Thermoplastic resin, optical film made of the same, diol compound, diester compound

Abstract

To provide a resin that has reverse wavelength dispersibility and expresses high orientation properties, an optical film obtained by using the same, and a diol compound and a diester compound used for the production of the resin.SOLUTION: A thermoplastic resin has a structural unit represented by formula (1). In formula (1), A1-A8 each independently show C or N, where at least one of them is N. R1-R8 each independently are H, an alkyl group, a heteroaryl group, etc. R9-R10 each independently are a direct bond or an optionally substituted alkylene group. X is O, C=O, or an amino group. n shows an integer value of 0-5.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a resin excellent in various properties such as optical properties, heat resistance, and moldability, as well as an optical film obtained using the same, and a diol compound and a diester compound used in producing the resin. [Background technology]

[0002] In recent years, there has been an increasing demand for optical transparent resins used in optical systems such as optical lenses, optical films, and optical recording media. In particular, the spread of thin flat panel displays (FPDs) such as liquid crystal displays and organic electroluminescence displays has been remarkable, and various optical films have been developed and used to improve display quality, such as by improving contrast and color, widening the viewing angle, and preventing external light reflection.

[0003] In organic EL displays, quarter-wave plates are used to prevent reflection of external light. In order to suppress coloring and enable a clean black display, the retardation film used in quarter-wave plates is required to have broadband wavelength dispersion characteristics (reverse wavelength dispersion) that can obtain ideal retardation characteristics at each wavelength in the visible range. As an example of a corresponding example, it has been disclosed that a broadband retardation film can be obtained by laminating two types of retardation films with different wavelength dispersions of birefringence so that their slow axes are perpendicular to each other (Patent Document 1). Also, a method has been disclosed in which a 1 / 2 wavelength plate and a 1 / 4 wavelength plate are laminated so that their slow axes are arranged in a specific manner (Patent Document 2). Furthermore, a broadband retardation film made of cellulose acetate having a specific degree of acetylation (Patent Document 3) and a retardation film made of a polycarbonate copolymer containing a bisphenol structure having a fluorene ring in the side chain and exhibiting reverse wavelength dispersion in which the retardation decreases as the wavelength becomes shorter (Patent Document 4).

[0004] In recent years, many resins having the above-mentioned fluorene ring in the side chain have been reported, and they have been proposed as useful materials for optical applications, taking advantage of the optical properties and heat resistance derived from the fluorene ring. These resins often use 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, which are relatively easily available monomers (e.g., Patent Documents 5 and 6).

[0005] Furthermore, resins having new structures have also been developed. Patent Document 7 discloses a diamine compound having a fluorene ring in the side chain, and further describes a stretched film of a polyimide resin using the same. Patent Document 8 discloses a polycarbonate resin using a fluorene compound that does not contain an aromatic ring on the main chain. Patent Document 9 discloses a dihydroxy compound or a diester compound having two fluorene rings in the same molecule, and further describes a stretched film of a polycarbonate resin or a polyester resin using the same. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 5-27118 [Patent Document 2] Japanese Patent Application Publication No. 10-68816 [Patent Document 3] JP 2000-137116 A [Patent Document 4] Patent No. 3325560 [Patent Document 5] Patent No. 5119250 [Patent Document 6] Patent No. 5204200 [Patent Document 7] JP 2008-112124 A [Patent Document 8] JP 2008-222965 A [Patent Document 9] JP 2015-25111 A Summary of the Invention [Problem to be solved by the invention]

[0007] The development of the FPD field is remarkable, and there is a demand for further improvement in the optical performance of retardation films and for the film to be made thinner. In addition, there is a demand for cost reduction of materials and improvement in productivity in each process such as film formation, stretching, lamination, etc. Accordingly, retardation films are required to have various characteristics. For example, materials used for retardation films are required to have the necessary wavelength dispersion while also having various characteristics such as low photoelastic coefficient, high heat resistance, melt processability, and mechanical strength, and furthermore, materials that have a large intrinsic birefringence, excellent flexibility and stretchability, and can obtain a high degree of molecular orientation by stretching are required.

[0008] However, the method of laminating retardation films as in Patent Document 1 and Patent Document 2 results in a thick polarizing plate. In addition, each retardation film must be laminated so that the slow axis is arranged in a specific manner, which causes a problem of deterioration in productivity and yield of the polarizing plate. The retardation films in Patent Document 3 and Patent Document 4 have reverse wavelength dispersion properties, and a single film can provide broadband retardation characteristics, but the cellulose acetate in Patent Document 3 has insufficient heat resistance and also has a problem of image spots caused by dimensional deformation due to moisture absorption.

[0009] It is known that the retardation films made of polycarbonate resins having fluorene rings described in Patent Documents 4 to 6 are useful as retardation films exhibiting reverse wavelength dispersion properties and circular polarizing plates for preventing external light reflection in image display devices. However, the present inventors have found that the resins using 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are difficult to stretch to obtain a high degree of orientation because the film is brittle, and that the resins using 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene have relatively good stretchability, but have a somewhat high photoelastic coefficient and poor reliability at high temperatures.

[0010] As a means of improving various properties, it is possible to change the copolymerization components or adjust the ratio, but 9,9-bis(4-hydroxy-3-methylphenyl)fluorene has a property that the resin becomes brittle while being very heat resistant, and it was difficult to improve the flexibility of the resin while maintaining a moderate heat resistance. In addition, in the case of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, in order to express the desired reverse wavelength dispersion, it is necessary to contain these monomer components at about 50 to 70% by weight, and the degree of freedom of molecular design by copolymerization is low, making it difficult to achieve both properties such as heat resistance and mechanical strength and optical properties.

[0011] Furthermore, the resin described in Patent Document 8 is insufficient in properties such as reverse wavelength dispersion, photoelastic coefficient, and heat resistance. The resin described in Patent Document 9 has a low photoelastic coefficient and high orientation, but in recent years, there has been a demand for a resin that exhibits even higher orientation and allows for thinner members. An object of the present disclosure is to solve the above-mentioned problems and to provide a resin excellent in various characteristics such as optical properties, heat resistance, and moldability, in particular a resin having reverse wavelength dispersion and exhibiting high orientation, as well as an optical film obtained using the same, and a diol compound and a diester compound used in the production of the resin. [Means for solving the problem]

[0012] The present inventors conducted intensive research to solve the above problems, and as a result, discovered that a resin containing a specific structural unit exhibits excellent properties, thereby completing the present disclosure.

[0013] [1] A thermoplastic resin having a structural unit represented by the following formula (1): [ka]

[0014] (1) In the formula, A 1 ~A 8Each independently represents =CH- or =N-. 1 ~A 8 At least one of the groups contains =N-. 1 ~R 8 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl or ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. 1 ~R 8 At least two adjacent groups among R may be bonded to each other to form a ring. 9 and R 10 each independently represents a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. X is an oxygen atom, a carbonyl group, or an amino group which may be substituted, and n is an integer value of 0 to 5.

