthyl group or a phenyl group is substituted on both sides (2,7-positions) of a fluorene skeleton and a specific alicyclic monomer unit is prepared, and that the anomalous dispersion characteristics (partial dispersion ratio θgF) are high in a region where the Abbe number is relatively high.

[0011] However, depending on the design of the optical lens, if the anomalous dispersion characteristics (partial dispersion ratio θgF or ΔθgF) are too high, it may be difficult to correct or reduce chromatic aberration on the short wavelength side (especially blue). Since there is a tendency for the anomalous dispersion characteristics (partial dispersion ratio θgF or ΔθgF) to increase as the refractive index or Abbe number increases, there has been a demand for a material that has a high refractive index or low Abbe number but does not cause an excessive increase in the anomalous dispersion characteristics (partial dispersion ratio θgF or ΔθgF) in order to improve the degree of freedom in design.

[0012] Therefore, an object of the present disclosure is to provide a dicarboxylic acid or a derivative thereof capable of forming a resin exhibiting appropriate (neither too high nor too low) anomalous dispersion characteristics (partial dispersion ratio θgF or ΔθgF) even if the refractive index is high or the Abbe number is low, as well as a production method and uses thereof. [Means for solving the problem]

[0013] As a result of intensive research to achieve the above object, the present inventors have found that when a resin is prepared from a specific dicarboxylic acid or a derivative thereof, the resulting resin exhibits moderately high anomalous dispersion characteristics even if the refractive index of the resulting resin is high or the Abbe number is low, and have completed the present invention (or the present disclosure). That is, the present disclosure may include the following aspects, etc.

[0014] Aspect [1]: A dicarboxylic acid represented by the following formula (1) or a derivative thereof.

[0015] [ka]

[0016] (In the formula, Z 1 indicates an arene ring, R 1 represents a substituent, m1 represents an integer of 0 or more, k represents an integer from 1 to 4; R 2a and R 2b each independently represents a non-aromatic substituent; m2a represents an integer of 0 to 3; m2b represents an integer of 0 to 4; k+m2a is less than or equal to 4, A 1a and A 1b each independently represents an alkylene group.

[0017] Aspect [2]: In the formula (1), Z 1 is C 6-14 Represents an arene ring; R 1 represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m1 represents an integer of 0 to 4, k represents an integer of 1 to 2; R 2a and R 2b each independently represents an aliphatic hydrocarbon group, a halogen atom, or a cyano group; m2a represents an integer of 0 to 2; m2b represents an integer of 0 to 2; A 1a and A 1b is independently C1-6 The dicarboxylic acid or derivative thereof according to embodiment [1], wherein the dicarboxylic acid represents an alkylene group.

[0018] Aspect [3]: A compound having a fluorene skeleton and Z 1 The method for producing a dicarboxylic acid or a derivative thereof according to embodiment [1] or [2], comprising a coupling step of carrying out a coupling reaction with a compound having an arene ring skeleton corresponding to the above formula:

[0019] Aspect [4]: ​​A resin containing a dicarboxylic acid component as a resin raw material or a polymerization component, wherein the dicarboxylic acid unit (A), which is a structural unit derived from the dicarboxylic acid component, contains at least a first dicarboxylic acid unit (A1) represented by the following formula (1P).

[0020] [ka]

[0021] [In the formula, Z 1 , R 1 , m1, k, R 2a and R 2b , m2a and m2b, k+m2a, and A 1a and A 1b are the same as formula (1) described in the above embodiment [1] or [2].

[0022] Aspect [5]: The resin according to aspect [4], wherein the proportion of the first dicarboxylic acid units (A1) is 30 mol % or more based on the total amount of the dicarboxylic acid units (A).

[0023] Aspect [6]: The resin according to aspect [4] or [5], wherein the dicarboxylic acid unit (A) comprises at least one selected from a second dicarboxylic acid unit (A2) represented by the following formula (2) and a third dicarboxylic acid unit (A3) represented by the following formula (3).

[0024] [ka]

[0025] (In the formula, R 3 represents a non-aromatic substituent, m3 represents an integer of 0 to 8, A 2a and A 2b each independently represents an alkylene group.

[0026] [ka]

[0027] (In the formula, A 3 represents a direct bond or an alkylene group, A 4a and A 4b each independently represents an alkylene group; n4a and n4b each independently represent an integer of 0 or more; A 5a and A 5b each independently represents an alkylene group; R 4a and R 4b each independently represents a substituent, and m4a and m4b each independently represent an integer of 0 to 6.

[0028] Aspect [7]: In the formula (2), R 3 represents an aliphatic hydrocarbon group, a halogen atom or a cyano group, m3 represents an integer of 0 to 2, A 2a and A 2b is independently C 1-6 represents an alkylene group, In the formula (3), A 3 is a direct bond or C 1-4 represents an alkylene group, A 4a and A 4b is independently C 2-6 An alkylene group is represented, and n4a and n4b each independently represent an integer of 0 to 10. A 5a and A 5b is independently C 1-8 represents an alkylene group, R 4a and R 4beach independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group, and m4a and m4b each independently represent an integer of 0 to 3.

[0029] Aspect [8]: The resin according to aspect [6] or [7], wherein the ratio of the first dicarboxylic acid units (A1) to the total amount of the second dicarboxylic acid units (A2) and the third dicarboxylic acid units (A3) is the former / latter (molar ratio) = 30 / 70 to 80 / 20.

[0030] Aspect [9]: The resin according to any one of aspects [4] to [8], wherein the resin raw material or polymerization component is a polyester-based resin containing a diol component, and the diol unit (B), which is a structural unit derived from the diol component, includes at least one selected from a first diol unit (B1) represented by the following formula (4), a second diol unit (B2) represented by the following formula (5), and a third diol unit (B3) represented by the following formula (6).

[0031] [ka]

[0032] (In the formula, R 5 represents a substituent, m5 represents an integer of 0 to 8, Z 2a and Z 2b each independently represents an arene ring, R 6a and R 6b each independently represents a substituent; m6a and m6b each independently represent an integer of 0 or more; A 6a and A 6b each independently represents an alkylene group, and n6a and n6b each independently represent an integer of 0 or more.

[0033] [ka]

[0034] (In the formula, A7 represents a direct bond or an alkylene group, A 8a and A 8b each independently represents an alkylene group; n8a and n8b each independently represent an integer of 0 or more; R 7a and R 7b each independently represents a substituent, and m7a and m7b each independently represent an integer of 0 to 6. [ka]

[0035] (In the formula, A 9 represents an alkylene group, and n9 represents an integer of 1 or more.

[0036] Aspect

[10] : In the formula (4), R 5 represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m5 represents an integer of 0 to 2, Z 2a and Z 2b is independently C 6-14 Represents an arene ring; R 6a and R 6b each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m6a and m6b each independently represent an integer of 0 to 2; A 6a and A 6b is independently C 2-6 An alkylene group is represented, and n6a and n6b each independently represent an integer of 0 to 10. In the formula (5), A 7 is a direct bond or C 1-4 represents an alkylene group, A 8a and A 8b is independently C 2-6 An alkylene group is represented, and n8a and n8b each independently represent an integer of 0 to 10. R 7a and R 7beach independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m7a and m7b each independently represent an integer of 0 to 3; In the formula (6), A 9 is C 2-6 The resin according to embodiment [9], wherein n9 represents an alkylene group, and n9 represents an integer of 1 to 10.

[0037] Aspect

[11] : the total ratio of the first diol unit (B1), the second diol unit (B2) and the third diol unit (B3) is 30 mol% or more based on the total amount of the diol units (B); The resin according to embodiment [9] or

[10] , wherein a ratio of the total amount of the first diol units (B1) and the second diol units (B2) to the third diol units (B3) is the former / latter (molar ratio)=50 / 50 to 99 / 1.

[0038] Aspect

[12] : The refractive index nd is 1.58 or more, The Abbe number νd is 25 or less, The resin according to any one of aspects [4] to

[11] , wherein the partial dispersion ratio θgF is 0.655 to 0.725.

[0039] Aspect

[13] : the weight average molecular weight Mw is 10,000 to 100,000, The glass transition temperature Tg is 130 to 180°C. The absolute value of birefringence of the stretched film uniaxially stretched under the conditions of a stretching temperature (glass transition temperature Tg+10) °C, a stretching speed of 25 mm / min, and a stretching ratio of 3 times is 100 × 10 at a wavelength of 600 nm. -4 The resin according to any one of aspects [4] to

[12] , which is as follows:

[0040] Aspect

[14] : A method for producing the resin according to any one of aspects [4] to

[13] , by polymerizing a polymerization component containing at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1).

[0041] Aspect

[15] : A molded article comprising the resin according to any one of aspects [4] to

[13] .

[0042] Aspect

[16] : The molded article according to aspect

[15] , which is an optical component.

[0043] Embodiment

[17] : The molded article according to embodiment

[15] or

[16] , which is an optical lens.

[0044] In addition, the present disclosure may achieve the following secondary objectives (solve secondary problems).

[0045] In other words, another object of the present disclosure is to provide a dicarboxylic acid or a derivative thereof capable of forming a resin that can achieve a good balance between a high refractive index and low birefringence (low absolute value of birefringence), which are optical properties that trade off each other, as well as a production method and uses thereof.

[0046] Yet another object of the present disclosure is to provide a dicarboxylic acid or a derivative thereof capable of forming a resin that has a good balance between heat resistance and moldability (or productivity), which are in a trade-off relationship with each other, and a production method and use thereof.

[0047] In the present specification and claims, the term "derivative" of a dicarboxylic acid is used to mean not only ester-forming or amide-forming derivatives of dicarboxylic acid such as esters (dicarboxylic acid esters), acid halides (dicarboxylic acid halides), and acid anhydrides (dicarboxylic acid anhydrides), but also compounds (low molecular weight compounds) that can be converted from dicarboxylic acids by conventional methods, such as amides (dicarboxylic acid amides) and salts (dicarboxylic acid salts). The esters may be monoesters (half esters) or diesters.

[0048] Examples of the dicarboxylate ester include dicarboxylate alkyl esters, particularly lower alkyl esters, specifically C esters such as methyl esters, ethyl esters, and t-butyl esters. 1-4Examples of the dicarboxylic acid halide include acid chloride and acid bromide. Examples of the dicarboxylic acid salt include metal salts, specifically, alkali metal salts such as sodium salts, and ammonium salts.

[0049] In the present specification and claims, the term "dicarboxylic acid component" is used to mean not only dicarboxylic acids but also derivatives usable as polymerization components, such as the above-mentioned ester (or amide) forming derivatives.

[0050] Furthermore, in this specification and claims, "dicarboxylic acid unit" and "structural unit derived from dicarboxylic acid component" mean a unit (or divalent group) obtained by removing OH (hydroxyl group) from each of the two carboxyl groups of the corresponding dicarboxylic acid, and "dicarboxylic acid component" (including compounds exemplified as dicarboxylic acid component) may be used synonymously with the corresponding "dicarboxylic acid unit". Similarly, "diol unit" and "structural unit derived from diol component" mean a unit (or divalent group) obtained by removing hydrogen atoms from each of the two hydroxyl groups of the corresponding diol, and "diol component" (including compounds exemplified as diol component) may be used synonymously with the corresponding "diol unit".

[0051] In this specification and claims, unless otherwise specified, the terms "low birefringence" and "low birefringence" mean that the absolute value of the birefringence is small (that is, close to 0).

[0052] In addition, in the present specification and claims, the number of carbon atoms of a substituent is defined as C1, C6, C 10 For example, an alkyl group with one carbon atom is called a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is called a "C 6-10 "Aryl group" etc.

[0053] Furthermore, in this specification and claims, the term "independently" means that a plurality of components are independent components. For example, A 1a and A 1b In this case, they may be the same alkylene group or different alkylene groups.

[0054] In this specification and claims, the numerical range indicated by "X to Y" may include the numerical values ​​X and Y. Effect of the Invention

[0055] According to the present disclosure, it is possible to provide a dicarboxylic acid or a derivative thereof capable of forming a material resin that exhibits moderate (neither too high nor too low) anomalous dispersion characteristics (partial dispersion ratio θgF or ΔθgF) even if the refractive index is high or the Abbe number is low, as well as a production method and use thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0056] [Dicarboxylic acid component or its derivative] The dicarboxylic acid of the present disclosure is represented by the following formula (1):

[0057] [ka]

[0058] (In the formula, Z 1 indicates an arene ring, R 1 represents a substituent, m1 represents an integer of 0 or more, k represents an integer from 1 to 4; R 2a and R 2b each independently represents a non-aromatic substituent; m2a represents an integer of 0 to 3; m2b represents an integer of 0 to 4; k+m2a is less than or equal to 4, A 1a and A 1b each independently represents an alkylene group.

[0059] In the formula (1), Z 1 Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (1) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a condensed polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), etc.

[0060] 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 fused tricyclic C arene rings such as anthracene ring and phenanthrene ring. 14-20 A preferred fused polycyclic arene ring is a fused polycyclic C ring such as a naphthalene ring. 10-14 It is an arene ring.

[0061] Examples of the ring assembly arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring assembly arene rings are C 12-18 This is a biarene ring.

[0062] In the present specification and claims, a "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems; for example, as described above, a phenylnaphthalene ring, a binaphthyl ring, and the like are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as a naphthalene ring (non-ring assembly arene ring).

[0063] Preferred Ring Z 1 As for C 6-14 arene rings, and more preferably C rings such as benzene rings, naphthalene rings, and biphenyl rings.6-12 C such as an arene ring, more preferably a benzene ring or a naphthalene ring 6-10 arene rings, and particularly preferably naphthalene rings. 1 When is a condensed polycyclic arene ring such as a naphthalene ring, it is easy to prepare a resin that satisfies a good balance of a high refractive index, a low Abbe number, and a low birefringence, and there is a tendency that an excessive increase in the anomalous dispersion characteristic (partial dispersion ratio θgF) is suppressed and it is easy to adjust it to a moderately high range.

[0064] When k is 2 or more, two or more rings Z 1 The types may be the same or different from each other.

[0065] Also, Z 1 may be substituted at any one of positions 1 to 4 of the fluorene skeleton, but is usually substituted at position 2 or 3. When k is 1, the preferred substitution position (or bonding position) is the 2-position.

[0066] In addition, Z to the fluorene skeleton 1 The bond position of Z 1 When is a naphthalene ring, it may be either the 1-position or the 2-position of the naphthalene ring, and the 2-position of the naphthalene ring is preferred because it makes it easy to prepare a resin that has a high refractive index, a low Abbe number, and a low birefringence in a well-balanced manner, and because it is possible to suppress an excessive increase in the anomalous dispersion characteristic (partial dispersion ratio θgF) and adjust it to an appropriately high range.

[0067] R 1 Examples of the substituent represented by the formula (non-reactive group or non-polymerizable group) include a halogen atom, a hydrocarbon group (or a group [-R h ]), the group [-OR h ](wherein, R h represents a hydrocarbon group), the group [-SR h ](wherein, R h represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, a substituted amino group (mono- or di-substituted amino group), and the like.

[0068] In this specification and claims, Rh The hydrocarbon groups represented by the following formula (I) each represent an independent hydrocarbon group, and may be the same or different from each other.

[0069] Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0070] Hydrocarbon group (or group [-R h ]) may be a saturated or unsaturated hydrocarbon group, an aliphatic (including alicyclic) or aromatic hydrocarbon group, and may be a chain (straight or branched) or cyclic hydrocarbon group, or a hydrocarbon group having a structure that combines a chain and a cyclic structure. Representative hydrocarbon groups R h Examples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0071] Examples of the alkyl group (linear or branched alkyl group) include C alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. 1-10 Alkyl groups are preferred, and C 1-6 Alkyl groups, more preferably C 1-4 It is an alkyl group.

[0072] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are included.

[0073] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group), etc. 1-4 Examples include alkyl-phenyl groups.

[0074] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4Examples of such groups include alkyl groups.

[0075] The group [-OR h ] and [-SR h ], R h The hydrocarbon group represented by R 1 Examples of the hydrocarbon groups include the same hydrocarbon groups as those exemplified above, including preferred embodiments thereof, such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0076] The group [-OR h ] is, for example, the hydrocarbon group R h Examples of the alkoxy group include an alkoxy group, a cycloalkyloxy group, an aryloxy group, and an aralkyloxy group. Examples of the alkoxy group (linear or branched alkoxy group) include C alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include C aryloxy groups such as phenoxy groups. 6-10 Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 An example of such a group is an alkyloxy group.