[0015] [2] The thermoplastic resin according to [1], preferably containing 1% by weight or more and 70% by weight or less of the structural unit represented by the formula (1).

[0016] [3] Preferably, the absolute value of the photoelastic coefficient is 20×10 -12 Pa -1 The thermoplastic resin according to [1] or [2] below.

[0017] [4] The thermoplastic resin according to any one of [1] to [3], preferably having a glass transition temperature of 110° C. or higher and 160° C. or lower.

[0018] [5] Preferably, the thermoplastic resin according to any one of [1] to [4] is at least one selected from the group consisting of polycarbonate, polyester, and polyester carbonate.

[0019] [6] Preferably, the thermoplastic resin according to any one of [1] to [5] further contains at least one of a structural unit represented by the following formula (10) and a structural unit represented by the following formula (11): [ka] [ka]

[0020] [7] The thermoplastic resin according to any one of [1] to [6], wherein the structural unit represented by the formula (1) is at least one selected from the group consisting of the following formulas (V-1), (V-2), and (V-3): [ka] [ka] [ka]

[0021] [8] A transparent film containing the resin according to any one of [1] to [7].

[0022] [9][8] A retardation film in which the transparent film is stretched in at least one direction.

[0023]

[10] Preferably, the retardation film according to [9], wherein the ratio (R450 / R550) of the retardation at a wavelength of 450 nm (R450) to the retardation at a wavelength of 550 nm (R550) satisfies the following formula (I): 0.50 ≦ R450 / R550 ≦ 1.02 (I)

[0024]

[11] A circularly polarizing plate comprising the retardation film according to [9] or

[10] .

[0025]

[12] A diol compound represented by the following general formula (7): [ka] (7) In the formula, A 1 ~A 8 Each independently represents =CH- or =N-. 1 ~A 8 At least one of the groups contains =N-. 1 ~R 8 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl or ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. 1 ~R 8 At least two adjacent groups among R may be bonded to each other to form a ring. 9 and R 10 each independently represents a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms; n represents an integer value of 0 to 5.

[0026]

[13] Preferably, the formula (7) is at least one of the following formula (W-1) and the following formula (W-2): [ka] [ka]

[0027]

[14] A diester compound represented by the following general formula (8). [ka] (8) In the formula, A 1 ~A 8Each independently represents =CH- or =N-. 1 ~A 8 At least one of the groups contains =N-. 1 ~R 8 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl group or ethynyl group having 2 to 10 carbon atoms, R is a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. 1 ~R 8 At least two adjacent groups among R may be bonded to each other to form a ring. 9 and R 10 R each independently represents a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. 11 and R 12 R is a hydrogen atom, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms. 11 and R 12 may be the same or different, and n represents an integer value of 0 to 5.

[0028]

[15] Preferably, the formula (8) is at least one of the following formula (X-1) and the following formula (X-2): [ka] [ka] Effect of the Invention

[0029] The resin of the present disclosure has an excellent balance of various properties such as optical properties, heat resistance, and moldability. Therefore, the resin of the present disclosure can be suitably used for optical films such as retardation films. It can be particularly suitably used for ¼ wavelength plates and ½ wavelength plates that require broadband properties. Furthermore, the resin of the present disclosure has excellent orientation properties, so the thickness of the optical film can be made thinner. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] The embodiment of the present disclosure will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiment of the present disclosure, and the present disclosure is not limited to the following content as long as it does not exceed the gist of the disclosure. In this disclosure, the term "structural unit" refers to a partial structure sandwiched between adjacent linking groups in a polymer, and a partial structure sandwiched between a polymerizable reactive group present at the end portion of a polymer and a linking group adjacent to the polymerizable reactive group. In this disclosure, the term "repeating structural unit" refers to a structural unit including the structural unit and a linking group adjacent to it.

[0031] The resin of the present disclosure is a thermoplastic resin having a structural unit represented by the following formula (1): In this specification, the structural unit represented by formula (1) may be referred to as "structural unit (a)".

[0032] [ka]

[0033] (1) In the formula, A 1 ~A 8 Each independently represents =CH- or =N-. 1 ~A 8 At least one of the groups contains =N-. 1 ~R 8are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl group having 2 to 10 carbon atoms, an optionally substituted ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. 1 ~R 8 At least two adjacent groups among R may be bonded to each other to form a ring. 9 and R 10 each independently represents a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. X is an oxygen atom, a carbonyl group, or an amino group which may be substituted, and n is an integer value of 0 to 5.

[0034] [Structural unit (a)] In structural unit (a), A 1 ~A 8 each independently represents =CH- or =N-; A 1 ~A 8 At least one of the rings is an azafluorene ring containing =N-. 1 ~A 8 The number of nitrogen atoms contained in A is preferably 2 or less, and more preferably 1. 1 ~A 8 By containing nitrogen atoms, it becomes possible to develop high intrinsic birefringence and develop high orientation (birefringence) by stretching, particularly when the resin of the present disclosure is used as a reverse wavelength dispersion retardation film. On the other hand, if the number of nitrogen atoms is too large, the water absorption rate of the resin of the present disclosure containing the structural unit (a) becomes high, and the dimensional stability of the molded product may deteriorate. A 1 ~A 8 The position of =N- in A is not particularly limited. 1 , A 4 , A5 , A 8 It is preferred that at least one of the groups consisting of is =N-; 4 and A 5 It is more preferable that at least one of the groups is =N-. In this case, it is possible to develop a higher intrinsic birefringence, particularly when the resin of the present disclosure is used as a reverse wavelength dispersion retardation film.

[0035] In structural unit (a), R 1 ~R 8 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl group having 2 to 10 carbon atoms, an optionally substituted ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. 1 ~R 8 At least two adjacent groups among these may be bonded to each other to form a ring.

[0036] R 1 ~R 8Specific structures of are not limited to these, but are listed below. Examples of the alkyl group having 1 to 10 carbon atoms which may be substituted include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-decyl; branched alkyl groups such as isopropyl, 2-methylpropyl, 2,2-dimethylpropyl, and 2-ethylhexyl; and cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl. The number of carbon atoms in the alkyl group having 1 to 10 carbon atoms which may be substituted is preferably 4 or less, and more preferably 2 or less. Within this range, steric hindrance between azafluorene rings is unlikely to occur, and desired optical properties derived from the azafluorene ring tend to be obtained.

[0037] Examples of the substituent that the alkyl group may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamino group, etc.), a nitro group, a cyano group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an alkoxy group having 1 to 10 carbon atoms (e Examples of the aryl group include alkyl groups (e.g., methyl, ethyl, isopropyl, etc.), alkoxy groups having 1 to 10 carbon atoms (e.g., methoxy, ethoxy, etc.), acyl groups having 1 to 10 carbon atoms (e.g., acetyl, benzoyl, etc.), acylamino groups having 1 to 10 carbon atoms (e.g., acetamide, benzoylamide, etc.), aryl groups having 6 to 11 carbon atoms (e.g., phenyl, naphthyl, etc.) which may have at least one substituent selected from the group consisting of nitro and cyano groups. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, unsubstituted groups are preferred.

[0038] Examples of the optionally substituted aryl group having 6 to 11 carbon atoms include aryl groups such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The number of carbon atoms in the optionally substituted aryl group having 6 to 11 carbon atoms is preferably 8 or less, and more preferably 7 or less. When the number is within this range, steric hindrance between the azafluorene rings is unlikely to occur, and desired optical properties derived from the azafluorene rings tend to be obtained.

[0039] Examples of the substituent that the aryl group may have include an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.); a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, Examples of the substituent include an aryl group having 6 to 11 carbon atoms (e.g., a phenyl group, a naphthyl group, etc.) which may have at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.), ... alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, non-substitution is preferable.

[0040] Examples of the optionally substituted heteroaryl group having 3 to 10 carbon atoms include heteroaryl groups such as an imidazoyl group, a 2-pyridyl group, a 2-thienyl group, and a 2-furyl group. The number of carbon atoms in the optionally substituted heteroaryl group having 3 to 10 carbon atoms is preferably 8 or less, and more preferably 6 or less. When the number is within this range, steric hindrance between the azafluorene rings is unlikely to occur, and desired optical properties derived from the azafluorene rings tend to be obtained.

[0041] Examples of the substituent that the heteroaryl group may have include an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.); a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); Examples of the substituent include an aryl group having 6 to 11 carbon atoms (e.g., a phenyl group, a naphthyl group, etc.) which may have at least one substituent selected from the group consisting of a fluorine atom, an iodine atom), an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, non-substitution is preferable.

[0042] Examples of the optionally substituted acyl group having 1 to 10 carbon atoms include aliphatic acyl groups such as formyl, acetyl, propionyl, 2-methylpropionyl, 2,2-dimethylpropionyl, and 2-ethylhexanoyl; and aromatic acyl groups such as benzoyl, 1-naphthylcarbonyl, 2-naphthylcarbonyl, and 2-furylcarbonyl. The number of carbon atoms in the optionally substituted acyl group having 1 to 10 carbon atoms is preferably 4 or less, and more preferably 2 or less. Within this range, steric hindrance between azafluorene rings is unlikely to occur, and desired optical properties derived from the azafluorene ring tend to be obtained.

[0043] Examples of the substituent that the acyl group may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an aryl group having 1 to 1 carbon atoms (e.g., a phenyl group ... Examples of the substituent include an alkyl group having 0 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), an aryl group having 6 to 11 carbon atoms (e.g., a phenyl group, a naphthyl group, etc.) which may have at least one substituent selected from the group consisting of a nitro group, a cyano group, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, it is preferable that the substituent is unsubstituted.

[0044] Examples of the optionally substituted alkoxy group having 1 to 10 carbon atoms include alkoxy groups such as a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group; and acyloxy groups such as an acetoxy group. The number of carbon atoms in the optionally substituted alkoxy group having 1 to 10 carbon atoms is preferably 4 or less, and more preferably 2 or less. When within this range, steric hindrance between the azafluorene rings is unlikely to occur, and desired optical properties derived from the azafluorene ring tend to be obtained.

[0045] Examples of the substituent that the alkoxy group may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), Examples of the substituent include alkyl groups (e.g., methyl, ethyl, isopropyl, etc.), alkoxy groups having 1 to 10 carbon atoms (e.g., methoxy, ethoxy, etc.), acyl groups having 1 to 10 carbon atoms (e.g., acetyl, benzoyl, etc.), acylamino groups having 1 to 10 carbon atoms (e.g., acetamide, benzoylamide, etc.), aryl groups having 6 to 11 carbon atoms (e.g., phenyl, naphthyl, etc.) which may have at least one substituent selected from the group consisting of nitro, cyano, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, non-substitution is preferable.

[0046] Examples of the optionally substituted aryloxy group having 6 to 11 carbon atoms include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. The number of carbon atoms in the optionally substituted aryloxy group having 6 to 11 carbon atoms is preferably 8 or less, and more preferably 7 or less. When it is within this range, steric hindrance between the azafluorene rings is unlikely to occur, and desired optical properties derived from the azafluorene rings tend to be obtained.

[0047] Examples of the substituent that the aryloxy group may have include an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.); a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); Examples of the substituent include an aryl group having 6 to 11 carbon atoms (e.g., a phenyl group, a naphthyl group, etc.) which may have at least one substituent selected from the group consisting of a fluorine atom, an iodine atom), an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, it is preferable that the substituent is unsubstituted.

[0048] Examples of the amino group which may be substituted include an amino group; an aliphatic amino group such as an N-methylamino group, an N,N-dimethylamino group, an N-ethylamino group, an N,N-diethylamino group, an N,N-methylethylamino group, an N-propylamino group, an N,N-dipropylamino group, an N-isopropylamino group, or an N,N-diisopropylamino group; an aromatic amino group such as an N-phenylamino group or an N,N-diphenylamino group; an acylamino group such as a formamide group, an acetamide group, a decanoylamide group, a benzoylamide group, or a chloroacetamide group; and an alkoxycarbonylamino group such as a benzyloxycarbonylamino group or a tert-butyloxycarbonylamino group. Among these, an N,N-dimethylamino group, an N-ethylamino group, or an N,N-diethylamino group is preferred, and an N,N-dimethylamino group is more preferred, since they do not have a highly acidic proton, have a small molecular weight, and tend to increase the proportion of azafluorene rings in the optical material.

[0049] Examples of the substituent that the amino group may have include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom); alkoxy groups having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group, etc.); acyl groups having 1 to 10 carbon atoms (e.g., acetyl group, benzoyl group, etc.); acylamino groups having 1 to 10 carbon atoms (e.g., acetamide group, benzoylamide group, etc.); nitro group; cyano group; halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy groups having 1 to 10 carbon atoms (e.g., methoxy group, ethoxy group, etc.), acyl groups having 1 to 10 carbon atoms (e.g., acetyl group, benzoyl group, etc.), acylamino groups having 1 to 10 carbon atoms (e.g., acetamide group, benzoylamide group, etc.), Examples of the alkyl group include alkyl groups (e.g., methyl, ethyl, isopropyl, etc.), alkoxy groups having 1 to 10 carbon atoms (e.g., methoxy, ethoxy, etc.), acyl groups having 1 to 10 carbon atoms (e.g., acetyl, benzoyl, etc.), acylamino groups having 1 to 10 carbon atoms (e.g., acetamide, benzoylamide, etc.), aryl groups having 6 to 11 carbon atoms (e.g., phenyl, naphthyl, etc.) which may have at least one substituent selected from the group consisting of nitro, cyano, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different.