[0077] The group [-SR h ] is, for example, the hydrocarbon group R h Examples of the alkylthio group include a C alkylthio group, a cycloalkylthio group, an arylthio group, and an aralkylthio group. Examples of the alkylthio group include a C alkylthio group, such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10Examples of the arylthio group include a C thiophenoxy group. 6-10 Examples of the aralkylthio group include C arylthio groups such as benzylthio groups. 6-10 Aryl-C 1-4 Examples of such groups include alkylthio groups.

[0078] Acyl groups include C such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

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

[0080] These groups R 1 Representative examples of the R include halogen atoms, hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. 1 Examples of the alkyl group include an alkyl group and an alkoxy group. Specifically, C 1-6 C such as alkyl group and methoxy group 1-4 Alkoxy groups are exemplified, among which alkyl groups, particularly C such as methyl groups, are preferred. 1-4 The alkyl group is preferred. 1 is an aryl group, the group R 1 is the ring Z 1 may form a ring assembly arene ring together with

[0081] R 1 The number of substitutions m1 is an integer equal to or greater than 0, and Z 1For example, it can be selected from integers of about 0 to 7, preferably from integers of 0 to 6, 0 to 5, 0 to 4, 0 to 3, and 0 to 2 in the following stepwise order, more preferably 0 or 1, and particularly preferably 0. When the number of substitutions m1 is 2 or more, the number of substitutions m2 is 2 or more. 1 Two or more groups R 1 The types of R may be the same or different from each other. 1 The substitution position of Z is not particularly limited. 1 The selection may be made according to the type of

[0082] group [-Z 1 -(R 1 ) m1 ](hereinafter simply Z 1 The number of substitutions k of the group (also referred to as a "containing group") is, for example, an integer of about 1 to 3, preferably 1 or 2, and more preferably 1. When k is 2 or more, 2 or more Z 1 The types of the contained groups may be the same or different.

[0083] R 2a ,R 2b The non-aromatic substituent (non-aromatic non-reactive group or non-polymerizable group) represented by the formula: 1 Any substituent other than the containing group may be used, and representative examples include non-aromatic hydrocarbon groups, halogen atoms such as fluorine atoms, chlorine atoms and bromine atoms, and cyano groups.

[0084] The non-aromatic hydrocarbon group is the same as R 1 Among the hydrocarbon groups exemplified as R, non-aromatic groups and the like can be mentioned, and specifically, aliphatic hydrocarbon groups such as alkyl groups and cycloalkyl groups can be mentioned. 2a and R 2b Examples of the alkyl group include an aliphatic hydrocarbon group, a halogen atom, and a cyano group, and more preferably C 1-6 Alkyl groups such as alkyl groups, especially C groups such as methyl groups, ethyl groups, and t-butyl groups 1-4 It is an alkyl group.

[0085] R 2a,R 2b The number of substitutions m2a and m2b may each independently be an integer of about 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. m2a and m2b may be different from each other, but are preferably the same. When m2a is 2 or more, 2 or more R 2a may be the same or different; when m2b is 2 or more, 2 or more R 2b The types of R may be the same or different. 2a and R 2b The types of R may be the same or different, and are preferably the same. 2a ,R 2b The substitution position of R is not particularly limited as long as it is any one of the 1- to 8-positions of the fluorene skeleton. 2a is Z 1 It is sufficient that the substituent is present at a position other than the substitution position of the containing group.

[0086] k+m2a is, for example, an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1.

[0087] Base A 1a and A 1b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C 1, C 2, C 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10, C 11, C 12, C 13, C 14, C 15, C 16, C 17, C 18, C 19, C 20, C 21, C 22, C 23, C 24, C 25, C 36, C 26, C 37, C 27, C 38, C 39, C 41, C 42, C 43, C 44, C 45, C 46, C 47, C 48, C 49, C 51, C 52, C 53, C 54, C 55, C 56, C 57, C 58, C 1-8 Examples of the alkylene group include a C alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a 2-methylpropane-1,3-diyl group. 1-6 An alkylene group is preferable, and C 1-4 An alkylene group, more preferably C 2-4 Alkylene groups, especially C groups such as ethylene and propylene. 2-3 An alkylene group is preferred, and an ethylene group is particularly preferred. 1a and A 1b may be different from each other, but are preferably the same.

[0088] Representative dicarboxylic acids or derivatives thereof represented by the formula (1) include Z 1 is C 6-14 Represents an arene ring; R 1 represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m1 represents an integer of 0 to 4, k represents an integer of 1 to 2; R 2a and R 2b each independently represents an aliphatic hydrocarbon group, a halogen atom, or a cyano group; m2a represents an integer of 0 to 2; m2b represents an integer of 0 to 2; A 1a and A 1b is independently C 1-6 A dicarboxylic acid or a derivative thereof exhibiting an alkylene group; Preferably, in the formula (1), Z 1 C is a benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 Represents an arene ring; R 1 represents a hydrocarbon group, m1 represents an integer of 0 to 2, k is 1, R 2a and R 2b each independently represents an aliphatic hydrocarbon group, m2a represents 0 or 1, m2b represents 0 or 1, A 1a and A 1b is independently C 1-4 A dicarboxylic acid or a derivative thereof exhibiting an alkylene group; More preferably, in the formula (1), Z 1 is C 6-10 Represents an arene ring; R 1 represents an alkyl group or a cycloalkyl group, m1 represents an integer of 0 to 2, k is 1, R 2a and R 2b independently represents an alkyl group or a cycloalkyl group, m2a represents 0 or 1, m2b represents 0 or 1, A 1a and A 1b is independently C 2-4 A dicarboxylic acid or a derivative thereof exhibiting an alkylene group; Particularly preferably, in the formula (1), Z 1 represents a naphthalene ring, R 1 represents an alkyl group, m1 represents an integer of 0 to 2, k is 1, R 2a and R 2b independently represents an alkyl group, m2a represents 0 or 1, m2b represents 0 or 1, A 1a and A 1b is independently C 2-3 It is a dicarboxylic acid or a derivative thereof which exhibits an alkylene group.

[0089] Specific examples of the dicarboxylic acid represented by the formula (1) include dicarboxylic acids in which k is 1, 9,9-bis(carboxyalkyl)-arylfluorenes or derivatives thereof, and more specifically, 9,9-bis(carboxyalkyl)-phenylfluorene, 9,9-bis(carboxyalkyl)-naphthylfluorene, etc.

[0090] Examples of the 9,9-bis(carboxyalkyl)-phenylfluorene include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-1-phenylfluorene, 9,9-bis(2-carboxyethyl)-2-phenylfluorene, 9,9-bis(2-carboxyethyl)-3-phenylfluorene, 9,9-bis(2-carboxyethyl)-4-phenylfluorene, and 9,9-bis(2-carboxypropyl)-2-phenylfluorene. 2-6 alkyl)-phenylfluorene.

[0091] Examples of 9,9-bis(carboxyalkyl)-naphthylfluorene include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-1-(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2-(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-3-(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-4-(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2-(2-naphthyl)fluorene, and 9,9-bis(2-carboxyethyl)-2-(1-naphthyl)fluorene. 2-6 alkyl)-naphthylfluorene and the like.

[0092] Among these dicarboxylic acids represented by the above formula (1), 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-2-phenylfluorene is preferred. 2-4 Alkyl)-2-phenylfluorene;9,9-bis(carboxy C 2-4 alkyl)-2-naphthylfluorene is preferred, and 9,9-bis(carboxy C alkyl) such as 9,9-bis(2-carboxyethyl)-2-(2-naphthyl)fluorene and 9,9-bis(2-carboxyethyl)-2-(1-naphthyl)fluorene is preferred. 2-4 Among them, 9,9-bis(carboxy C)-2-(2-naphthyl)fluorene such as 9,9-bis(2-carboxyethyl)-2-(2-naphthyl)fluorene and 9,9-bis(2-methoxycarbonylethyl)-2-(2-naphthyl)-fluorene is more preferred, since it is easy to prepare a resin that satisfies a good balance between a high refractive index, a low Abbe number, and a low birefringence, and the anomalous dispersion characteristic (partial dispersion ratio θgF) can be adjusted to a moderately high range by suppressing an excessive increase in the anomalous dispersion characteristic. 2-3 C alkyl)-2-(2-naphthyl)fluorene or a derivative thereof (e.g., an ester-forming derivative such as an alkyl ester, in particular, a C methyl ester, an ethyl ester, etc. 1-4 Alkyl esters) are particularly preferred.

[0093] The refractive index of the dicarboxylic acid represented by the formula (1) or its derivative at a temperature of 25° C. and a wavelength of 589 nm may be, for example, about 1.57 to 1.67, and preferably ranges from 1.6 to 1.66, 1.61 to 1.65, 1.62 to 1.64, and 1.625 to 1.635 in the following stepwise manner.

[0094] The dicarboxylic acid or derivative thereof represented by the formula (1) may be crystalline or amorphous. When crystalline, the melting point may be, for example, about 100 to 200°C, and preferably 150 to 180°C, 155 to 170°C, and 160 to 165°C in the following stepwise manner.

[0095] The 5% weight loss temperature of the dicarboxylic acid represented by the formula (1) or its derivative may be, for example, about 250 to 400°C, and preferably 300 to 350°C, 310 to 340°C, and 320 to 330°C in the following stepwise manner.

[0096] In this specification and claims, the refractive index, melting point and 5% weight loss temperature of the dicarboxylic acid represented by the formula (1) or its derivatives can be measured by the method described in the examples below.

[0097] (Method of producing dicarboxylic acid or its derivative) The method for producing the dicarboxylic acid or a derivative thereof according to the present disclosure is not particularly limited, and may be a conventional method, for example, a method for producing a compound having a fluorene skeleton and Z 1 arene ring skeleton (and optionally a group [-(R 1 ) m1 ]) 1 ,R 1 and a compound containing an arene ring skeleton corresponding to m1) is subjected to a coupling reaction to form a structure (Z 1 ,R 1and m1), etc. Therefore, the compound having a fluorene skeleton may be a compound having a reactive group capable of coupling reaction with the compound having an arene ring skeleton at at least one substitution position selected from the 1-4-positions of the fluorene skeleton. In addition, the 9,9-position of the compound having a fluorene skeleton does not necessarily have to be a group [-A 1a -C(=O)-OH],[-A 1b -C(=O)-OH] or a derivative thereof (such as an ester) may be unsubstituted, and the 9,9-positions may be unsubstituted. After the coupling step, a group [-A 1a -C(=O)-OH],[-A 1b -C(=O)-OH] or a derivative group thereof (such as an ester) may be introduced.

[0098] A representative method may involve a coupling reaction (or cross-coupling reaction) between a dicarboxylic acid represented by the following formula (I) or a derivative thereof (hereinafter also simply referred to as compound (I)) and a compound represented by the following formula (II) (hereinafter also simply referred to as compound (II)) according to the following reaction formula:

[0099] [ka]

[0100] (In the formula, X 1 represents a reactive group capable of forming a carbon-carbon bond (or a direct bond) by a coupling reaction; X 2 is the reactive group X 1 and a reactive group capable of forming a carbon-carbon bond by a coupling reaction; Z 1 , R 1 , m1, k, R 2a , R 2b , m2a, m2b, k+m2a, A 1a and A 1b are the same as those in the above formula (1), including preferred embodiments.)

[0101] The coupling reaction is not particularly limited, and examples thereof include conventional coupling reactions, such as Suzuki-Miyaura coupling reaction, Migita-Kosugi-Stille coupling reaction, Negishi coupling reaction, Hiyama coupling reaction, and other coupling reactions using a palladium catalyst (or palladium(0) catalyst), Kumada-Tamao-Corriu coupling reaction, and other nickel catalyst (or nickel(0) catalyst) coupling reactions. Among these coupling reactions, the Suzuki-Miyaura coupling reaction is often used.

[0102] Reactive Group X 1 and X 2 can be appropriately selected depending on the type of the coupling reaction. In the case of synthesis by Suzuki-Miyaura coupling reaction, one reactive group, for example, group X 1 Examples of the fluorinated alkanesulfonyloxy group include a halogen atom or a fluorinated alkanesulfonyloxy group. Examples of the halogen atom include an iodine atom, a bromine atom, and a chlorine atom. Examples of the fluorinated alkanesulfonyloxy group include a fluorinated C such as a trifluoromethanesulfonyloxy group (or a group [-OTf]). 1-4 Examples thereof include an alkanesulfonyloxy group.

[0103] These one reactive groups may be used alone or in combination of two or more. Of these one reactive groups, a halogen atom is preferred, an iodine atom or a bromine atom is more preferred, and a bromine atom is more preferred.

[0104] In the Suzuki-Miyaura coupling reaction, the one reactive group and the other reactive group capable of coupling, for example, a group X 2Examples of the boronic acid group include boron-containing groups such as a boronic acid group (dihydroxyboryl group or group [-B(OH)2]) and a boronic acid ester group. Examples of the boronic acid ester group include dialkoxyboryl groups such as a dimethoxyboryl group, a diisopropoxyboryl group, and a dibutoxyboryl group; and cyclic boronic acid ester groups such as a pinacolatoboryl group (or group [-Bpin]), a 1,3,2-dioxaborinane-2-yl group, and a 5,5-dimethyl-1,3,2-dioxaborinane-2-yl group.

[0105] These other reactive groups may be used alone or in combination of two or more. Of the other reactive groups, the group [-B(OH)2] is preferred.

[0106] In addition, X 1 and X 2 X may be any reactive group as long as it is a pair of reactive groups capable of coupling reaction with each other, 1 is the other reactive group such as a boronic acid group, and X 2 may be one of the reactive groups such as a halogen atom, but X 1 is one of the reactive groups such as a halogen atom, and X 2 is preferably the other reactive group such as a boronic acid group.

[0107] Representative examples of the compound (I) include the dicarboxylic acid esters exemplified above as the ester-forming derivatives. Compound (I) includes compounds corresponding to the preferred embodiments of the dicarboxylic acid represented by the formula (1) or its derivatives, such as 9,9-bis(C fluorene)s such as 9,9-bis(2-methoxycarbonylethyl)-2-bromofluorene, 9,9-bis(2-ethoxycarbonylethyl)-2-bromofluorene, and 9,9-bis(2-methoxycarbonylpropyl)-2-bromofluorene. 1-4 Alkoxy-carbonyl-C 2-6 alkyl)-halofluorene.

[0108] Compound (I) may be prepared, for example, according to the method described in JP-A-2005-89422. For example, 9H-halofluorenes not substituted at the 9-position, such as 2-bromofluorene, may be reacted with (meth)acrylic acid or its ester, such as methyl acrylate, or with haloacetate, such as methyl bromoacetate, in the presence of a base catalyst, such as trimethylbenzylammonium hydroxide. The reaction may be carried out in a solvent as necessary, and examples of the solvent include ketones, such as methyl isobutyl ketone (MIBK), ethers, such as 1,4-dioxane, and alcohols, such as methanol. The reaction may be carried out in the air or in an inert gas atmosphere, such as nitrogen gas or rare gas, preferably in an inert gas atmosphere, and the reaction temperature may be, for example, about 10 to 100° C. After the reaction is completed, compound (I) may be purified from the reaction mixture by a conventional separation and purification method, or may be subjected to a coupling reaction without purification, in order to improve productivity.

[0109] Representative examples of the compound (II) include compounds corresponding to the preferred embodiment of the dicarboxylic acid represented by the formula (1) or its derivatives, such as phenylboronic acid, 1-naphthylboronic acid, and 2-naphthylboronic acid, with 2-naphthylboronic acid being preferred. As the compound (II), commercially available products can be used.

[0110] The ratio of compound (I) to compound (II) may be, for example, the former / latter (molar ratio)=about 1 / 1 to 1 / 10, and is preferably 1 / 1 to 1 / 5, 1 / 1.05 to 1 / 2, and 1 / 1.1 to 1 / 1.5 in the following stepwise manner.