[0050] Examples of the vinyl group having 2 to 10 carbon atoms which may be substituted and the ethynyl group having 2 to 10 carbon atoms which may be substituted include a vinyl group, a 2-methylvinyl group, a 2-ethylvinyl group, a 2-propylvinyl group, a 2,2-dimethylvinyl group, a 2-phenylvinyl group, a 2-acetylvinyl group, an ethynyl group, a methylethynyl group, a tert-butylethynyl group, a phenylethynyl group, an acetylethynyl group, and a trimethylsilylethynyl group. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, non-substitution is preferable. Among these, a vinyl group, a 2-methylvinyl group, an ethynyl group, and a 2-methylethynyl group are more preferable because they have a small molecular weight and tend to increase the proportion of azafluorene rings in the optical material.

[0051] Examples of the substituent that the vinyl group and ethynyl group may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), a nitro group, a cyano group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), an aryl group having 1 to 10 carbon atoms (e.g., an aryl group ... Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, an isopropyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.), an aryl group having 6 to 11 carbon atoms (e.g., a phenyl group, a naphthyl group, etc.) which may have at least one substituent selected from the group consisting of a nitro group, a cyano group, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3.

[0052] Examples of the silicon atom having a substituent include trialkylsilyl groups such as trimethylsilyl group and triethylsilyl group, and trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group. Among these, trialkylsilyl groups are preferred because they can be handled stably. Examples of the sulfur atom having a substituent include a sulfo group; alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group; arylsulfonyl groups such as a phenylsulfonyl group and a p-tolylsulfonyl group; alkylsulfinyl groups such as a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, and an isopropylsulfinyl group; arylsulfinyl groups such as a phenylsulfinyl group and a p-tolylsulfinyl group; alkylthio groups such as a methylthio group and an ethylthio group; a phenylthio group, a p -arylthio groups such as tolylthio groups; alkoxysulfonyl groups such as methoxysulfonyl groups and ethoxysulfonyl groups; aryloxysulfonyl groups such as phenoxysulfonyl groups; aminosulfonyl groups; alkylsulfonyl groups such as N-methylaminosulfonyl groups, N-ethylaminosulfonyl groups, N-tert-butylaminosulfonyl groups, N,N-dimethylaminosulfonyl groups, and N,N-diethylaminosulfonyl groups; arylaminosulfonyl groups such as N-phenylaminosulfonyl groups and N,N-diphenylaminosulfonyl groups. The sulfo group may form a salt with lithium, sodium, potassium, magnesium, ammonium, or the like. Among these, methylsulfinyl groups, ethylsulfinyl groups, or phenylsulfinyl groups are preferred, and methylsulfinyl groups are more preferred, since they do not have a highly acidic proton, have a small molecular weight, and tend to increase the proportion of azafluorene rings in the optical material.

[0053] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, or a bromine atom is preferred, and a chlorine atom or a bromine atom is more preferred, since they are relatively easy to introduce and tend to increase the reactivity of the methylene group of the azafluorene due to their electron-withdrawing properties.

[0054] The above mentioned R 1 ~R 8 Among these, it is preferable that at least two adjacent groups are bonded to each other to form a ring. In this case, the optical properties of the resin can be further improved. From the same viewpoint, it is more preferable that the ring formed is an aromatic ring. That is, it is more preferable that the azafluorene ring in the structural unit (a) has an aromatic ring as a condensed ring. By having an aromatic ring as a condensed ring, the π-conjugated system of the azafluorene ring can be expanded, so that the optical properties of the resin can be further improved. From the same viewpoint, it is more preferable that the ring formed contains one or more aromatic rings that are benzene rings or six-membered rings containing heteroatoms.

[0055] The azafluorene ring in the structural unit (a) preferably has only a nitrogen atom as a heteroatom (specifically, an atom other than carbon) forming the ring. In other words, the heteroatom forming the azafluorene ring is preferably a nitrogen atom. In this case, the water absorption rate of the resin can be reduced, and therefore the balance between excellent optical properties and dimensional stability is particularly excellent.

[0056] In structural unit (a), R 9 and R 10 R each independently represents a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. 9 and R 10 Specific structures of R include, but are not limited to, linear alkylene groups such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene; branched alkylene groups (R 9 and R 10where the numerical values ​​of the substitution positions are determined starting from the carbon on the fluorene ring side); alicyclic alkylene groups having linear or branched alkylene group bonds at any two positions in an alicyclic structure, such as cyclopropane, cyclohexane, decahydronaphthalene, and adamantane; and heterocyclic alkylene groups having linear or branched alkylene group bonds at any two positions in a heterocyclic structure, such as tetrahydrofuran, tetrahydropyran, and 1,3-dioxane. Specific structures of the bonds of the linear or branched alkylene group at any two positions are listed below, and include, but are not limited to, linear alkylene groups such as a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, and an n-hexylene group; and branched alkylene groups such as a 1-methylethylene group, a 2-methylethylene group, a 1-ethylethylene group, a 2-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,1-dimethylethylene group, a 2,2-dimethylpropylene group, and a 3-methylpropylene group (wherein the numerical value of the substitution position is determined from the carbon bonded to the ring structure).

[0057] Examples of the substituent that the alkylene group may have include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.); an acyl group having 1 to 10 carbon atoms (e.g., an acetyl group, a benzoyl group, etc.); an acylamino group having 1 to 10 carbon atoms (e.g., an acetamide group, a benzoylamide group, etc.); a nitro group; a cyano group; a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), Examples of the substituent include alkyl groups (e.g., methyl, ethyl, isopropyl, etc.), alkoxy groups having 1 to 10 carbon atoms (e.g., methoxy, ethoxy, etc.), acyl groups having 1 to 10 carbon atoms (e.g., acetyl, benzoyl, etc.), acylamino groups having 1 to 10 carbon atoms (e.g., acetamide, benzoylamide, etc.), aryl groups having 6 to 11 carbon atoms (e.g., phenyl, naphthyl, etc.) which may have at least one substituent selected from the group consisting of nitro, cyano, etc. The number of the substituents is not particularly limited, but is preferably 1 to 3. When there are two or more substituents, the types of the substituents may be the same or different. In addition, from the viewpoint of enabling industrially inexpensive production, it is preferable that the compound is unsubstituted.

[0058] R 9 and R 10 The selection of R has a particularly significant effect on the expression of reverse wavelength dispersion. The resin of the present disclosure exhibits the strongest reverse wavelength dispersion when the azafluorene rings are oriented perpendicular to the main chain direction (e.g., stretching direction). In order to bring the orientation state of the azafluorene rings closer to the above state and to express strong reverse wavelength dispersion, it is necessary to select R 9 and R 10 R is preferably an optionally substituted alkylene group having 1 to 20 carbon atoms. The optionally substituted alkylene group having 1 to 20 carbon atoms preferably has 1 to 3 carbon atoms. 9 The number of carbon atoms in R is more preferably 2 to 3, and particularly preferably 2. 10The number of carbon atoms is preferably 1 to 2, and particularly preferably 1. If the number of carbon atoms is greater than this range, the azafluorene rings cannot be oriented in a preferred direction, and desired optical properties may not be obtained. Similarly, if the number of carbon atoms is smaller, the desired optical properties may not be obtained, and the thermal stability may be impaired, leading to the risk of decomposition due to heat during polymerization reactions or melt molding. Also, R 9 and R 10 When is not an alkylene group but a divalent aromatic group such as an arylene group, the photoelastic coefficient of the resin becomes larger and the optical properties become inferior compared to when it is an alkylene group.

[0059] In the structural unit (a), X is an oxygen atom, a carbonyl group, or an amino group which may be substituted. That is, the monomers containing the structural unit (a) are dihydroxy compounds, dicarboxylic acid compounds, diester compounds, and diamine compounds, respectively. In other words, examples of monomers capable of forming the structural unit (a) include dihydroxy compounds, dicarboxylic acid compounds, diester compounds, and diamine compounds. X is preferably an oxygen atom or a carbonyl group, and more preferably a carbonyl group. When X is a carbonyl group, the resin tends to have excellent properties such as thermal stability, heat resistance, and reverse wavelength dispersion.

[0060] In the structural unit (a), n is 0 to 5, more preferably 0 to 2, further preferably 0 to 1, and particularly preferably 1. Within this range, a compound with high purity and a clear structure is easily obtained in the synthesis of the monomer, and a resin using this is easily able to exhibit high heat resistance and optical properties, particularly a low photoelastic coefficient and reverse wavelength dispersion with high expression efficiency.

[0061] The azafluorene ring in the structural unit (a) is 1 ~R 8 Among these, it is preferable that at least two adjacent groups among the above be bonded to each other to form an aromatic ring as a condensed ring. 1 ~A 8It is more preferable that an aromatic ring is further condensed to the six-membered ring containing one or more nitrogen atoms as a nitrogen atom. In this case, when there is a six-membered ring that does not contain a nitrogen atom, it is particularly preferable that an aromatic ring is condensed to the six-membered ring that does not contain a nitrogen atom. Since the π-conjugated system of the azafluorene ring can be expanded, the optical properties of the resin can be further improved. Specifically, A 5 and A 8 At least one of is =N-, and A 1 ~A 4 ,A 6 ,A 7 are both =CH- and R 6 and R 7 are preferably bonded to each other to form an aromatic ring, and in this case, R 1 ~R 4 It is particularly preferred that at least two adjacent groups among A are bonded to each other to form an aromatic ring as a condensed ring. 1 and A 4 At least one of is =N-, and A 2 , A 3 ,A 5 ~A 8 are both =CH- and R 2 and R 3 are preferably bonded to each other to form an aromatic ring, and in this case, R 5 ~R 8 Among these, it is particularly preferable that at least two adjacent groups among these be bonded to each other to form an aromatic ring as a condensed ring. Specific examples of the structural unit (a) include the structures shown in the following group [A].

[0062] [ka]

[0063] Among these, the structural units shown in the following group [B] are more preferable. In this case, the resin has excellent optical properties, heat resistance, thermal stability, and mechanical properties. Furthermore, in this case, the synthesis of the monomer can be performed relatively inexpensively, and a high-purity monomer can be easily obtained.

[0064] [ka]

[0065] The oligofluorene structural unit in the present disclosure has the following characteristics compared to the structural unit derived from 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (structural formula (4) below) and the structural unit derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (structural formula (5) below) that have been widely used in the past. Aromatic components such as phenyl groups, which were previously incorporated into the main chain of a polymer, are no longer incorporated into the main chain of the polymer, reducing the photoelastic coefficient.

[0066] The aromatic component incorporated in the main chain exhibits positive wavelength dispersion with larger birefringence at shorter wavelengths, which offsets the reverse wavelength dispersion derived from the fluorene rings in the side chains, lowering the reverse wavelength dispersion of the resin as a whole. By not incorporating the aromatic component in the main chain, however, it is possible to express stronger reverse wavelength dispersion. By replacing the fluorene ring in the side chain with an azafluorene ring, it is possible to more strongly exhibit reverse wavelength dispersion.

[0067] By introducing two (aza)fluorene rings into the structural unit, the resin can be endowed with high heat resistance and a low photoelastic coefficient. -Since the main chain is composed of flexible alkylene chains, it is possible to impart flexibility and melt processability to the resin.

[0068] [ka]

[0069] [ka]

[0070] [Resin of the present disclosure] The resin of the present disclosure is a thermoplastic resin containing a structural unit (a). Preferably, it is a polycondensation or polyaddition thermoplastic resin, specifically a resin having at least one bond selected from the group consisting of a carbonate bond, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, and an imide bond, i.e., polycarbonate, polyester, polyamide, polyether, epoxy, polyurethane, and polyimide. More preferably, it is a polycondensation thermoplastic resin, specifically a resin having at least one bond selected from the group consisting of a carbonate bond, an ester bond, an amide bond, and an imide bond, i.e., polycarbonate, polyester, polyamide, and polyimide. More preferably, it is a resin having a carbonate bond and / or an ester bond, i.e., polycarbonate, polyester, and polyestercarbonate. These resins are excellent in heat resistance, mechanical properties, and melt processability. In addition, copolymerization of a plurality of monomers including the monomer that is the raw material of the structural unit (a) has the advantage that various physical properties such as optical properties, heat resistance, and mechanical properties can be easily controlled within desired ranges.

[0071] Methods for introducing the structural unit (a) of the present disclosure into a resin include a method of polymerizing a diol, dicarboxylic acid, diester, or diamine having the structural unit (a) in its molecular structure with another diol, diester, isocyanate, epoxy, or the like. Specifically, a polycarbonate can be obtained by polymerization of a combination of a diol and a carbonate diester represented by the following formula (6). A polyester can be obtained by polymerization of a combination of a diol and a diester. A polyester carbonate can be obtained by polymerization of a combination of a diol, a diester, and a carbonate diester.