[0111] The coupling reaction may be carried out in the presence of a catalyst. In the case of synthesis by the Suzuki-Miyaura coupling reaction, examples of the catalyst include metal catalysts such as palladium catalysts. Examples of the palladium catalyst include palladium(0) catalysts such as tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4], bis(tri-t-butylphosphine)palladium(0) [or Pd(P(t-Bu)3)2], bis(dibenzylideneacetone)palladium(0) [Pd(dba)2], tris(dibenzylideneacetone)dipalladium(0) [Pd2(dba)3], and tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd2(dba)3·CHCl3]; palladium(II) chloride, palladium acetate, etc. Palladium(II) catalysts such as palladium(II) compounds such as [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or PdCl2(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl2(PPh3)2], and bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl2(P(o-tolyl)3)2] can be used alone or in combination. These catalysts can be used alone or in combination.

[0112] The catalyst may directly exhibit catalytic activity in the reaction system, or may be a catalyst precursor that is converted to a catalyst in the reaction system. For example, a palladium(II) catalyst such as palladium(II) acetate may be reduced to zero valence by a reducing compound such as a phosphine, amine, or organometallic reagent in the reaction system and act as a catalyst.

[0113] Among these catalysts, palladium (II) catalysts such as palladium (II) acetate are preferred because of their excellent operability (stability in air). The proportion of the catalyst may be, for example, about 0.00001 to 0.05 mol in terms of metal relative to 1 mol of compound (I), and is preferably 0.00005 to 0.015 mol, 0.0001 to 0.001 mol, and 0.0003 to 0.0007 mol in the following stepwise manner.

[0114] The coupling reaction may be carried out in the presence of a ligand together with a catalyst such as the palladium catalyst. Examples of the ligand include conventional ligands used in coupling reactions, such as phosphines and carbenes, with phosphines being preferred. Examples of the phosphines include trialkyl phosphines such as tributylphosphine, tricycloalkyl phosphines such as tricyclohexylphosphine, triaryl phosphines such as triphenylphosphine, diphenyl-biphenylyl-phosphine, tritolylphosphine, tris(mono- or dimethoxyphenyl)phosphine, tris(fluorophenyl)phosphine, and tris[di(trifluoromethyl)phenyl]phosphine, bis(diphenylphosphino)alkanes such as dppe and dppp, phosphines having a ferrocene skeleton such as dppf, and phosphines having a binaphthyl skeleton such as BINAP. These ligands may be used alone or in combination of two or more. Among these ligands, triaryl phosphines such as triphenylphosphine and tritolylphosphine are preferred. The proportion of the ligand may be, for example, about 1 to 10 mol relative to 1 mol of the catalyst, and is preferably 1.3 to 5 mol, 1.5 to 3 mol, and 1.8 to 2.5 mol in the following stepwise manner.

[0115] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base, such as a metal carbonate or hydrogen carbonate, a metal hydroxide, a metal fluoride, a metal phosphate, a metal organic acid salt, or a metal alkoxide.

[0116] Examples of metal carbonates or hydrogen carbonates include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, and thallium (I) carbonate.

[0117] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, and thallium(I) hydroxide.

[0118] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0119] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0120] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate.

[0121] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0122] These bases can be used alone or in combination of two or more. Among these, alkali metal carbonates such as sodium carbonate and potassium carbonate are preferred. The ratio of the base to 1 mole of compound (I) may be, for example, about 0.1 to 50 moles, preferably 1 to 25 moles, more preferably 1.5 to 6 moles, and particularly preferably 2 to 3 moles.

[0123] The coupling reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These phase transfer catalysts can be used alone or in combination. Among these phase transfer catalysts, TBAB is preferred.

[0124] The coupling reaction may be carried out in the absence or presence of a solvent inert to the reaction. Examples of the solvent include water, alcohols such as methanol and ethanol, ethers such as cyclic ethers and chain ethers, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile and benzonitrile, amides such as N,N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, sulfoxides such as dimethyl sulfoxide, and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0125] Examples of cyclic ethers include 1,4-dioxane and tetrahydrofuran. Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of the glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0126] Examples of the aliphatic hydrocarbons include hexane, heptane, dodecane, etc. Examples of the alicyclic hydrocarbons include cyclohexane, etc. Examples of the aromatic hydrocarbons include toluene, xylene, etc.

[0127] These solvents may be used alone or in combination of two or more. Among these solvents, a mixed solvent of water and aromatic hydrocarbons such as toluene is usually used, and a mixed solvent of water and toluene is preferred.

[0128] The coupling reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen or a rare gas such as helium or argon. The reaction temperature is, for example, 50 to 200° C., preferably 60 to 100° C., more preferably 70 to 90° C., particularly preferably 75 to 85° C. The reaction time is not particularly limited and may be, for example, about 1 to 10 hours.

[0129] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as washing, extraction, filtration, dehydration, concentration, decantation, recrystallization, reprecipitation, chromatography, adsorption, or a combination of these methods.

[0130] [Resin having dicarboxylic acid unit (A)] The resin of the present disclosure can be formed by using a dicarboxylic acid component (A) containing at least the dicarboxylic acid represented by the formula (1) or a derivative thereof as a polymerization component or a resin raw material (precursor component). Therefore, the resin is a resin having a (corresponding) dicarboxylic acid unit (A) which is a structural unit derived from the dicarboxylic acid component (A), and contains at least a structural unit derived from the dicarboxylic acid represented by the formula (1) or a derivative thereof, i.e., at least a first dicarboxylic acid unit (A1) represented by the formula (1P) described later.

[0131] From the viewpoint of moldability, the resin is preferably a thermoplastic resin, and representative examples thereof include polyester resins such as polyester resins containing at least a diol component as a polymerization component, polyester carbonate resins, and polyamide resins containing a diamine component as a polymerization component.

[0132] Optical resin materials are often required to have excellent water absorption resistance (or low moisture absorption) because if the refractive index or dimensions change due to moisture absorption, the optical properties become unstable and the material cannot be used for precision optical components. Therefore, among these resins, polyester resins such as polyester resins and polyester carbonate resins are preferred from the viewpoint of water absorption resistance (or low moisture absorption), and among these, polyester resins are even more preferred from the viewpoint of ease of improving the refractive index and glass transition temperature (or heat resistance).

[0133] (Dicarboxylic acid unit (A)) (A1) First Dicarboxylic Acid Unit When the resin contains the first dicarboxylic acid unit (A1) represented by the following formula (1P), it is easy to adjust the anomalous dispersion characteristic (partial dispersion ratio θgF) to a moderately high range by suppressing an excessive increase, and it is easy to prepare a resin that satisfies a good balance of a high refractive index, a low Abbe number, low birefringence, and high heat resistance.

[0134] [ka]

[0135] [In the formula, Z 1 , R 1 , m1, k, R 2a and R 2b , m2a and m2b, k+m2a, and A 1a and A 1b are the same as those in the above formula (1), including preferred embodiments.]

[0136] Representative examples of the first dicarboxylic acid unit (A1) include the dicarboxylic acid units corresponding to those exemplified as representative or specific dicarboxylic acids or their derivatives represented by the above formula (1), and the same applies to the preferred embodiments. These first dicarboxylic acid units (A1) may be used alone or in combination of two or more kinds.

[0137] (A2) Second dicarboxylic acid unit The dicarboxylic acid unit (A) may or may not contain a second dicarboxylic acid unit (A2) represented by the following formula (2) in addition to the first dicarboxylic acid unit (A1). When the second dicarboxylic acid unit (A2) is combined, it is easier to suppress an excessive increase in the anomalous dispersion characteristic (partial dispersion ratio θgF). In addition, when the second dicarboxylic acid unit (A2) is combined, an excessive increase in the glass transition temperature Tg can be suppressed without significantly decreasing the refractive index (or significantly increasing the Abbe number) or significantly increasing the birefringence, so that a good balance between heat resistance and moldability (or productivity) can be achieved while maintaining a high refractive index (or low Abbe number) and low birefringence.

[0138] [ka]

[0139] (In the formula, R 3 represents a non-aromatic substituent, m3 represents an integer of 0 to 8, A 2a and A 2b each independently represents an alkylene group.

[0140] In the formula (2), R 3 Examples of the non-aromatic substituent (non-aromatic non-reactive group or non-polymerizable group) represented by the formula (1) include R 2a ,R 2b Examples of the groups include the same groups as those exemplified as above, including preferred embodiments thereof.

[0141] R 3 The number of substitutions m3 is, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0. When m3 is 2 or more, 2 or more R 3 The types of may be the same or different. In addition, when R is present in both of the two benzene rings forming the fluorene skeleton, 3 When R on one benzene ring is substituted, 3 The type of R of the other benzene ring 3The types of R may be the same or different, and are preferably the same. 3 The substitution position is not particularly limited, and may be, for example, the 2-position, the 3-position, or the 2,7-position.

[0142] A 2a ,A 2b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (1) include 1a ,A 1b Examples of the groups include the same groups as those exemplified as above, including preferred embodiments thereof.

[0143] Representative examples of the second dicarboxylic acid unit (A2) include those represented by the formula (2) below: 3 represents an aliphatic hydrocarbon group, a halogen atom or a cyano group, m3 represents an integer of 0 to 2, A 2a and A 2b is independently C 1-6 Examples of units include units representing alkylene groups; Preferably, R 3 represents an aliphatic hydrocarbon group such as an alkyl group or a cycloalkyl group, m3 represents an integer of 0 to 2, A 2a and A 2b is independently C 1-4 Examples of units include units representing alkylene groups; More preferably, R 3 is C 1-6 m3 represents an integer of 0 to 2; A 2a and A 2b is independently C 2-4 Examples of units include units representing alkylene groups; Particularly preferably, m3 represents 0, A 2a and A 2b is independently C 2-3 and units representing alkylene groups.

[0144] Specific examples of the second dicarboxylic acid component (A2) forming the second dicarboxylic acid unit (A2) include 9,9-bis(carboxyalkyl)fluorenes, more specifically, 9,9-bis(carboxyalkyl)fluorenes such as 9,9-bis(2-carboxyethyl)fluorene and 9,9-bis(2-carboxypropyl)fluorene. 2-6 alkyl)fluorene, preferably 9,9-bis(carboxy C 2-4 alkyl)fluorene, or ester-forming derivatives thereof.

[0145] These second dicarboxylic acid units (A2) may be used alone or in combination of two or more kinds.

[0146] (A3) a third dicarboxylic acid unit The dicarboxylic acid unit (A) may or may not contain a third dicarboxylic acid unit (A3) represented by the following formula (3) in addition to the first dicarboxylic acid unit (A1). When the third dicarboxylic acid unit (A3) is combined, it is easier to suppress an excessive increase in the anomalous dispersion characteristic (partial dispersion ratio θgF). In addition, when the third dicarboxylic acid unit (A3) is combined, an excessive increase in the glass transition temperature Tg can be suppressed without significantly decreasing the refractive index (or significantly increasing the Abbe number) or significantly increasing the birefringence, so that the heat resistance and moldability (or productivity) can be well balanced while having a high refractive index (or low Abbe number) and low birefringence.

[0147] [ka]

[0148] (In the formula, A 3 represents a direct bond (single bond) or an alkylene group, A 4a and A 4b each independently represents an alkylene group; n4a and n4b each independently represent an integer of 0 or more; A 5a and A 5b each independently represents an alkylene group; R4a and R 4b each independently represents a substituent, and m4a and m4b each independently represent an integer of 0 to 6.

[0149] In the formula (3), A 3 The alkylene group (straight-chain or branched-chain alkylene group) in the formula (I) is a C alkylene group such as a methylene group or an ethylene group. 1-6 An alkylene group is preferably C 1-4 Alkylene group, more preferably C 1-2 It is an alkylene group.

[0150] Preferred A 3 As a direct bond (single bond) or C 1-2 An alkylene group is exemplified, and a direct bond (single bond) or a methylene group is more preferred, and a direct bond (single bond) is particularly preferred.

[0151] A 4a ,A 4b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. 2-6 Alkylene groups and the like are preferably C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 Alkylene groups, particularly ethylene groups, are preferred.

[0152] Alkyleneoxy group [-(A 4a O)-],[-(A 4bThe repeat numbers (number of added moles) n4a and n4b of the formula (O)-] may each be selected from an integer of about 0 to 15, for example, and are preferably 0 to 10, 0 to 8, 0 to 6, 0 to 4, and 0 to 2 in the following stepwise manner, and more preferably 0 or 1, and particularly 0. In this specification and claims, the "repeat number (number of added moles)" may be an average value (arithmetic mean value, additive mean value) or an average number of added moles. Therefore, n4a and n4b may each be selected from a range of about 0 to 15, for example, and are preferably 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, and particularly 0 in the following stepwise manner. When n4a and n4b are in a moderate range that is not too large, the heat resistance and refractive index tend not to decrease.

[0153] In addition, n4a and n4b may be the same or different. When n4a is 2 or more, it is possible to use two or more groups [-(A 4a The types of groups [-(A 4b The types of A)- may be different from each other, but are preferably the same. 4a and A 4b The types may be the same or different, but are preferably the same.

[0154] A 5a ,A 5b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as methylene group, ethylene group, propylene group (1,2-propanediyl group), trimethylene group, 1,2-butanediyl group, tetramethylene group, and hexamethylene group. 1-8 Alkylene groups, etc., are preferably selected from the following stepwise manner: 1-8 Alkylene group, C 1-6 Alkylene group, C 1-5 Alkylene group, C 1-4 Alkylene group, C 2-4 Alkylene group, such as propylene group 2-3 An alkylene group is more preferred. 5a and A 5bThe types may be the same or different, but are preferably the same.

[0155] The group [-O-(A 4a O) n4a -A 5a -C(=O)-], [-O-(A 4b O) n4b -A 5b The bonding position (substitution position) of the oxygen atom (ether bond) in the --C(=O)-- (i.e., the divalent group forming the main chain of the resin) to the naphthalene ring is not particularly limited. 3 When the bonding position of is assumed to be the 1-position, the 2-position is preferred.

[0156] R 4a ,R 4b Examples of the substituent (non-reactive group or non-polymerizable group) represented by the formula (1) include R 1 Examples of the groups include the same groups as those exemplified as above, including preferred embodiments thereof.

[0157] R 4a ,R 4b The numbers of substitutions m4a and m4b may each independently be an integer of, for example, about 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0. m4a and m4b may be different from each other, but are preferably the same. When m4a is 2 or more, 2 or more R 4a may be the same or different; when m4b is 2 or more, 2 or more R 4b The types of R may be the same or different from each other. 4a and R 4b The types of R may be the same or different, and are preferably the same. 4a ,R 4b The substitution position of A is not particularly limited, and 3 and the group [-O-(A 4a O) n4a -A 5a -C(=O)-], [-O-(A 4b O) n4b -A5b It is sufficient that the substitution is made at a position other than the bonding position with --C(.dbd.O)--.

[0158] Representative examples of the third dicarboxylic acid unit (A3) include those represented by the formula (3): 3 is a direct bond or C 1-4 represents an alkylene group, A 4a and A 4b is independently C 2-6 An alkylene group is represented, and n4a and n4b each independently represent an integer of 0 to 10. A 5a and A 5b is independently C 1-8 represents an alkylene group, R 4a and R 4b each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group, and m4a and m4b each independently represent an integer of 0 to 3; Preferably, A 3 is a direct bond or C 1-2 represents an alkylene group, A 4a and A 4b is independently C 2-4 An alkylene group is represented, and n4a and n4b each independently represent an integer of 0 to 4. A 5a and A 5b is independently C 1-6 represents an alkylene group, R 4a and R 4b each independently represents a hydrocarbon group, and m4a and m4b each independently represent an integer of 0 to 2; More preferably, A 3 represents a direct bond or a methylene group, A 4a and A 4b is independently C 2-3 An alkylene group is represented, and n4a and n4b each independently represent an integer of 0 to 2. A 5a and A 5b is independently C 1-5represents an alkylene group, R 4a and R 4b each independently represents an alkyl group, and m4a and m4b each independently represent an integer of 0 to 2; Particularly preferably, A 3 indicates a direct bond, A 4a and A 4b is independently C 2-3 an alkylene group; n4a and n4b each represent 0 or 1; A 5a and A 5b is independently C 1-4 represents an alkylene group, R 4a and R 4b is independently C 1-4 represents an alkyl group, and m4a and m4b each independently represent 0 or 1.

[0159] Specific examples of the third dicarboxylic acid component (A3) forming the third dicarboxylic acid unit (A3) include bis(carboxyalkoxy)-1,1′-binaphthyl, specifically, bis(carboxy-C) such as 2,2′-bis(carboxymethoxy)-1,1′-binaphthyl and 2,2′-bis(3-carboxy-n-propyloxy)-1,1′-binaphthyl. 1-6 alkoxy)-1,1'-binaphthyl, or ester-forming derivatives thereof.

[0160] These third dicarboxylic acid units (A3) may be used alone or in combination of two or more kinds.

[0161] (A4) A fourth dicarboxylic acid unit In addition, the dicarboxylic acid unit (A) may or may not contain a fourth dicarboxylic acid unit (A4) [not belonging to the category of the first to third dicarboxylic acid units (A1) to (A3)] different from the first dicarboxylic acid unit (A1), the second dicarboxylic acid unit (A2), and the third dicarboxylic acid unit (A3), as necessary.

[0162] Examples of the fourth dicarboxylic acid unit (A4) include structural units derived from an aromatic dicarboxylic acid component (excluding the first to third dicarboxylic acid units (A1) to (A3)), an alicyclic dicarboxylic acid component, an aliphatic dicarboxylic acid component, etc.

[0163] Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, 9,9-bis(carboxyalkyl)-diarylfluorenes which may have a substituent, 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 benzene dicarboxylic acids such as 4-methylisophthalic acid; 1-4 Alkyl-benzene dicarboxylic acids and the like.

[0164] 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, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, etc.; diarylalkane dicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethane dicarboxylic acid, etc. 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 ether 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.

[0165] 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.

[0166] The 9,9-bis(carboxyalkyl)-diarylfluorene which may have a substituent includes 9,9-bis(carboxyalkyl)-diphenylfluorene which may have a substituent, 9,9-bis(carboxyalkyl)-dinaphthylfluorene which may have a substituent, etc. Examples of the substituent, including preferred embodiments, are R 1 The number of the substituents may be one or more, and when there are a plurality of the substituents, the types of the substituents may be the same or different.

[0167] Examples of the 9,9-bis(carboxyalkyl)-diphenylfluorene include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-1,8-diphenylfluorene, 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-carboxyethyl)-3,6-diphenylfluorene, 9,9-bis(2-carboxyethyl)-4,5-diphenylfluorene, and 9,9-bis(2-carboxypropyl)-2,7-diphenylfluorene. 2-6 alkyl)-diphenylfluorene.

[0168] Examples of the 9,9-bis(carboxyalkyl)-dinaphthylfluorene include 9,9-bis(carboxy C) such as 9,9-bis(2-carboxyethyl)-1,8-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-3,6-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-4,5-di(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-di(2-naphthyl)fluorene, and 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene. 2-6 alkyl)-dinaphthylfluorene and the like.

[0169] 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. 5-10 Examples 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.

[0170] Examples of the aliphatic dicarboxylic acid component include linear or branched alkane dicarboxylic acids, specifically, C alkane dicarboxylic acids such as succinic acid, adipic acid, suberic acid, sebacic acid, and decane dicarboxylic acid. 2-12 Alkane-dicarboxylic acids, etc.; linear or branched unsaturated aliphatic dicarboxylic acids, specifically, C such as maleic acid, fumaric acid, and itaconic acid 2-10 alkene-dicarboxylic acids; and ester-forming derivatives thereof.

[0171] The fourth dicarboxylic acid unit (A4) may be contained alone or in combination of two or more kinds.

[0172] Among the fourth dicarboxylic acid units (A4), aromatic dicarboxylic acid components are preferred, 9,9-bis(carboxyalkyl)-diarylfluorene or an ester-forming derivative thereof which may have a substituent is more preferred, and 9,9-bis(carboxyalkyl)-dinaphthylfluorene or an ester-forming derivative thereof which may have a substituent is even more preferred.

[0173] The proportion of the fourth dicarboxylic acid unit (A4) is, for example, 50 mol % or less, preferably 30 mol % or less, and more preferably 10 mol % or less, based on the total dicarboxylic acid units (A), and may be, for example, about 0.1 to 5 mol %, and it is particularly preferable that the fourth dicarboxylic acid unit (A4) is not substantially contained.

[0174] In particular, when the fourth dicarboxylic acid unit (A4) is 9,9-bis(carboxyalkyl)-diarylfluorene or a derivative thereof which may have a substituent, in particular 9,9-bis(carboxyalkyl)-dinaphthylfluorene or a derivative thereof which may have a substituent, the proportion of the fourth dicarboxylic acid unit (A4) is, for example, 1 to 50 mol %, preferably 3 to 30 mol %, further preferably 5 to 20 mol %, and more preferably 7 to 15 mol %, based on the total dicarboxylic acid units (A).

[0175] The ratio of the first dicarboxylic acid unit (A1) can be selected from the range of about 10 to 100 mol% based on the total dicarboxylic acid unit (A), and may be, for example, 30 mol% or more, 40 mol% or more, 50 mol% or more, 70 mol% or more, 90 mol% or more, or 100 mol% in the following stepwise manner, and more preferably, 25 to 90 mol%, 30 to 80 mol%, 35 to 70 mol%, 40 to 65 mol%, 45 to 60 mol%, or 45 to 55 mol% in the following stepwise manner. If the ratio of the first dicarboxylic acid unit (A1) is in a moderate range that is not too small, it is easy to adjust the anomalous dispersion characteristic (partial dispersion ratio θgF) to a moderately high range, and it also tends to be easy to prepare a resin that satisfies a good balance between a high refractive index or a low Abbe number, low birefringence, and high heat resistance. When the proportion of the first dicarboxylic acid unit (A1) is within a suitable range, it is easy to adjust the anomalous dispersion characteristic (partial dispersion ratio θgF) to a suitable high range by suppressing an excessive increase in the anomalous dispersion characteristic (partial dispersion ratio θgF), and it is easy to improve the moldability (productivity) by suppressing an excessive increase in the glass transition temperature Tg.

[0176] It is preferable that the dicarboxylic acid unit (A) contains at least one selected from the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3), since it is easy to achieve a well-balanced combination of moderately high anomalous dispersion characteristics (partial dispersion ratio θgF), a high refractive index (or a low Abbe number), low birefringence, high heat resistance, and high moldability (or productivity).

[0177] The total proportion of the first dicarboxylic acid unit (A1) and the second dicarboxylic acid unit (A2) relative to the total dicarboxylic acid units (A) may be, for example, 1 mol % or more, specifically about 10 to 100 mol %, and is preferably 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more in the following stepwise manner, and is particularly preferably substantially 100 mol %.

[0178] The proportion of the total amount of the first dicarboxylic acid unit (A1) and the third dicarboxylic acid unit (A3) relative to the total dicarboxylic acid units (A) may be, for example, 1 mol % or more, specifically about 10 to 100 mol %, and is preferably 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more in the following stepwise manner, and is particularly preferably substantially 100 mol %.

[0179] The total proportion of the first dicarboxylic acid unit (A1), the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3) may be, for example, 1 mol % or more, specifically, may be selected from the range of about 10 to 100 mol %, based on the total dicarboxylic acid units (A), and is preferably 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more in the following stepwise manner, and is particularly preferably substantially 100 mol %.

[0180] The ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) may be, for example, the former / latter (molar ratio) = about 1 / 99 to 100 / 0, specifically about 5 / 95 to 95 / 5, and is preferably the following stepwise ratios: 25 / 75 to 90 / 10, 30 / 70 to 80 / 20, 35 / 70 to 75 / 25, 40 / 60 to 70 / 30, 40 / 60 to 65 / 35, 45 / 55 to 60 / 40, 45 / 55 to 55 / 45. If the ratio of the second dicarboxylic acid unit (A2) is in a moderate range that is not too small, it is easy to adjust the anomalous dispersion characteristic (partial dispersion ratio θgF) to a moderately high range by suppressing an excessive increase in the anomalous dispersion characteristic, and also tends to suppress an excessive increase in the glass transition temperature Tg, thereby improving moldability (productivity). When the proportion of the second dicarboxylic acid unit (A2) is within an appropriate range that is not too high, it is easy to adjust the anomalous dispersion characteristics (partial dispersion ratio θgF) to an appropriately high range, it is easy to suppress an increase in birefringence, and it is also easy to suppress a decrease in heat resistance, and it tends to be easy to achieve a good balance between a high refractive index or a low Abbe number, low birefringence, and high heat resistance.

[0181] The ratio of the first dicarboxylic acid unit (A1) to the third dicarboxylic acid unit (A3) may be, for example, the former / latter (molar ratio)=about 10 / 90 to 100 / 0, specifically about 30 / 70 to 99 / 1, and preferably the following stepwise ratios: 50 / 50 to 95 / 5, 60 / 40 to 90 / 10, 65 / 35 to 85 / 15, and 70 / 30 to 80 / 20. When the ratio of the third dicarboxylic acid unit (A3) is in a moderate range that is not too small, it is easy to adjust the anomalous dispersion characteristic (partial dispersion ratio θgF) to a moderately high range by suppressing an excessive increase in the anomalous dispersion characteristic, and also tends to suppress an excessive increase in the glass transition temperature Tg, thereby improving moldability (productivity). When the proportion of the third dicarboxylic acid unit (A3) is within an appropriate range that is not too high, it is easy to adjust the anomalous dispersion characteristics (partial dispersion ratio θgF) to an appropriately high range, it is easy to suppress an increase in birefringence, and it is also easy to suppress a decrease in heat resistance, and it tends to be easy to achieve a good balance between a high refractive index or a low Abbe number, low birefringence, and high heat resistance.

[0182] The ratio of the first dicarboxylic acid units (A1) to the total amount of the second dicarboxylic acid units (A2) and the third dicarboxylic acid units (A3) is about 1 / 99 to 100 / 0 (molar ratio), specifically, 10 / 90 to 99 / 1, 20 / 80 to 95 / 5, and preferably the following stepwise ratios: 25 / 75 to 90 / 10, 30 / 70 to 80 / 20, 35 / 65 to 70 / 30, 40 / 60 to 65 / 35, 45 / 65 to 60 / 40, 45 / 65 to 55 / 45. When the total ratio of the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3) is within a suitable range, it is easy to adjust the anomalous dispersion characteristics (partial dispersion ratio θgF) to a suitable high range by suppressing an excessive increase, and it is easy to improve moldability (productivity) by suppressing an excessive increase in the glass transition temperature Tg. When the total ratio of the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3) is within a suitable range, it is easy to adjust the anomalous dispersion characteristics (partial dispersion ratio θgF) to a suitable high range, it is easy to suppress an increase in birefringence, and it is easy to suppress a decrease in heat resistance, and it is easy to achieve a good balance between a high refractive index or a low Abbe number, low birefringence, and high heat resistance.

[0183] The ratio of the second dicarboxylic acid unit (A2) to the third dicarboxylic acid unit (A3) may be, for example, the former / latter (molar ratio) = 0 / 100 to 100 / 0, specifically about 10 / 90 to 90 / 10, and preferably the following stepwise ratios: 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, 40 / 60 to 60 / 40, and 45 / 55 to 55 / 45. When the ratio of the second dicarboxylic acid unit (A2) is in a moderate range that is not too small, the deterioration of heat resistance tends to be easily suppressed. When the ratio of the third dicarboxylic acid unit (A3) is in a moderate range that is not too small, the excessive increase in glass transition temperature Tg tends to be easily suppressed, and moldability (productivity) tends to be easily improved.

[0184] The ratio of the total amount of the first to fourth dicarboxylic acid units (A1) to (A4) may be 100 mol% based on the total amount of the dicarboxylic acid units (A). The ratio of the dicarboxylic acid units (A) [the total amount of the first to fourth dicarboxylic acid units (A1) to (A4)] based on the total amount of the structural units of the resin (the total amount of the structural units derived from all the polymerization components constituting the resin) may be, for example, 1 mol% or more, specifically about 10 to 50 mol%, and preferably 20 to 50 mol%, 30 to 50 mol%, and 40 to 50 mol% in the following stepwise manner.

[0185] (Diol unit (B)) The resin preferably contains, in addition to the dicarboxylic acid unit (A), a diol unit (B) which is a structural unit derived from the diol component (B) as a polymerization component, and is therefore preferably a polyester resin containing the dicarboxylic acid unit (A) and the diol unit (B).

[0186] (B1) First Diol Unit The type of diol unit (B) is not particularly limited, but may or may not contain a first diol unit (B1) represented by the following formula (4) as necessary. Combining the first diol unit (B1) seems to facilitate improvement of the refractive index and heat resistance (glass transition temperature) without significantly increasing (maintaining or reducing) the birefringence.

[0187] [ka]

[0188] (In the formula, R 5 represents a substituent, m5 represents an integer of 0 to 8, Z 2a and Z 2b each independently represents an arene ring, R 6a and R 6b each independently represents a substituent; m6a and m6b each independently represent an integer of 0 or more; A 6a and A 6b each independently represents an alkylene group, and n6a and n6b each independently represent an integer of 0 or more.

[0189] In the formula (4), R 5 Examples of the substituent (non-reactive group or non-polymerizable group) represented by the formula (1) include R 1 Representative examples of R 5 Examples of the alkyl group include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, and the like, and are preferably a halogen atom, a hydrocarbon group, or a cyano group, and more preferably a hydrocarbon group such as an alkyl group or an aryl group. The alkyl group is preferably a linear or branched alkyl group, for example, a C alkyl group such as a methyl group, an ethyl group, or a t-butyl group. 1-6 Alkyl groups and C groups such as methyl groups. 1-4 The alkyl group is preferred. The aryl group is, for example, C phenyl group. 6-10 Examples of the alkyl group include an aryl group.

[0190] R 5 The number of substitutions m5 is, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0. When m5 is 2 or more, 2 or more R 5 The types of may be the same or different. In addition, when R is present in both of the two benzene rings forming the fluorene skeleton, 5When R on one benzene ring is substituted, 5 The type of R of the other benzene ring 5 The types of R may be the same or different, and are preferably the same. 5 The substitution position is not particularly limited, and may be, for example, the 2-position, the 3-position, or the 2,7-position.

[0191] Z 2a ,Z 2b Examples of the arene ring represented by the formula (1) include Z 1 The preferred arene rings are the same as those exemplified as the arene rings. 2a ,Z 2b is C 6-14 arene rings, more preferably benzene rings, naphthalene rings, biphenyl rings, etc. 6-12 arene rings, and more preferably benzene rings, naphthalene rings, etc. 6-10 Arene rings, particularly naphthalene rings, are preferred due to their high refractive index. 2a ,Z 2b Polycyclic arene rings, e.g., naphthalene rings and biphenyl rings, etc. 10-14 A polycyclic arene ring is likely to improve the refractive index, and a condensed polycyclic arene ring such as a naphthalene ring is preferred. 2a and Z 2b may be the same or different, and are preferably the same.

[0192] In addition, Z bonded to the 9-position of the fluorene ring 2a and Z 2b The substitution position of is not particularly limited, and for example, Z 2a ,Z 2b When is a benzene ring, it may be at any position, and Z 2a ,Z 2b When is a naphthalene ring, it is either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably the 2-position; Z 2a ,Z 2b When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0193] R 6a ,R 6b Examples of the substituent (non-reactive group or non-polymerizable group) represented by the formula (1) include R 1 The examples of R include the same groups as those exemplified as above, including preferred embodiments thereof. 6a ,R 6b Examples of the alkyl group include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group. Among these, preferred are groups such as an alkyl group (straight-chain or branched-chain alkyl group), a cycloalkyl group, and an aryl group, and an alkoxy group (straight-chain or branched-chain alkoxy group) [-OR h More preferably, C such as a methyl group. 1-6 C such as alkyl group and cyclohexyl group 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 C such as aryl group and methoxy group 1-4 Among them, alkyl groups and aryl groups are preferred, and C groups such as methyl groups are particularly 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 2a , Z 2b may form a ring assembly arene ring together with

[0194] R 6a ,R 6b The substitution numbers m6a and m6b of the ring Z 2a , Z 2b can be appropriately selected depending on the type of R, and may be, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0. m6a and m6b may be different from each other, but are preferably the same. In addition, when m6a is 2 or more, 2 or more R 6a may be the same or different from each other; when m6b is 2 or more, R 6bThe types of R may be the same or different. 6a and R 6b The types may be the same or different from each other.