[0072] [ka]

[0073] In the formula (6), R 13 and R 14 R is an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms. 13 and R 14 may be the same or different. Examples of monomers that serve as raw materials for the structural unit (a) include diols represented by the following formula (7) and diesters represented by the following formula (8). The diols represented by the formula (7) and the diesters represented by the formula (8) are appropriately referred to as "azafluorene monomers."

[0074] [ka]

[0075] [ka]

[0076] In the formulas (7) and (8), A 1 ~A 8 , R 1 ~R 10 , and n are the same as in formula (1). 11 and R 12 R is a hydrogen atom, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms. 11 and R 12 may be the same or different. From the viewpoint of ease of synthesis, R 11 and R 12 are preferably identical. Among them, it is preferable to use the specific diester represented by the formula (8) above. The specific diester has relatively better thermal stability than the specific diol represented by the formula (7) above, and the azafluorene rings in the polymer tend to be oriented in a preferred direction, thereby exhibiting stronger reverse wavelength dispersion.

[0077] On the other hand, when comparing polycarbonate and polyester, polycarbonate obtained by polymerization of diol and carbonic acid diester tends to have a better balance between heat resistance and mechanical properties. Therefore, as the resin of the present disclosure, polyester carbonate in which the specific diester having the structural unit (a) is incorporated into polycarbonate is particularly preferred. R in the above formula (8) 11 and R 12 When R in formula (8) is a hydrogen atom or an alkyl group such as a methyl group or an ethyl group, the polymerization reaction may not occur easily under the polymerization conditions of a polycarbonate that are usually used. 11 and R 12 is preferably an aryl group.

[0078] In the diol represented by the formula (7), when n is 0, R 9 is preferably an alkylene group having 1 to 20 carbon atoms which may be substituted. In this case, the diol represented by the formula (7) has excellent stability, and there is no risk that the diol will be decomposed by the heat during the resin polymerization, making it impossible to obtain a resin. From the same viewpoint, when n is 0, R 9 is more preferably an optionally substituted alkylene group having 1 to 3 carbon atoms, and further preferably an optionally substituted alkylene group having 2 to 3 carbon atoms.

[0079] In addition, when the polymerization reaction is carried out using the carbonic acid diester represented by the formula (6), R 13 , R 14 and R in the formula (8) 11 , R 12It is preferable that R have the same structure. In this case, the same components are eliminated from the carbonic acid diester represented by formula (6) and the diester represented by formula (8) during the polymerization reaction, so that the eliminated components can be easily recovered and reused. In addition, from the viewpoint of polymerization reactivity and usefulness in reuse, R 11 ~R 14 It is particularly preferred that R is a phenyl group. 11 ~R 14 When is a phenyl group, the component which is eliminated during the polymerization reaction is phenol.

[0080] Specific examples of the azafluorene ring in the formulas (7) and (8) include structures shown in the following group [I].

[0081] [ka]

[0082] Among these (specifically, group [I]), preferred azafluorene rings are shown in group “J” below.

[0083] [ka]

[0084] Among these (specifically, group [J]), particularly preferred azafluorene rings are shown in group “K” below.

[0085] [ka]

[0086] R in Equation (8) 11 and R 12 With respect to the above, "an optionally substituted aryl group having 6 to 11 carbon atoms", "an optionally substituted heteroaryl group having 3 to 10 carbon atoms" and "an optionally substituted alkyl group having 1 to 10 carbon atoms" are R 1 ~R 8 The substituents are the same as those in R11 and R 12 is particularly preferably a methyl group or an ethyl group. In this case, polyester and polyester carbonate can be efficiently synthesized by removing the low-boiling alcohol generated by the transesterification of the diester compound represented by formula (8) and the dihydroxy compound. On the other hand, from the viewpoint that the transesterification reaction easily proceeds and the polyester carbonate can be synthesized in one step by adding the diester compound, the dihydroxy compound, and the carbonic acid diester all at once to the reactor, R 11 and R 12 R is preferably an optionally substituted aryl group having 6 to 11 carbon atoms. 11 and R 12 is particularly preferably a phenyl group. In this case, the phenyl group can be distilled off as phenol after the synthesis of the polyester carbonate. 11 and R 12 In the case where R is an optionally substituted aryl group having 6 to 11 carbon atoms, it is preferable to use diaryl carbonates described later as the carbonic acid diester from the viewpoint of reactivity during polymerization, and from the viewpoint of easy removal of by-products, R 11 and R 12 It is more preferred that the aryl group in the above-mentioned aryl group is the same as the aryl group in the diaryl carbonate.

[0087] In the azafluorene monomers represented by formula (7) and formula (8), n represents an integer value of 0 to 5. From the viewpoint that as the value of n increases, the solubility decreases and purification becomes difficult, the value of n is preferably 2 or less, more preferably 0 or 1, and particularly preferably 1.

[0088] <Specific structure> Examples of the azafluorene monomers represented by the formulas (7) and (8) are listed in the following group [L].

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] Of these, preferred azafluorene monomers are shown in the "M" group below.

[0093] [ka]

[0094] In the azafluorene monomer of the present disclosure, when two aromatic rings that share a bond with a five-membered ring contained in the azafluorene ring are asymmetric with respect to the five-membered ring (i.e., sandwiched between the five-membered ring), isomers exist depending on the orientation of the azafluorene ring. These isomers may be used alone or in combination of two or more.

[0095] <Physical properties of azafluorene monomer> The physical properties of the azafluorene monomer of the present disclosure are not particularly limited, but it is preferable that the azafluorene monomer satisfies the physical properties exemplified below.

[0096] When the resin of the present disclosure is used for optical materials such as optical lenses, the refractive index of the azafluorene monomer at a wavelength of 587 nm is preferably 1.61 or more. In this case, the optical lens obtained by using a composition containing a polyester carbonate resin or a polyester resin can be made thinner. A higher refractive index of the azafluorene monomer is advantageous in making the lens thinner. Therefore, the refractive index of the azafluorene monomer at a wavelength of 587 nm is more preferably 1.62 or more, even more preferably 1.63 or more, and particularly preferably 1.64 or more. The refractive index of the azafluorene monomer at a wavelength of 587 nm is usually 1.75 or less.

[0097] The Abbe number of the azafluorene monomer is preferably 25 or less. In this case, it is advantageous to use the composition containing the polyester carbonate resin or polyester resin as an optical material such as an imaging optical lens. The lower the Abbe number of the monomer, the more advantageous it is to design an imaging optical lens. Therefore, the Abbe number of the azafluorene monomer is more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. The Abbe number of the azafluorene monomer is usually 13 or more.

[0098] When a composition containing a polyester carbonate resin or a polyester resin is used for an optical material, it is preferable that the refractive index of the azafluorene monomer at a wavelength of 587 nm is 1.61 or more, and the Abbe number of the azafluorene monomer is 25 or less. In this case, the influence of the formula aberration can be avoided in making the optical material smaller and thinner. From the viewpoint of improving this effect, it is more preferable that the refractive index of the azafluorene monomer at a wavelength of 587 nm is 1.62 or more, and the Abbe number of the azafluorene monomer is 22 or less, more preferably that the refractive index of the azafluorene monomer at a wavelength of 587 nm is 1.63 or more, and the Abbe number of the azafluorene monomer is 20 or less, and it is particularly preferable that the refractive index of the azafluorene monomer at a wavelength of 587 nm is 1.64 or more, and the Abbe number of the azafluorene monomer is 18 or less.

[0099] <Method of Producing Azafluorene Monomer> Although there are no particular limitations on the method for producing the azafluorene monomer of the present disclosure, the azafluorene monomer can be produced, for example, by Production Method A or Production Method B shown in the following formula.

[0100] [ka]

[0101] In each structural formula, A 1~A 8 Each independently represents =CH- or =N-. 1 ~A 8 At least one of the groups contains =N-. 1 ~R 8 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl group having 2 to 10 carbon atoms, an optionally substituted ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. 1 ~R 8 At least two adjacent groups among R may be bonded to each other to form a ring. 9 and R 10 R each independently represents a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. 11 and R 12 R is a hydrogen atom, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms. 11 and R 12 may be the same or different, and n represents an integer value of 0 to 5.

[0102] <Manufacturing method A> In production method A, azafluorenes (I) are used as raw materials and converted to 9-hydroxymethylazafluorenes (III). Then, olefins (IV) are synthesized by dehydration, and the olefins (IV) are reacted with azafluorenyl anions. This produces azaoligofluorene compounds (II). The azafluorene compounds (II) thus obtained can be converted into azafluorene monomers (1) according to step (ii).

[0103] For example, a method is known in which 9-hydroxymethylfluorene is converted to dibenzofulvene, and then anionic polymerization is performed to synthesize a mixture of oligofluorenes (Tamaki Nakano, Kazuyuki Takewaki, Tohru Yade, and Yoshio Okamoto “Dibenzofulvene, a 1,1-Diphenylethylene Analogue, Gives a π-Stacked Polymer by Anionic, Free-Radical, and Cationic Catalysts” Journal of the American Chemical Society, 1155 Sixteenth,Street NW Washington, DC 20036, ACS Publications, 25 August 2001, 123, p.9182-9183). By referring to these methods, azafluorene compound (II) can be produced by replacing fluorene with azafluorenes (I).

[0104] The method for producing the raw material azafluorenes (I) is not particularly limited, but for example, the following methods are known. 11H-Indeno[1,2-b]quinolines can be synthesized, for example, by reducing 2-nitrobenzaldehyde to 2-aminobenzaldehyde, followed by reaction of 2-aminobenzaldehyde with 1-indanone under basic conditions (Nada Marquise, Guillaume Bretel, Frédéric Lassagne, Floris Chevallier, Thierry Roisnel, Vincent Dorcet, Yury S. Halauko, Oleg A. Ivashkevich, Vadim E. Matulis, Philippe C. Gros and Florence Mongin. “Deproto-metallation using mixed lithium-zinc and lithium-copper bases and computed CH acidity of 2-substituted quinolines.” RSC Advances. ,Royal Society of Chemistry, Thomas Graham House (290), Science Park, Milton Road, Cambridge, CB4 0WF. ,16 April 2014. 4, 19602-19612.) In a similar manner, for example, 7H-benz[6,7]indeno[1,2-b]quinoline can be prepared by reacting 2-aminobenzaldehyde with 2,3-dihydro-1H-benz[e]inden-1-one under basic conditions.11H-Indeno[1,2-b]quinoxalines are synthesized by reacting benzene-1,2-diamines with indan-1,2-dione (see Frederic Lassagne, Floris Chevallier, Thierry Roisnel, Vincent Dorcet, Florence Mongin, Luis R. Domingo. “A Combined Experimental and Theoretical Study of the Ammonium Bifluoride Catalyzed egioselective Synthesis of Quinoxalines and Pyrido[2,3-b]pyrazines.” Synthesis, Georg Thieme Verlag KG., 19 May 2015. 47, p. 2680-2689). 3,3'-Methylene-2,2-biquinoline is synthesized, for example, by reacting 2-aminobenzaldehyde with 1,2-cyclopentanedione under basic conditions (see Jacques Royer, Henri Philippe Husson. "Asymmetric synthesis. 2. Practical method for the asymmetric synthesis of indolizidine alkaloids: total synthesis of (-)-monomorine I." The Journal of Organic Chemistry, 1155 Sixteenth Street NW Washington, DC 20036, ACS Publications., 1 March 1985., 50, 5, p.670-673.). <Manufacturing method B> In manufacturing method B, azafluorene compound (II) is synthesized by carrying out a crosslinking reaction (step (i)) of raw material azafluorenes (I). Then, an ester group is introduced into azafluorene compound (II) (step (ii)) to produce azafluorene monomer (1).

[0105] [ka]

[0106] In the formula, A 1 ~A 8 , R 1 ~R 12 and n is A in formula (7) and formula (8). 1 ~A 8 , R 1 ~R 12 and similar to n. Hereinafter, Production Method B will be described separately into step (i) a method for producing an azafluorene compound (II) and step (ii) a method for producing an azafluorene monomer (1).

[0107] <Step (i): Method for producing azafluorene compound (II)> The azafluorene compound having a methylene bridge represented by the following general formula (II) is produced, for example, from an azafluorene (I) and a formaldehyde in the presence of a base according to the reaction represented by the following formula:

[0108] [ka]

[0109] In the formula, A 1 ~A 8 , R 1 ~R 8 and n is A in formula (1). 1 ~A 8 , R 1 ~R 8 and similar to n.

[0110] <Formaldehyde> The formaldehyde used in step (i) is not particularly limited as long as it is a substance capable of supplying formaldehyde to the reaction system. Specifically, gaseous formaldehyde, formaldehyde aqueous solution, paraformaldehyde polymerized from formaldehyde, trioxane, etc. are mentioned. Among these, it is preferable to use formaldehyde aqueous solution or paraformaldehyde. In this case, industrially inexpensive production is possible, and the formaldehyde can be easily handled and accurately weighed.

[0111] (Definition of theoretical quantity) To produce an azafluorene compound (II) having a desired value of n, the theoretical amount (molar ratio) of formaldehyde relative to the starting azafluorene (I) is expressed as n / (n+1).