[0195] R 6a ,R 6b The substitution position of Z is not particularly limited. 2a ,Z 2b In the above, the 9-position of the fluorene ring and the group [-O-(A 6a O) n6a -],[-O-(A 6b O) n6b -] (i.e., the ether bond (-O-) forming the main chain) is not required to be substituted at a position other than the bond position. For example, Z 2a ,Z 2b 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-).

[0196] A 6a ,A 6b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (3) include 4a ,A 4b Examples of the groups include the same groups as those exemplified as above, including preferred embodiments thereof.

[0197] Alkyleneoxy group [-(A 6a O)-],[-(A 6bThe repeat numbers (number of moles added) n6a and n6b of the formula (O)-] may each be 0 or more, and may be selected from, for example, an integer of about 0 to 15, and preferably are, in the following stepwise order, an integer of 0 to 10, an integer of 0 to 8, an integer of 0 to 6, an integer of 0 to 4, an integer of 0 to 2, and more preferably 0 or 1. In addition, when the repeat numbers n6a and n6b are each 1 or more, the polymerization reactivity is easily improved, and may each be selected from, for example, an integer of about 1 to 15, and preferably are, in the following stepwise order, an integer of 1 to 10, an integer of 1 to 8, an integer of 1 to 6, an integer of 1 to 4, an integer of 1 to 3, and more preferably 1 or 2, and particularly preferably 1. In addition, in the present specification and claims, the "repetition number (number of moles added)" may be an average value (arithmetic mean value, arithmetic mean value) or an average number of moles added. Therefore, n6a and n6b may be selected from the range of about 0 to 15, preferably in the following stepwise manner, such as 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1, or may be selected from integers of about 1 to 15, preferably in the following stepwise manner, such as 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, and 1 to 2. When n6a and n6b are in a moderate range that is not too large, there is a tendency to easily suppress a decrease in refractive index and heat resistance.

[0198] In addition, n6a and n6b may be the same or different. When n6a is 2 or more, two or more alkyleneoxy groups [-(A 6a The types of alkyleneoxy groups [-(A 6b The types of A)- may be different from each other, but are preferably the same. 6a and A 6b The types may be the same or different, but are preferably the same.

[0199] The group [-O-(A 6a O) n6a -],[-O-(A 6b O) n6b -] (i.e., the ether bond forming the main chain) of ring Z 2a ,Z 2b The substitution position for Z is not particularly limited.2a ,Z 2b The group [-O-(A 6a O) n6a -],[-O-(A 6b O) n6b -] Ring Z 2a ,Z 2b The substitution position for Z 2a ,Z 2b When 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 preferably the 4-position, of the phenyl group bonded to the 9-position of the fluorene ring. 2a ,Z 2b When Z is a naphthalene ring, it is often substituted at any one of the 5- to 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 Z is substituted with respect to this substitution position in a 1,5-position or 2,6-position relationship, particularly in a 2,6-position relationship. 2a ,Z 2b When is a ring assembly arene ring, the group [-O-(A 6a O) n6a -],[-O-(A 6b O) n6b 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 2a ,Z 2b is a biphenyl ring (or Z 2a ,Z 2b is a benzene ring, m6a and m6b are 1, R 6a ,R 6b In the case where A is a phenyl group, it is preferred that the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, and the 6-position of the biphenyl ring is bonded to a group [-O-(A 6a O) n6a -],[-O-(A 6b O) n6b -] is preferred.

[0200] Representative examples of the first diol unit (B1) include those represented by the formula (4):5 represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group, m5 represents an integer of 0 to 2, Z 2a and Z 2b is independently C 6-14 Represents an arene ring; R 6a and R 6b each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m6a and m6b each independently represent an integer of 0 to 2; A 6a and A 6b is independently C 2-6 represents an alkylene group, and n6a and n6b each independently represent an integer of 0 to 10; Preferably, R 5 represents a hydrocarbon group, m5 represents an integer of 0 to 2, Z 2a and Z 2b are independently C such as benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 Represents an arene ring; R 6a and R 6b each independently represents a hydrocarbon group; m6a and m6b each independently represent an integer of 0 to 2; A 6a and A 6b is independently C 2-4 represents an alkylene group, and n6a and n6b each independently represent an integer of 0 to 6; More preferably, R 5 is C 1-6 Alkyl groups such as alkyl groups or C 6-10 m5 represents an integer of 0 to 2; Z 2a and Z 2b are independently C such as benzene ring, naphthalene ring, etc. 6-10 Represents an arene ring; R 6a and R 6b is independently C 1-6 Alkyl groups such as alkyl groups or C 6-12m6a and m6b each independently represent an integer of 0 to 2; A 6a and A 6b is independently C 2-3 represents an alkylene group, and n6a and n6b each independently represent an integer of 0 to 2; Particularly preferably, R 5 is C 1-4 m5 represents an integer of 0 to 2; Z 2a and Z 2b are independently C such as benzene ring, naphthalene ring, etc. 6-10 Represents an arene ring; R 6a and R 6b are independently C such as methyl group 1-4 m6a and m6b each independently represent an integer of 0 to 2; A 6a and A 6b each independently represents an ethylene group or a propylene group; n6a and n6b each independently represent 0 or 1; and the like.

[0201] Specific examples of the first diol component (B1) forming the first diol unit (B1) include 9,9-bis(hydroxyaryl)fluorenes in which n6a and n6b are 0 in the formula (4) above; and 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes in which n6a and n6b are 1 or more, for example, about 1 to 10.

[0202] In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

[0203] 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.

[0204] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0205] 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 and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene and the like.

[0206] Examples of the 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene.

[0207] 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.

[0208] 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.

[0209] 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 and 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene and the like.

[0210] 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-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.

[0211] 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 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.

[0212] 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, and 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]fluorene. 2-4 alkoxy-naphthyl]fluorene and the like.

[0213] These first diol units (B1) may be used alone or in combination of two or more. Preferred first diol units (B1) are 9,9-bis[hydroxy(mono- to penta)C 2-4 Alkoxy C 6-12 aryl]fluorene; more preferably 9,9-bis[hydroxy(poly)alkoxyaryl]fluorene; 2-4 Alkoxy C 6-12 9,9-bis(hydroxyalkoxyaryl)fluorenes such as 9,9-bis[aryl]fluorene; more preferably 9,9-bis(hydroxyC 2-4 It is a structural unit derived from alkoxy-naphthyl)fluorene.

[0214] (B2) Second diol unit The diol unit (B) may or may not contain a second diol unit (B2) represented by the following formula (5). When the second diol unit (B2) is contained, it is easier to suppress an excessive increase in the anomalous dispersion characteristic (partial dispersion ratio θgF). In addition, when the second diol unit (B2) is combined, it is possible to suppress an excessive increase in the glass transition temperature Tg without significantly decreasing the refractive index (or significantly increasing the Abbe number) or significantly increasing the birefringence, so that it tends to be possible to achieve a good balance between heat resistance and moldability (or productivity) while having a high refractive index (or low Abbe number) and low birefringence.

[0215] [ka]

[0216] (In the formula, A 7 represents a direct bond or an alkylene group, A 8a and A 8b each independently represents an alkylene group; n8a and n8b each independently represent an integer of 0 or more; R 7a and R 7beach independently represents a substituent, and m7a and m7b each independently represent an integer of 0 to 6.

[0217] In the formula (5), A 7 Examples of the alkylene group represented by the formula (3) include 3 Examples of the groups include the same groups as those exemplified as above, including preferred embodiments thereof.

[0218] A 8a and A 8b Examples of the alkylene group represented by the formula (3) include 4a ,A 4b Examples of the groups include the same groups as those exemplified as above, including preferred embodiments thereof.

[0219] Alkyleneoxy group [-(A 8a O)-],[-(A 8b The range of the repeating number (number of moles added) n8a, n8b of the alkyleneoxy group [-(A 4a O)-],[-(A 4b O)-], the same ranges as those of the repeating numbers (number of moles added) n4a and n4b, including preferred embodiments thereof, are included.

[0220] The group [-O-(A 8a O) n8a -],[-O-(A 8b O) n8b The bonding position (substitution position) of the oxygen atom (ether bond) in the divalent group forming the main chain of the resin with respect to the naphthalene ring is not particularly limited. 7 When the bonding position of each of the above is taken as the 1-position, the bonding position of each of the above is preferably the 2-position.

[0221] R 7a ,R 7b Examples of the substituent (non-reactive group or non-polymerizable group) represented by the formula (1) include R 1 Examples of the groups include the same groups as those exemplified as above, including preferred embodiments thereof.

[0222] R7a ,R 7b The range of the substitution numbers m7a and m7b is, for example, R 4a ,R 4b The number of substitutions m4a and m4b, including preferred embodiments, are in the same range as above.

[0223] Representative examples of the second diol unit (B2) include those represented by the formula (5): 7 is a direct bond or C 1-4 represents an alkylene group, A 8a and A 8b is independently C 2-6 An alkylene group is represented, and n8a and n8b each independently represent an integer of 0 to 10. R 7a and R 7b each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group, and m7a and m7b each independently represent an integer of 0 to 3; Preferably, A 7 is a direct bond or C 1-2 represents an alkylene group, A 8a and A 8b is independently C 2-4 An alkylene group is represented, and n8a and n8b each independently represent an integer of 0 to 4. R 7a and R 7b each independently represents a hydrocarbon group, and m7a and m7b each independently represent an integer of 0 to 2; More preferably, A 7 represents a direct bond or a methylene group, A 8a and A 8b is independently C 2-3 An alkylene group is represented, and n8a and n8b each independently represent an integer of 0 to 2. R 7a and R 7b each independently represents an alkyl group, and m7a and m7b each independently represent an integer of 0 to 2; Particularly preferably, A 7 indicates a direct bond, A 8a and A 8b is independently C 2-3 represents an alkylene group, n8a and n8b represent 0 or 1; R 7a and R 7b is independently C 1-4 represents an alkyl group, and m7a and m7b each independently represent 0 or 1.

[0224] Specific examples of the second diol acid component (B2) forming the second diol unit (B2) include dihydroxy-1,1'-binaphthyl such as 2,2'-hydroxy-1,1'-binaphthyl, or ester-forming derivatives thereof; bis(hydroxy-1,1'-binaphthyl) such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2-3 alkoxy)-1,1'-binaphthyl, or ester-forming derivatives thereof.

[0225] These second diol units (B2) may be used alone or in combination of two or more kinds.

[0226] (B3) a third diol unit The diol unit (B) may or may not contain a third diol unit (B3) represented by the following formula (6). When the third diol unit (B3) is contained, the polymerization reaction tends to proceed efficiently and it is easy to adjust the molecular weight to a high level.

[0227] [ka]

[0228] (In the formula, A 9 represents an alkylene group, and n9 represents an integer of 1 or more.

[0229] In the formula (6), A 9Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a tetramethylene group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 1,8-octanediyl group, and a 1,10-decanediyl group. 2-12 Alkylene groups, etc., are preferably selected from the following stepwise manner: 2-10 Alkylene group, C 2-8 Alkylene group, C 2-6 Alkylene group, C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 An alkylene group is preferred, and an ethylene group is particularly preferred.

[0230] Alkyleneoxy group [-(A 9 The repeat number n9 of the alkyleneoxy group [(-A)-] may be selected from integers of about 1 to 10, for example, and is preferably an integer of 1 to 4, an integer of 1 to 3, or an integer of 1 to 2 in the following stepwise manner, with 1 being particularly preferred. The repeat number n9 may be an average value (arithmetic mean value or additive mean value) and may be selected from a range of about 1 to 10, for example, and is preferably an integer of 1 to 4, an integer of 1 to 3, or an integer of 1 to 2 in the following stepwise manner. When n9 is within a moderate range that is not too large, there is a tendency that a decrease in refractive index and heat resistance can be suppressed. When n9 is 2 or more, two or more alkyleneoxy groups [(-A 9 O-) may be different from each other, but are preferably the same.

[0231] Representative examples of the second diol unit (B3) include those represented by the formula (6): 9 is C 2-6 represents an alkylene group, and n9 represents an integer of 1 to 10; Preferably, A 9 is C 2-6 An alkylene group, and n9 is an integer of 1 to 4. More preferably, A 9 is C 2-4 represents an alkylene group, and n9 represents an integer of 1 or 2; Particularly preferably, A 9 is C 2-3 An alkylene group, n9 being 1.

[0232] Specific examples of the third diol component (B3) forming the third diol unit (B3) include alkanediols (or alkylene glycols), polyalkanediols (or polyalkylene glycols), and the like.

[0233] As the alkylene glycol, for example, there is a compound represented by the formula (6) in which n9 is 1 and A 9 C 111 corresponds to the alkylene group of the above-mentioned examples of linear or branched alkylene glycol, specifically, 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, 1,10-decanediol, etc. 2-12 Alkylene glycol and the like are examples of the alkylene group A. 9 The same applies to the corresponding

[0234] As the polyalkylene glycol, for example, in the formula (6), n9 is 2 or more, preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4; 9 Polylinear or branched alkylene glycols corresponding to the alkylene groups exemplified above, specifically di- or deca-C alkylene glycols such as diethylene glycol, dipropylene glycol, and triethylene glycol. 2-12 Alkylene glycol, etc., preferably di- or hexaC 2-6 Alkylene glycol, more preferably di- or tetra-C 2-4 Alkylene glycols are included.

[0235] These third diol units (B3) may be contained alone or in combination of two or more. Preferred third diol units (B3) include2-6 is a linear or branched alkylene glycol, such as alkylene glycol, preferably C 2-4 C alkylene glycol, more preferably ethylene glycol, propylene glycol, etc. 2-3 It is preferred that the alkylene glycol comprises units derived from alkylene glycol, particularly ethylene glycol.

[0236] (B4) Fourth diol unit The diol unit (B) may or may not contain a fourth diol unit (B4) [not belonging to the category of the first to third diol units (B1) to (B3)] different from the first diol unit (B1), the second diol unit (B2), and the third diol unit (B3), as necessary.

[0237] Examples of the fourth diol unit (B4) include structural units derived from an aromatic diol component, an alicyclic diol component, and an alkylene oxide (or alkylene carbonate, haloalkanol) adduct of these diol components.

[0238] Examples of the aromatic diol component (excluding the first diol component (B1) and the second diol (B2)) 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.

[0239] Examples of the alicyclic diol component include cycloalkane diols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; and hydrogenated products of the above aromatic diols such as hydrogenated bisphenol A.

[0240] Examples of the alkylene oxide (corresponding alkylene carbonate or 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.

[0241] These fourth diol units (B4) may be contained alone or in combination of two or more kinds.

[0242] The proportion of the fourth diol unit (B4) relative to the total diol units (B) is, for example, 50 mol % or less, preferably 30 mol % or less, and more preferably 10 mol % or less, and may be, for example, about 0.1 to 5 mol %, and it is particularly preferable that the fourth diol unit (B4) is not substantially contained.

[0243] The diol unit (B) preferably contains at least one selected from the first diol unit (B1), the second diol unit (B2) and the third diol unit (B3), and particularly preferably contains at least one selected from the first diol unit (B1) and the third diol unit (B3), from the viewpoints of facilitating improvement in heat resistance and refractive index and facilitating improvement in polymerization reactivity to obtain a high molecular weight.

[0244] The total proportion of the first diol unit (B1), the second diol unit (B2) and the third diol unit (B3) relative to the total diol units (B) may be, for example, 1 mol % or more, specifically about 10 to 100 mol %, and is preferably 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more, and particularly 100 mol %, in the following stepwise manner.

[0245] The proportion of the total amount of the first diol unit (B1) and the third diol unit (B3) relative to the total amount of the diol units (B) may be, for example, 1 mol % or more, specifically about 10 to 100 mol %, and is preferably 30 mol % or more, 50 mol % or more, 70 mol % or more, 90 mol % or more, and particularly 100 mol %, in the following stepwise manner.

[0246] The ratio of the first diol unit (B1) may be, for example, about 1 to 100 mol%, specifically about 30 to 100 mol%, based on the total diol unit (B), and is preferably 50 to 99 mol%, 70 to 98 mol%, 80 to 95 mol%, and 85 to 90 mol% in the following stepwise manner. When the ratio of the first diol unit (B1) is in a moderate range that is not too small, the heat resistance and refractive index tend to be easily improved, and when it is in a moderate range that is not too large, the decrease in molecular weight and moldability (productivity) due to the decrease in polymerization reactivity tends to be easily suppressed.

[0247] The ratio of the first diol unit (B1) and the second diol unit (B2) can be selected from the range of the former / latter (molar ratio) = 1 / 99 to 100 / 0, and may be, for example, about 10 / 90 to 100 / 0, preferably 50 / 50 to 100 / 0, more preferably 60 / 40 to 100 / 0, more preferably 70 / 30 to 100 / 0, and may be, for example, 60 / 40 to 90 / 10, preferably 70 / 30 to 80 / 20, but 100 / 0 [only the first diol unit (B1)] is particularly preferred. When the ratio of the first diol unit (B1) is not too small [the ratio of the second diol unit (B2) is not too large] in a moderate range, the heat resistance and refractive index tend to be easily improved.

[0248] The ratio of the total amount of the first diol unit (B1) and the second diol unit (B2) to the third diol unit (B3) can be selected from the range of the former / latter (molar ratio) = 0 / 100 to 100 / 0, for example, about 1 / 99 to 100 / 0, preferably 30 / 70 to 100 / 0, 50 / 50 to 99 / 1, 70 / 30 to 98 / 2, 80 / 20 to 95 / 5, 85 / 15 to 90 / 10 in the following stepwise manner. When the ratio of the total amount of the first diol unit (B1) and the second diol (B2) is not too small [the ratio of the third diol unit (B3) is not too large], it tends to be easy to improve the heat resistance and refractive index. When the proportion of the third diol unit (B3) is not too small [the proportion of the total amount of the first diol unit (B1) and the second diol unit (B2) is not too large] within a suitable range, there is a tendency that the polymerization reactivity is improved, and the molecular weight and moldability (productivity) are easily improved.

[0249] The ratio of the first diol unit (B1) to the third diol unit (B3) can be selected from the range of the former / latter (molar ratio) = 0 / 100 to 100 / 0, for example, about 1 / 99 to 100 / 0, preferably 30 / 70 to 100 / 0, 50 / 50 to 99 / 1, 70 / 30 to 98 / 2, 80 / 20 to 95 / 5, 85 / 15 to 90 / 10 in the following stepwise manner. When the ratio of the first diol unit (B1) is not too small [the ratio of the third diol unit (B3) is not too large], it tends to be easy to improve the heat resistance and refractive index. When the ratio of the third diol unit (B3) is not too small [the ratio of the first diol unit (B1) is not too large], it tends to be easy to improve the polymerization reactivity, and to improve the molecular weight and moldability (productivity).

[0250] The ratio of the total amount of the first to fourth diol units (B1) to (B4) may be 100 mol% based on the total amount of the diol units (B). The ratio of the diol units (B) [the total amount of the first to fourth diol units (B1) to (B4)] based on the total amount of the structural units of the resin (the total amount of the structural units derived from all the polymerization components constituting the resin) may be, for example, 1 mol% or more, specifically about 10 to 50 mol%, and preferably 20 to 50 mol%, 30 to 50 mol%, and 40 to 50 mol% in the following stepwise manner.

[0251] The ratio of the dicarboxylic acid units (A) to the diol units (B) in the resin is the former / latter (molar ratio)=1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and is preferably approximately equimolar.

[0252] (Carbonate unit (C)) When the resin is a polyester resin containing diol units (B), it may further contain carbonate units (C) to form a polyestercarbonate resin, if necessary.

[0253] In this specification and claims, the term "carbonate unit" refers to a structural unit derived from a carbonate bond-forming component capable of forming a carbonate bond [-OC(=O)-O-] by reaction with a diol component, etc., i.e., a carbonyl group [-C(=O)-]. In other words, a carbonate bond can be formed together with the terminal oxygen atoms of two diol units bonded adjacent to the carbonate unit (carbonyl group).

[0254] Therefore, the carbonate bond-forming component (C) may be any compound capable of forming a carbonate bond by reaction with the diol component (B). Representative examples of the carbonate bond-forming component (C) include phosgenes such as phosgene and triphosgene, and carbonate diesters such as diphenyl carbonate.

[0255] These carbonate bond forming components (C) may be used alone or in combination of two or more. Among these carbonate bond forming components (C), carbonic acid diesters such as diphenyl carbonate are preferred from the viewpoint of safety.

[0256] The ratio of the total amount of dicarboxylic acid units (A) and carbonate units (C) in the resin to the diol units (B) is the former / latter (molar ratio) = 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and is preferably almost equimolar. The ratio of dicarboxylic acid units (A) to carbonate units (C) (also referred to as A / C) (molar ratio) may be selected from the range of about A / C = 100 / 0 to 1 / 99, for example, 90 / 10 to 10 / 90, and is preferably 80 / 20 to 20 / 80, 70 / 30 to 30 / 70, and 60 / 40 to 40 / 60 in the following stepwise manner.

[0257] (Other structural units (D)) The resin does not have to contain other structural units (D) different from the dicarboxylic acid units (A), the diol units (B), and the carbonate units (C), but may contain them, if necessary, within a range that does not impair the effects of the present disclosure.

[0258] The other structural unit (D) may be, depending on the type of resin, for example, a structural unit derived from a polymerization component such as a diamine component, an aminocarboxylic acid component or a lactam component, or a diisocyanate component. In the case of a polyester-based resin, for example, examples of the structural unit (D) include a structural unit derived from a hydroxycarboxylic acid component or a corresponding lactone component, or a polyfunctional polymerization component having three or more polymerizable groups (carboxyl groups and / or hydroxyl groups).

[0259] Examples of the hydroxycarboxylic acid component include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid, aliphatic hydroxycarboxylic acids (hydroxyalkanoic acids) such as lactic acid, 3-hydroxybutyric acid, 6-hydroxyhexanoic acid, and ester-forming derivatives thereof. Examples of the corresponding lactone component include lactones corresponding to hydroxyalkanoic acids such as ε-caprolactone.

[0260] 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.

[0261] The proportion of such other structural units (D) is, for example, 50 mol% or less, preferably 0 to 30 mol%, 0 to 10 mol%, 0.01 to 5 mol%, stepwise relative to all structural units (the total amount of dicarboxylic acid units (A), diol units (B), carbonate units (C) and other structural units (D)), and it is preferable that the other structural units (D) are not substantially contained.

[0262] [Resin manufacturing method] The method for producing the resin is not particularly limited except that the dicarboxylic acid component (A) containing at least the first dicarboxylic acid component (A1) is used as a polymerization component or resin raw material, and a conventional method can be used depending on the type of resin and other polymerization components (copolymerization components), etc. For example, in the case of a polyester-based resin such as a polyester resin, the dicarboxylic acid component (A) corresponding to the above-mentioned dicarboxylic acid unit, the diol component (B) corresponding to the above-mentioned diol unit, etc., and, if necessary, the carbonate bond forming component (C) can be reacted to produce (polymerize or polycondense), and the resin 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, an interfacial polymerization method, etc.

[0263] Depending on the polymerization method, the reaction may be carried out in the presence or absence of a solvent, but if the solvent remains in the obtained resin, it may corrode the mold during molding. In addition, depending on the polymerization method, if by-products such as salts remain, it may cause the resin (or its molded product) to become cloudy, and may be defective in applications that require high transparency, such as optical components. Therefore, from the viewpoint of improving moldability (productivity) and transparency, a melt polymerization method (or a molten polymer) is preferable, which can effectively suppress the remaining or mixed-in solvents and salts.

[0264] The ratio of the dicarboxylic acid component (A) to the diol component (B) 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 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 introduction ratio. For example, the second diol component (B2) such as ethylene glycol that can be distilled from the reaction system may be used in excess of the ratio (or introduction ratio) introduced into the polyester resin.

[0265] When the carbonate bond forming component (C) is used, the ratio of the total amount of the dicarboxylic acid component (A) and the carbonate bond forming component (C) to the diol component (B) is, for example, the former / latter (molar ratio) = 1 / 1.2 to 1 / 0.8, preferably 1 / 1.1 to 1 / 0.9. The carbonate bond forming component (C) may be used in a slightly excessive amount relative to the planned introduction ratio in consideration of volatilization and decomposition during the reaction, and the carbonate bond forming component (C) may be used in an excess of, for example, 0.1 to 5 mol%, preferably 2 to 3 mol%, relative to the total amount of the dicarboxylic acid unit (A) and the carbonate unit (C) (total amount planned to be introduced into the resin).

[0266] The polymerization 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; oxides, etc., or hydrates thereof may 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 (or titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0267] 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.

[0268] 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 (or 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.

[0269] The reaction may be carried out in an atmosphere of an inert gas, such as nitrogen gas, or a rare gas such as helium or argon. The reaction may also be carried out under reduced pressure, for example, at a pressure of 1×10 2 ~1×10 4 The reaction can be carried out at a pressure of about 1 Pa. The transesterification reaction can be carried out under an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction can be carried out under reduced pressure. The reaction temperature can be selected depending on the polymerization method, and for example, the reaction temperature in the melt polymerization method is about 150 to 320°C, preferably 250 to 310°C, and more preferably 270 to 300°C.

[0270] After completion of the reaction, the produced thermoplastic resin may be separated and purified by a conventional method, for example, a separation and purification means such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination of these.

[0271] [Resin characteristics and uses] (characteristic) The resin containing the first dicarboxylic acid unit (A1) can exhibit appropriate anomalous dispersion characteristics (partial dispersion ratio θgF or ΔθgF) that are not too high, even if it has a high refractive index or a low Abbe number.

[0272] The resin has a relatively high refractive index, and the refractive index nd of the resin may be, for example, 1.58 or more at a temperature of 20° C. and a wavelength of 587.6 nm, and may be preferably in the following stepwise ranges: 1.6 or more, 1.62 or more, 1.64 or more, or about 1.65 to 1.7, and more preferably 1.66 to 1.695, 1.67 to 1.69, and 1.675 to 1.685.

[0273] The resin has a relatively low Abbe number, and the Abbe number vd of the resin at a temperature of 20° C. may be, for example, 25 or less, and preferably ranges stepwise from 22 or less, to 20 or less, to 19 or less, to 16 to 18.5, to 16.5 to 18, and to 17 to 17.5.

[0274] Generally, in the region of high refractive index or low Abbe number, the anomalous dispersion characteristic (partial dispersion ratio θgF) tends to increase, but the resin of the present disclosure exhibits moderately high (not too high, not too low) anomalous dispersion characteristic, and it is easy to effectively correct or reduce chromatic aberration even on the short wavelength side (especially blue). The partial dispersion ratio θgF value of the resin may be, for example, about 0.65 to 0.73 at a temperature of 20°C, and is preferably in the following stepwise order: 0.655 to 0.725, 0.66 to 0.72, 0.665 to 0.715, 0.67 to 0.71, 0.68 to 0.705, 0.69 to 0.7. In addition, the difference (ΔθgF value) with respect to θgF of the standard dispersion glass having the same Abbe number νd may be, for example, about 0.04 to 0.12, and preferably is in the following stepwise manner: 0.05 to 0.11, 0.06 to 0.105, 0.07 to 0.1, 0.075 to 0.095, 0.08 to 0.09. If the partial dispersion ratio θgF or ΔθgF is in a moderate range that is not too high, chromatic aberration on the short wavelength side (especially blue) tends to be more effectively reduced or corrected. If the partial dispersion ratio θgF or ΔθgF is in a moderate range that is not too low, chromatic aberration tends to be more effectively reduced or corrected.

[0275] The resin of the present disclosure can achieve a good balance between a high refractive index and low birefringence (small absolute value of birefringence), which are optical properties that are a trade-off between each other. The birefringence of a resin may be evaluated by the birefringence (birefringence when stretched three times or three-fold birefringence) of a stretched film obtained by uniaxially stretching a film formed from the resin alone at three times, as described later in the Examples. The absolute value of the birefringence when stretched three times is, for example, 0 to 200×10 at a measurement temperature of 20° C. and a wavelength of 600 nm. -4 For applications such as optical lenses, the range is preferably in the following order: 100×10 -4 Below, 80 x 10 -4 Below, 50 x 10 -4 Below, 30 x 10 -4 Below, 20 x 10 -4 The following is 10 x 10 -4 Below, 7 x 10 -4 Below, 5 x 10 -4 Below, 3 x 10 -4 Below, 1×10 -4 The lower limit of the absolute value of the birefringence when stretched 3 times may be 0 or more. However, depending on the application, for example, 1×10 -4 That's it, 10 x 10 -4 That's it, 20 x 10 -4 The above may be possible.

[0276] The resin of the present disclosure can also exhibit a moderately high glass transition temperature Tg, and can achieve a good balance between heat resistance and moldability (or productivity), which are in a trade-off relationship with each other. The glass transition temperature Tg of the resin may be, for example, about 100 to 200°C, and is preferably in the following stepwise order: 130 to 180°C, 140 to 175°C, 145 to 170°C, 150 to 168°C, and 155 to 165°C. If the Tg is in a moderate range that is not too low, discoloration (or coloring) during production and / or use due to a decrease in heat resistance tends to be easily suppressed, and deformation in a high-temperature environment after molding into a predetermined shape tends to be easily suppressed, and if the Tg is in a moderate range that is not too high, there is a tendency to easily suppress a decrease in moldability or productivity (particularly injection moldability).

[0277] The weight average molecular weight Mw of the resin may be, for example, about 5000 to 200000 in terms of standard polystyrene, and is preferably in the following stepwise order: 10000 to 100000, 20000 to 80000, 30000 to 70000, 35000 to 60000, and 40000 to 50000. When the weight average molecular weight Mw is in a moderate range that is not too low, there is a tendency for the deterioration of moldability (productivity) to be easily suppressed, and applications are less likely to be restricted.

[0278] In this specification and claims, the refractive index nd, Abbe number vd, partial dispersion ratio θgF value, ΔθgF value, birefringence when stretched 3 times, glass transition temperature Tg, and weight average molecular weight Mw can be measured by the methods described in the examples below.

[0279] The resin may be crystalline (crystalline polymer), but is preferably amorphous (amorphous polymer) because it is easier to reduce birefringence, particularly in applications such as optical lenses and other optical members.

[0280] (Resin composition and molded article thereof) The resin composition of the present disclosure may contain at least the resin of the present disclosure, and may or may not contain other components different from the resin of the present disclosure, as necessary. Examples of other components include other resins different from the resin of the present disclosure, conventional additives, and the like.

[0281] The resin different from the resin of the present disclosure may be a conventional curable resin, but is preferably a thermoplastic resin. Examples of thermoplastic resins include polyolefin resins different from those disclosed herein, specifically, linear olefin resins such as polyethylene resins and polypropylene resins, and cyclic olefin resins different from those disclosed herein; styrene resins, specifically, polystyrene (PS) such as general purpose polystyrene (GPPS) and syndiotactic polystyrene (SPS), and styrene copolymers, for example, rubber component-containing styrene resins (or rubber grafted styrene copolymers) such as MS resin, AS resin, high impact polystyrene (HIPS), ABS resin, AAS resin, ACS resin, AES resin, and MBS resin; (meth)acrylic resins, specifically, homopolymers or copolymers of (meth)acrylic monomers such as polymethyl methacrylate (PMMA); vinyl acetate resins, specifically, polyvinyl acetals such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl formal (PVF), and polyvinyl butyral (PVB); vinyl chloride resins, specifically, polyvinyl chloride (PVC), vinyl chloride- Vinyl chloride and / or vinylidene chloride homopolymers or copolymers such as vinyl acetate copolymers, vinylidene chloride-vinyl chloride copolymers, and vinylidene chloride-acrylonitrile copolymers; fluororesins, specifically, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymers (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers (PFA), ethylene-tetrafluoroethylene copolymers (ETFE), and ethylene-chlorotrifluoroethylene copolymers (ECTFE); polyester resins, specifically, polyalkylene arylate resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly 1,4-cyclohexyldimethylene terephthalate (PCT), and polyethylene naphthalate, polyarylate resins, and liquid crystalline polyesters;Polycarbonate resins (PC), specifically, bisphenol-type polycarbonate resins such as bisphenol A type; polyamide resins (PA), specifically, aliphatic polyamide resins such as polyamide 6 and polyamide 66, aromatic polyamide resins (aramid resins) such as polyphenylene isophthalamide; polyacetal resins (POM); polyphenylene ether resins (PPE); polyphenylene sulfide resins (PPS); polysulfone resins, specifically, polysulfone resins (PSF), polyethersulfone (PES), etc.; polyetherketone resins, specifically, polyetherketone resins (PEK), polyetheretherketone resins (PEEK), polyetherketoneetherketoneketone PEKEKK, etc.; phenoxy resins; polyketone resins such as aliphatic polyketone resins; cellulose derivatives, specifically cellulose esters such as nitrocellulose, cellulose acetate, cellulose acetate propionate, etc., cellulose ethers such as ethyl cellulose, etc.; thermoplastic polyimide resins, specifically polyetherimide (PEI), polyamideimide, etc.; polyethernitrile resins; thermoplastic elastomers (TPEs), specifically, for example, polystyrene-based TPEs, polyolefin-based TPEs (TPOs), polydiene-based TPEs, chlorine-based TPEs, fluorine-based TPEs, polyurethane-based TPEs (TPUs), polyester-based TPEs (TPEEs), polyamide-based TPEs (TPAs), etc.;

[0282] These other resins may be included alone or in combination of two or more. If necessary, the resin of the present disclosure may form a polymer alloy with other resins. The polymer alloy may also include a compatibilizer.

[0283] The proportion of the resin of the present disclosure relative to all resin components in the resin composition (total amount of the resin of the present disclosure and other resins) may be, for example, about 10 mass% or more, and is preferably in the following stepwise manner: 30 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, and 100 mass%.

[0284] The resin composition may contain various conventional additives, as necessary, such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant assistants, plasticizers, lubricants, stabilizers, release agents, antistatic agents, dispersants, compatibilizers, flow control agents, leveling agents, defoamers, surface modifiers, stress reducing agents, carbon materials, etc. Examples of the stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. These additives may be used alone or in combination of two or more.

[0285] The total proportion of these additives may be, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, or about 0.1 to 5 parts by mass, stepwise, relative to 100 parts by mass of the resin component in the resin composition.

[0286] The resin composition can be prepared by mixing the resin of the present disclosure and, if necessary, other components by a conventional method such as dry mixing or melt kneading, and the resin composition may be in the form of pellets or the like.

[0287] The present disclosure includes a molded article containing at least the resin of the present disclosure (or the resin composition of the present disclosure). The shape of the molded article is not particularly limited and may be selected according to the application. For example, the molded article may be in the form of a pellet, a one-dimensional structure such as a line (fiber or thread) or rod, a two-dimensional structure such as a film, sheet, or plate, a lens such as a block, a concave or convex lens, a three-dimensional structure such as a hollow (tubular or tubular), or a composite or complex shape that combines these shapes. The molded article has excellent optical properties and the like in a well-balanced manner, and can be effectively used as an optical member, particularly an optical lens.

[0288] The molded article can be produced by a conventional molding method depending on the type of resin, etc. For example, when the resin of the present disclosure is a thermoplastic resin, it can be produced by using a conventional molding method such as injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, compression molding, pressure molding, casting molding, calendar processing, and foam molding.

[0289] When molding into a lens shape, for example, the molding may be performed by compression molding, injection molding, injection compression molding, transfer molding, pressure molding, or the like.

[0290] The molded article may be a composite molded article including the resin (or resin composition) of the present disclosure and other components. The proportion of the resin composition of the present disclosure in the molded article is not particularly limited and may be, for example, about 10 to 100% by mass, or about 20 to 80% by mass. EXAMPLES

[0291] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of evaluation items and raw materials are shown below.

[0292] [Evaluation method] ( 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.

[0293] (HPLC) The HPLC (high performance or high performance liquid chromatograph) was performed using an LC-2010A HT manufactured by Shimadzu Corporation and an ODS-80TM manufactured by Tosoh Corporation as the column. The sample was dissolved in acetonitrile and measured, and the HPLC purity [area %] was calculated.

[0294] (Melting Point) Using a thermogravimetry-differential thermal analyzer (TG-DTA) ("TG-DTA8122" manufactured by Rigaku Corporation), measurements were performed under conditions of a nitrogen atmosphere, a measurement temperature of 30 to 300°C, and a heating rate of 10°C / min. From the obtained DTA chart, the peak top temperature of the endothermic peak due to melting was determined as the melting point.

[0295] (5% weight loss temperature) Using a thermogravimetry-differential thermal analyzer (TG-DTA) (Rigaku Corporation, "TG-DTA8122"), the temperature at which the sample lost 5% mass was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0296] (Refractive index nD) The refractive index nD was measured at a temperature of 25° C. and a wavelength of 589 nm (D line) using a refractometer ("RX-7000i" manufactured by Atago Co., Ltd.). The refractive index was calculated by dissolving the sample in cyclohexanone to prepare solutions with concentrations of mass%, 5 mass%, 10 mass%, and 15 mass%, and extrapolating the concentration to 100 mass% on a calibration curve (approximation line) prepared by measuring the refractive index of the obtained solutions and a concentration of 0 mass% (cyclohexanone only).

[0297] (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).

[0298] (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.

[0299] (Birefringence when stretched 3 times (3 times birefringence)) 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 strip of 10mm x 50mm, and the free end was 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).

[0300] (Refractive index nd) A test piece with a thickness of about 1 mm was molded by hot pressing the sample at 200 to 240° C. The refractive index nd of this test piece at a wavelength of 587.6 nm (d-line) was measured using a Kalnew precision refractometer (Shimadzu Device Manufacturing Co., Ltd., "KPR-2000") at a measurement temperature of 20° C. and a contact liquid with a refractive index of 1.52 as the contact liquid for the test piece.

[0301] (Abbe number νd) Using the test piece for which the refractive index nd at 587.6 nm (d-line) was measured, the refractive indices nF and nC were measured in the same manner as for the refractive index nd, except that the measurement wavelengths were changed to 486.1 nm (F-line) and 656.3 nm (C-line). The Abbe number νd was calculated from the refractive indices nF, nd, and nC at each wavelength obtained by the following formula.

[0302] νd=(nd-1) / (nF-nC)

[0303] (Partial dispersion ratio θgF) Using the test piece for which the refractive index nd at 587.6 nm (d-line) was measured, the refractive indices ng, nF, and nC were measured in the same manner as for the refractive index nd, except that the measurement wavelengths were changed to 435.8 nm (g-line), 486.1 nm (F-line), and 656.3 nm (C-line). From the refractive indices ng, nF, and nC at each wavelength obtained, the value of the partial dispersion ratio θgF was calculated by the following formula.

[0304] θgF=(ng-nF) / (nF-nC)

[0305] In addition, the ΔθgF value was calculated by the method described below. That is, when two types of optical glasses that do not exhibit anomalous dispersion, K7(νd,θgF)=(60.5,0.547) and F2(νd,θgF)=(36.3,0.583), are plotted on a graph with the Abbe number νd on the horizontal axis and the partial dispersion ratio θgF on the vertical axis, the straight line connecting the coordinates of these two standard dispersion glasses is expressed by the following formula.

[0306] θgF=-0.00149×νd+0.637

[0307] The θgF value of the standard dispersion glass obtained by substituting the Abbe number νd of the obtained resin into this formula was subtracted from the measured θgF value of the resin to calculate the ΔθgF value.

[0308] [Resin raw material] (Dicarboxylic acid component) 2-DNFDP-m: 2,7-di(2-naphthyl)-9,9-bis(2-methoxycarbonylethyl)fluorene, synthesized according to Example 1B described in International Publication No. 2020 / 213470 (Patent Document 1) 2-NFDP-m: 2-(2-naphthyl)-9,9-bis(2-methoxycarbonylethyl)fluorene, synthesized according to Example 1 (1A, 1B) described below. FDP-m: 9,9-bis(2-methoxycarbonylethyl)fluorene, 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. BINOL-butyric acid: 2,2'-bis(3-carboxy-n-propyloxy)-1,1'-binaphthyl, synthesized according to Synthesis Example 1 described below. (Diol component) BNEF: 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene BINOL-2EO: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl EG: Ethylene glycol The structural formula of each resin raw material (polymerization component) is shown below.

[0309] [ka]

[0310] [Example 1A] (Synthesis of BrFDP-m)

[0311] [ka]

[0312] In a reaction vessel containing a stirrer, a reflux tube, and a thermometer, 73.5g (300mmol) of 2-bromo-9H-fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 420g of methyl isobutyl ketone (MIBK) were added under a nitrogen atmosphere, and the mixture was heated to 50°C and dissolved. A mixed solvent of 6.3g of a 40% by mass methanol solution of trimethylbenzylammonium hydroxide ("Triton B" manufactured by Tokyo Chemical Industry Co., Ltd.) and 58g of MIBK was then added dropwise, and 56.9g (660mmol) of methyl acrylate was then added dropwise, followed by stirring at 50°C for 2 hours. After the reaction was completed, the mixture was washed twice with water, and the solvent MIBK was removed from the resulting organic layer by vacuum concentration (80°C, vacuum). Thereafter, methanol was added while maintaining the temperature at 60°C to obtain a homogeneous solution, and the temperature was gradually lowered to precipitate crystals. The obtained white crystals were 9,9-bis(2-methoxycarbonylethyl)-2-bromofluorene (BrFDP-m) represented by the above formula, and the yield was 103 g (yield: 82%, HPLC purity: 99 area %).

[0313] 1 H NMR (300MHz, CDCl3): δ(ppm)1.5-1.6(4H,t), 2.4(4H,m), 3.5(6H,s), 7.3(3H,m), 7.5(2H,d), 7.6(1H,d), 7.7(1H,m)

[0314] (Synthesis of 2-NFDP-m)

[0315] [ka]

[0316] In a reaction vessel equipped with a stirrer, reflux tube, and thermometer, 91.8 g (220 mmol) of the above BrFDP-m, 41.6 g (242 mmol) of 2-naphthylboronic acid, 1013 g of toluene, and 323.2 g of 2M sodium carbonate aqueous solution (572 mmol in terms of Na2CO3) were added and stirred, and then 25 mg (0.11 mmol) of palladium acetate and 58 mg (0.22 mmol) of triphenylphosphine were added, and the mixture was heated to 80°C under a nitrogen atmosphere and stirred for 6 hours. After confirming the disappearance of the raw materials, the aqueous layer was removed. The obtained organic layer was washed with 365 mL of ion-exchanged water three times. After draining, powdered activated carbon (Osaka Gas Chemicals Co., Ltd.'s "Tokusei Shirasagi") was added to the obtained organic layer to remove palladium, and insoluble matter was removed by filtration. The obtained organic layer was concentrated to remove 814 g of toluene, and then 200 g of isopropyl alcohol (IPA) was added, cooled to below 10°C with ice water, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain 93 g of 2-NFDP-m (yield: 91%, HPLC purity: 99.8 area%) as white crystals. 1 The H-NMR results are shown below.

[0317] 1 H-NMR (CDCl3, 300MHz): δ(ppm)1.6-1.7(4H,m), 2.5(4H,m), 3.4(6H,s), 7.4(3H,m), 7.5-7.6(2H,t), 7.7-8.0(8H,m), 8.1(1H,s)

[0318] The refractive index nD of the obtained 2-NFDP-m was 1.628, the melting point was 163°C, and the 5% weight loss temperature was 326.6°C.

[0319] [Example 1B] In Example 1 described in JP 2005-89422 A, the reaction was carried out in the same manner as described above except that methyl acrylate [37.9 g (0.44 mol)] was used instead of t-butyl acrylate, 2-bromo-9H-fluorene [49 g (0.20 mol)] was used instead of fluorene, and no purification operation was performed after the reaction was completed, to obtain a reaction mixture containing 9,9-bis(2-methoxycarbonylethyl)-2-bromofluorene (BrFDP-m). 2-NFDP-m was obtained in the same manner as described in the section (Synthesis of 2-NFDP-m) of Example 1A, except that the reaction mixture containing the obtained BrFDP-m was used instead of BrFDP-m. The obtained 2-NFDP-m was a white crystal, and the yield was 88% (total yield in two steps), and the HPLC purity was 99% or more. The refractive index nD, melting point, and 5% weight loss temperature of the obtained 2-NFDP-m were the same as those of Example 1A.

[0320] [Synthesis Example 1] In a reaction vessel equipped with a special stirrer, reflux condenser, and thermometer, 15 g of N,N-dimethylformamide (DMF), 11.4 g (58.4 mmol) of ethyl 4-bromobutyrate (Tokyo Chemical Industry Co., Ltd.), 7.3 g (25.5 mmol) of 1,1'-bi-2-naphthol (BINOL, Tokyo Chemical Industry Co., Ltd.), and 14.8 g (107 mmol) of potassium carbonate were added and stirred, and the mixture was heated to 80°C and stirred for 5 hours. After confirming the disappearance of the raw materials and intermediates by HPLC, the mixture was cooled to 50°C, and 22 g of MIBK and 30 g of ion-exchanged water were added and washed with water. Further, 18 g of ion-exchanged water was added, and the mixture was washed twice with water. Then, 20.4 g (77 mmol) of 15% by mass aqueous sodium hydroxide solution was added to the resulting organic layer of 2,2'-bis[3-(ethoxycarbonyl)-n-propoxy]-1,1'-bi-2-naphthol (or BINOL-ethyl butyrate) in MIBK, and the mixture was stirred for 3 hours at 80° C. After confirming that the ethyl ester of BINOL-ethyl butyrate had been converted to a carboxylic acid (or hydrolyzed), the mixture was cooled to 40° C. or lower, 13 g of tetrahydrofuran (THF) and 4.3 g of MIBK were added, and 8.2 g (79 mmol) of 35% by mass hydrochloric acid was added dropwise to adjust the pH to 2 or lower. The acid water (aqueous layer) was drained, and the resulting organic layer was washed six times with ion-exchanged water. The organic solvent was then removed by vacuum concentration, and IPA was added to cause crystallization. The resulting crystals were filtered to obtain 9.4 g of BINOL-butyric acid as white crystals (HPLC purity 99%, yield 80%).

[0321] [Reference example 1] In a reaction vessel, 14.77g (25mmol) of 2-DNFDP-m and 25.38g (75mmol) of FDP-m were charged as dicarboxylic acid components, 45.78g (85mmol) of BNEF and 13.35g (215mmol) of EG as diol components, 2.7mg (8μmol) of titanium (IV) tetrabutoxide as a catalyst for transesterification and polycondensation reaction, and 21.0mg (100μmol) of dibutyl phosphate as a heat stabilizer were charged, and the mixture was gradually heated to 240°C under a nitrogen gas atmosphere and stirred to carry out a transesterification reaction. After removing the alcohol component produced by the transesterification reaction, the temperature was gradually raised to 290°C and 130Pa, 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.

[0322] [Reference example 2] In a reaction vessel, 17.72 g (30 mmol) of 2-DNFDP-m and 10.15 g (30 mmol) of FDP-m were charged as dicarboxylic acid components, 27.47 g (51 mmol) of BNEF and 8.01 g (129 mmol) of EG as diol components, and 3.7 mg (11 μmol) of titanium (IV) tetrabutoxide were charged as a catalyst for transesterification and polycondensation reactions, and the mixture was gradually heated to 240 ° C. under a nitrogen gas atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, 13.7 mg (65 μmol) of dibutyl phosphate 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 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.

[0323] [Example 2] In a reaction vessel, 11.61 g (25 mmol) of 2-NFDP-m and 8.46 g (25 mmol) of FDP-m were charged as dicarboxylic acid components, 22.89 g (42.5 mmol) of BNEF and 6.67 g (107.5 mmol) of EG were charged as diol components, and 2.7 mg (8 μmol) of titanium (IV) tetrabutoxide was charged as a catalyst for transesterification and polycondensation reactions, and the mixture was gradually heated to 240 ° C. under a nitrogen gas atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, 10.5 mg (50 μmol) of dibutyl phosphate 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 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.

[0324] [Example 3] In a reaction vessel, 16.26g (35mmol) of 2-NFDP-m and 5.08g (15mmol) of FDP-m were charged as dicarboxylic acid components, 22.89g (42.5mmol) of BNEF and 6.67g (107.5mmol) of EG as diol components, and 3.1mg (9μmol) of titanium (IV) tetrabutoxide as a catalyst for transesterification and polycondensation reaction were charged, and the mixture was gradually heated to 240°C under a nitrogen gas atmosphere, stirred, and transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, 10.5mg (50μmol) of dibutyl phosphate was added as a heat stabilizer, and the temperature was gradually raised to 290°C and 130Pa, 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.

[0325] [Example 4] In a reaction vessel, 13.01g (28mmol) of 2-NFDP-m and 5.50g (12mmol) of BINOL-butyric acid were charged as dicarboxylic acid components, 19.39g (36mmol) of BNEF and 5.21g (84mmol) of EG as diol components, and 3.7mg (11μmol) of titanium (IV) tetrabutoxide as a catalyst for transesterification and polycondensation reaction were charged, and the mixture was gradually heated to 240°C under a nitrogen gas atmosphere, stirred, and transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, 9.5mg (45μmol) of dibutyl phosphate was added as a heat stabilizer, and the temperature was gradually raised to 290°C and 130Pa, 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.

[0326] [Example 5] In a reaction vessel, 13.94g (30mmol) of 2-NFDP-m, 3.38g (10mmol) of FDP-m and 4.59g (10mmol) of BINOL-butyric acid were charged as dicarboxylic acid components, 22.89g (42.5mmol) of BNEF and 6.67g (107.5mmol) of EG as diol components, and 4.4mg (13μmol) of titanium (IV) tetrabutoxide as a catalyst for transesterification and polycondensation reaction were charged, and the mixture was gradually heated to 240°C under a nitrogen gas atmosphere, stirred, and transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, 10.5mg (50μmol) of dibutyl phosphate was added as a heat stabilizer, and the temperature was gradually raised to 290°C and 130Pa, 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.

[0327] [Example 6] In a reaction vessel, 14.87g (32mmol) of 2-NFDP-m and 3.67g (8mmol) of BINOL-butyric acid were charged as dicarboxylic acid components, 19.39g (36mmol) of BNEF and 5.21g (84mmol) of EG as diol components, and 3.1mg (9μmol) of titanium (IV) tetrabutoxide were charged as a catalyst for transesterification and polycondensation reactions, and the mixture was gradually heated to 240°C under a nitrogen gas atmosphere, stirred, and transesterification was performed. After removing the alcohol component generated by the transesterification reaction, 9.5mg (45μmol) of dibutyl phosphate was added as a heat stabilizer, and the temperature was gradually raised to 290°C and 130Pa, 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.

[0328] [Example 7] In a reaction vessel, 12.54g (27mmol) of 2-NFDP-m and 6.09g (18mmol) of FDP-m were charged as dicarboxylic acid components, 14.54g (27mmol) of BNEF, 3.37g (9mmol) of BINOL-2EO and 6.14g (99mmol) of EG were charged as diol components, and 3.7mg (11μmol) of titanium (IV) tetrabutoxide was charged as a catalyst for transesterification and polycondensation reactions, and the mixture was gradually heated to 240°C under a nitrogen gas atmosphere and stirred to carry out transesterification. After removing the alcohol component produced by the transesterification reaction, 9.5mg (45μmol) of dibutyl phosphate was added as a heat stabilizer, and the temperature was gradually raised to 290°C and 130Pa, 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.

[0329] [Example 8] In a reaction vessel, 8.36g (18mmol) of 2-NFDP-m, 2.66g (4.5mmol) of 2-DNFDP-m and 10.32g (22.5mmol) of BINOL-butyric acid were charged as dicarboxylic acid components, 19.39g (36mmol) of BNEF and 6.14g (99mmol) of EG as diol components, and 3.4mg (10μmol) of titanium (IV) tetrabutoxide as a catalyst for transesterification and polycondensation reaction was charged, and the mixture was gradually heated to 240°C under a nitrogen gas atmosphere, stirred, and transesterification reaction was carried out. After removing the alcohol component produced by the transesterification reaction, 9.5mg (45μmol) of dibutyl phosphate was added as a heat stabilizer, and the temperature was gradually raised to 290°C and 130Pa, 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.

[0330] The polymer composition ratios (proportions (molar ratios) of constituent units derived from each polymerization component used in the preparation) of the polyester resins obtained in the Examples and Reference Examples and the evaluation results of each physical property value are shown in the following table. 1 The peaks in the H-NMR spectrum overlapped, making it difficult to calculate the exact polymer composition ratio. However, since there were no highly volatile monomer components other than EG, and no sublimation of by-products was confirmed during polymerization, it is estimated to be within the range shown in the table below based on the polymerization conditions such as the feed ratio and reaction method.

[0331] [Table 1]

[0332] As is clear from the results in Table 1, even when the refractive index nd was high or the Abbe number νd was low, the partial dispersion ratios θgF and ΔθgF were in a moderately large range in the Examples having dicarboxylic acid units (2-NFDP-m units) derived from 2-NFDP-m, as compared with the Reference Examples. This is particularly evident from a comparison between Reference Examples 1 and 2 and Example 2.

[0333] In Reference Examples 1-2 and Example 2, the dicarboxylic acid units are all composed of FDP-based dicarboxylic acid units, i.e., units derived from FDP-m, 2-NFDP-m in which one 2-naphthyl group is bonded to the fluorene skeleton of FDP-m, and / or 2-DNFDP-m in which two 2-naphthyl groups are bonded, and the proportions of each are different.

[0334] In Reference Example 2, the composition is 50 FDP-m units and 50 2-DNFDP-m units per 100 FDP-based dicarboxylic acid units. In other words, 100 (=50×2) 2-naphthyl groups are bonded to the fluorene skeleton per 100 FDP-based dicarboxylic acid units. Reference Example 1 corresponds to an example in which half of the 2-DNFDP-m units are replaced with FDP-m units, based on Reference Example 2, so 50 (=25×2) 2-naphthyl groups are bonded to the fluorene skeleton per 100 FDP-based dicarboxylic acid units. On the other hand, Example 2 corresponds to an example in which all 2-DNFDP-m units are replaced with 2-NFDP-m units, based on Reference Example 2, so 50 (=50×1) 2-naphthyl groups are bonded to the fluorene skeleton per 100 FDP-based dicarboxylic acid units. In other words, Reference Example 1 and Example 2 have the same number of 2-naphthyl groups bonded to the fluorene skeleton of the FDP-based dicarboxylic acid unit (half that of Reference Example 2), but can be considered to be isomers with different ways in which the 2-naphthyl groups are bonded.

[0335] Considering this point, the θgF value and ΔθgF value are considerably high in Reference Example 2, probably because the number of 2-naphthyl groups bonded to the fluorene skeleton is the largest. In Reference Example 1, the number of 2-naphthyl groups is half that of Reference Example 2, so the θgF value and ΔθgF value are lower than those of Reference Example 2, but are still on the higher side. On the other hand, unexpectedly, in Example 2, the θgF value and ΔθgF value are significantly lower than those of Reference Example 1, which has the same number of 2-naphthyl groups, and are in a moderate range that is neither too high nor too low. Such a tendency in Example 2 having 2-NFDP-m units was unexpected, even considering that the refractive index nd and Abbe number νd do not change significantly between Reference Example 1 and Example 2.

[0336] As described above, the embodiments show a moderately large partial dispersion characteristic, which makes it easy to correct chromatic aberration on the short wavelength side (especially blue), and can be effectively used for optical lenses, particularly optical lenses that combine multiple lenses to reduce or correct chromatic aberration.

[0337] In addition, the examples not only had moderately high partial dispersion characteristics, but also had a high refractive index nd or a low Abbe number νd and low birefringence, and also had a glass transition temperature Tg that could achieve both heat resistance and moldability. Among the examples, examples 2 and 5 are preferred, and example 2 is even more preferred, in that they can satisfy these characteristics in a well-balanced manner and have particularly good partial dispersion characteristics. [Industrial Applicability]

[0338] The dicarboxylic acid or derivative thereof of the present disclosure can be effectively used as a resin raw material or polymerization component, or as an additive (or resin additive) such as a refractive index improver or a heat resistance improver.

[0339] The resin of the present disclosure may also be used in various applications, such as coating agents or coating films, specifically, protective films for paints, inks, electronic devices, liquid crystal members, and the like; adhesives, pressure sensitive adhesives; resin fillers; electric and electronic materials or electric and electronic parts (electrical and electronic devices), specifically, antistatic agents, carrier transport agents, light emitting bodies, organic photoreceptors, thermosensitive recording materials, photochromic materials, holographic 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.

[0340] The resin of the present disclosure can be particularly effectively used as an optical member, such as an optical lens for glasses or a camera lens, a prism, a hologram, or an optical fiber.

[0341] Examples of optical lenses include glasses lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrating lenses, objective lenses, and rod lens arrays, and the optical lenses may be particularly suitable for use as camera lenses. Representative devices or equipment in which such optical lenses are mounted include devices with camera functions (particularly small devices or mobile devices) such as smartphones, mobile phones, digital cameras, tablet terminals, and personal computers (PCs); and in-vehicle cameras such as drive recorders and backup cameras (rear cameras).

Claims

1. A dicarboxylic acid represented by the following formula (1) or a derivative thereof: 【Chemistry 1】 (In the formula, Z １ indicates an arene ring, R １ represents a substituent, m1 represents an integer of 0 or more, k represents an integer of 1 to 4; R ２ａ and R ２ｂ each independently represents a non-aromatic substituent; m2a represents an integer of 0 to 3; m2b represents an integer of 0 to 4; k+m2a is 4 or less, A １ａ and A １ｂ each independently represents an alkylene group.

2. In the formula (1), Z １ is C ６－１４ Represents an arene ring; R １ represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group; m1 represents an integer of 0 to 4; k represents an integer of 1 to 2; R ２ａ and R ２ｂ each independently represents an aliphatic hydrocarbon group, a halogen atom, or a cyano group; m2a represents an integer of 0 to 2; m2b represents an integer of 0 to 2; A １ａ and A １ｂ is independent and C １－６ 2. A dicarboxylic acid or derivative thereof according to claim 1, which exhibits an alkylene group.

3. A compound having a fluorene skeleton and Z １ 3. The method for producing a dicarboxylic acid or a derivative thereof according to claim 1, further comprising a coupling step of carrying out a coupling reaction with a compound having an arene ring skeleton corresponding to the formula:

4. A resin using a dicarboxylic acid component as a resin raw material, wherein a dicarboxylic acid unit (A) which is a structural unit derived from the dicarboxylic acid component contains at least a first dicarboxylic acid unit (A1) represented by the following formula (1P): 【Chemistry 2】 [In the formula, Z １ , R １ , m1, k, R ２ａ and R ２ｂ , m2a and m2b, k + m2a, and A １ａ and A １ｂ are the same as formula (1) in claim 1.

5. 5. The resin according to claim 4, wherein the proportion of the first dicarboxylic acid units (A1) is 30 mol % or more based on the total dicarboxylic acid units (A).

6. The resin according to claim 4 or 5, wherein the dicarboxylic acid unit (A) comprises at least one selected from a second dicarboxylic acid unit (A2) represented by the following formula (2) and a third dicarboxylic acid unit (A3) represented by the following formula (3). 【Chemistry 3】 (In the formula, R ３ represents a non-aromatic substituent; m3 represents an integer of 0 to 8; A ２ａ and A ２ｂ each independently represents an alkylene group. 【Chemistry 4】 (In the formula, A ３ represents a direct bond or an alkylene group, A ４ａ and A ４ｂ each independently represents an alkylene group; n4a and n4b each independently represent an integer of 0 or more; A ５ａ and A ５ｂ each independently represents an alkylene group; R ４ａ and R ４ｂ each independently represents a substituent, and m4a and m4b each independently represent an integer of 0 to 6.

7. In the formula (2), R ３ represents an aliphatic hydrocarbon group, a halogen atom or a cyano group, m3 represents an integer of 0 to 2, A ２ａ and A ２ｂ is independent and C １－６ represents an alkylene group, In the formula (3), A ３ is a direct bond or C １－４ represents an alkylene group, A ４ａ and A ４ｂ is independent and C ２－６ An alkylene group is represented, and n4a and n4b each independently represent an integer of 0 to 10. A ５ａ and A ５ｂ is independent and C １－８ represents an alkylene group, R ４ａ and R ４ｂ The resin according to claim 6, wherein m4a and m4b independently represent an integer of 0 to 3.

8. The resin according to claim 6, wherein a ratio of the first dicarboxylic acid unit (A1) to the total amount of the second dicarboxylic acid unit (A2) and the third dicarboxylic acid unit (A3) is the former / latter (molar ratio)=30 / 70 to 80 / 20.

9. The resin raw material is a polyester-based resin containing a diol component, and the diol unit (B) which is a structural unit derived from the diol component includes at least one selected from a first diol unit (B1) represented by the following formula (4), a second diol unit (B2) represented by the following formula (5), and a third diol unit (B3) represented by the following formula (6). 【Chemistry 5】 (In the formula, R ５ represents a substituent, m5 represents an integer of 0 to 8, Z ２ａ and Z ２ｂ each independently represents an arene ring, R ６ａ and R ６ｂ each independently represents a substituent; m6a and m6b each independently represent an integer of 0 or more; A ６ａ and A ６ｂ each independently represents an alkylene group, and n6a and n6b each independently represent an integer of 0 or more. 【Chemistry 6】 (In the formula, A ７ represents a direct bond or an alkylene group, A ８ａ and A ８ｂ each independently represents an alkylene group; n8a and n8b each independently represent an integer of 0 or more; R ７ａ and R ７ｂ each independently represents a substituent, and m7a and m7b each independently represent an integer of 0 to 6. 【Chemistry 7】 (In the formula, A ９ represents an alkylene group, and n9 represents an integer of 1 or more.

10. In the formula (4), R ５ represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group or a substituted amino group; m5 represents an integer of 0 to 2; Z ２ａ and Z ２ｂ is independent and C ６－１４ Represents an arene ring; R ６ａ and R ６ｂ each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m6a and m6b each independently represent an integer of 0 to 2; A ６ａ and A ６ｂ is independent and C ２－６ n6a and n6b each independently represent an integer of 0 to 10; In the formula (5), A ７ is a direct bond or C １－４ represents an alkylene group, A ８ａ and A ８ｂ is independent and C ２－６ represents an alkylene group; n8a and n8b each independently represent an integer of 0 to 10; R ７ａ and R ７ｂ each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m7a and m7b each independently represent an integer of 0 to 3; In the formula (6), A ９ is C ２－６ The resin according to claim 9, wherein n9 is an alkylene group and n9 is an integer of 1 to 10.

11. the total amount of the first diol unit (B1), the second diol unit (B2) and the third diol unit (B3) is 30 mol % or more based on the total amount of the diol units (B); The resin according to claim 9, wherein a ratio of the total amount of the first diol unit (B1) and the second diol unit (B2) to the third diol unit (B3) is the former / latter (molar ratio)=50 / 50 to 99 / 1.

12. The refractive index nd is 1.58 or more, The Abbe number νd is 25 or less, The resin according to claim 4 or 5, wherein the partial dispersion ratio θgF is 0.655 to 0.

725.

13. The weight average molecular weight Mw is 10,000 to 100,000; The glass transition temperature Tg is 130 to 180° C. The absolute value of birefringence of a stretched film uniaxially stretched under the conditions of a stretching temperature (glass transition temperature Tg+10) ° C., a stretching speed of 25 mm / min, and a stretching ratio of 3 times is 100 × 10 at a wavelength of 600 nm. －４ 6. The resin of claim 4 or 5, wherein:

14. A method for producing the resin according to claim 4 or 5, comprising polymerizing a polymerization component containing at least a first dicarboxylic acid component corresponding to the first dicarboxylic acid unit (A1).

15. A molded article comprising the resin according to claim 4 or 5.

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

17. The molded article according to claim 15, which is an optical lens.

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