[0112] (Why it is better not to exceed the theoretical amount) When a theoretical excess of formaldehyde is used relative to azafluorenes (I), an azafluorene compound (IIa) having n exceeding the target value tends to be produced. As n increases, the solubility decreases, so that the more azafluorene compounds (IIa) having n exceeding the target value are present in the target product (specifically, azafluorene compound (II) having n as the target value), the greater the purification load tends to be. Therefore, it is usually preferable that the amount of formaldehyde used is n / (n+1) times the theoretical amount by mole or less.

[0113] (Why it is better not to go far below the theoretical amount) In addition, if the amount of formaldehyde used is significantly lower than the theoretical amount n / (n+1), the azafluorene compound (IIb) in which n does not satisfy the target value will be the main product, or the raw material azafluorene (I) will remain unreacted, and therefore it is known that the yield tends to decrease significantly.

[0114] Specifically, the amount of formaldehyde used is usually 0.1 times by mole or more, preferably 0.3 times by mole or more, more preferably 0.38 times by mole or more, relative to the azafluorenes (I) when n = 1. Also, the amount of formaldehyde used is usually 0.5 times by mole or less, preferably 0.46 times by mole or less, more preferably 0.42 times by mole or less, relative to the azafluorenes (I) when n = 1. In addition, the amount of formaldehyde used is usually 0.5 times or more by mole, preferably 0.55 times or more by mole, and more preferably 0.6 times or more by mole, relative to the azafluorenes (I) when n=2. In addition, the amount of formaldehyde used is usually 0.66 times or less by mole, preferably 0.65 times or less by mole, and more preferably 0.63 times or less by mole, relative to the azafluorenes (I) when n=2. In this way, it is known that the structure of the main product and the ratio of the products change greatly according to the amount of formaldehyde used, and the azafluorene compound (II) having the desired n number can be obtained in high yield by using the amount of formaldehyde used under limited conditions.

[0115] <base> Examples of the base used in step (i) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate, and potassium phosphate; organic lithium salts such as n-butyl lithium and tertiary butyl lithium; alkali metal alkoxide salts such as sodium methoxide, sodium ethoxide, and potassium tertiary butyl oxide; alkali metal hydrides such as sodium hydride and potassium hydride; tertiary amines such as triethylamine and diazabicycloundecene; and quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. These may be used alone or in combination of two or more.

[0116] Among these, preferred are alkali metal alkoxides having sufficient basicity in the reaction of step (i), and more preferred are sodium methoxide and sodium ethoxide, which are industrially inexpensive. Here, the alkali metal alkoxide may be in the form of a powder or a liquid such as an alcohol solution. Alternatively, the alkali metal alkoxide may be prepared by reacting an alkali metal with an alcohol.

[0117] The upper limit of the amount of base used relative to the raw material azafluorenes (I) is not particularly limited, but if the amount used is too large, the burden of stirring and purification after the reaction will increase. From this viewpoint, the amount of base used is usually 10 times the molar amount of the azafluorenes (I) or less, preferably 5 times the molar amount of the azafluorenes (I) or less, more preferably 1 times the molar amount of the azafluorenes (I). On the other hand, if the amount of base used is too small, the reaction will proceed slowly. Therefore, the amount of base used is usually 0.01 times the molar amount of the raw material azafluorenes (I) or more, preferably 0.1 times the molar amount of the azafluorenes (I) or more, more preferably 0.2 times the molar amount of the azafluorenes (I).

[0118] <Solvent> It is desirable to carry out step (i) using a solvent. Specific examples of solvents that can be used include alkylnitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, and tertiary butyl methyl ether; halogenated solvents such as 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethylsulfoxide and sulfolane; monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane (note that monocyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbons); methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dichloroethane, and 1,2-dichloroethane; Derivatives of monocyclic aliphatic hydrocarbons such as methylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, and 1,3,5-trimethylcyclohexane; polycyclic aliphatic hydrocarbons such as decalin (note that polycyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbon); acyclic aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane; aromatic hydrocarbons such as toluene, p-xylene, o-xylene, and m-xylene; and alcoholic solvents such as methanol, ethanol, isopropanol, n-butanol, tertiary butanol, hexanol, octanol, and cyclohexanol.

[0119] Among these, polar solvents are preferred because the solubility of anions generated from the azafluorenes (I) is high and the reaction tends to proceed well. Specifically, amide-based solvents or sulfoxide-based solvents are preferred. Among these, N,N-dimethylformamide is particularly preferred when producing an azafluorene compound (II) with n=1 or 2 (specifically, an oligoazafluorene compound (II)). This is because the solubility of the azafluorene compound (II) with n=1 or 2 in N,N-dimethylformamide is low, and the target product precipitates quickly after production, suppressing further reaction progress, and the selectivity of the target product tends to increase.

[0120] These solvents may be used alone or in combination of two or more (specifically, a mixed solvent of two or more). It is known that the solubility of the azafluorene compound (II) produced in step (i) in a solvent decreases as the value of n increases, and it is considered that the rapid precipitation of the target product inhibits further reaction. Therefore, it is preferable to appropriately adjust the amount of solvent used according to the value of n. In particular, when producing an azafluorene compound (II) with n=1 or 2, it is better not to use an excessive amount of solvent in order to increase the selectivity of the target product. For example, when using N,N-dimethylformamide, which is a particularly preferred solvent, the upper limit of the amount of solvent is usually 10 times the volume of the raw material azafluorene (I), preferably 7 times the volume, and more preferably 4 times the volume. On the other hand, if the amount of solvent used is too small, stirring becomes difficult and the reaction progresses slowly, so the lower limit is usually 1 time the volume of the raw material azafluorene (I), preferably 2 times the volume, and more preferably 3 times the volume.

[0121] <Reaction format> When carrying out the step (i), the reaction type is not particularly limited, and may be a batch reaction, a flow reaction, or a combination thereof.

[0122] <Reaction conditions> The reaction conditions in step (i) are appropriately adjusted so that an azafluorene compound (II) having a target n value is produced. In order to suppress the progress of the reaction of a product having n exceeding the target value, it is preferable to carry out the reaction at a low temperature as much as possible. On the other hand, if the temperature is too low, there is a possibility that a sufficient reaction rate cannot be obtained. When using N,N-dimethylformamide as a particularly preferred solvent and sodium ethoxide as a particularly preferred base and n=1 or 2, the upper limit of the reaction temperature is usually 30° C., preferably 20° C., and more preferably 10° C. On the other hand, the lower limit is usually −50° C., preferably −20° C., and more preferably 0° C. The lower limit of the reaction time in step (i) is generally 30 minutes, preferably 60 minutes, more preferably 2 hours. The upper limit of the reaction time is not particularly limited, but is generally 20 hours, preferably 10 hours, more preferably 5 hours.

[0123] <Isolation and purification of the target product> After the reaction is completed, the reaction solution is added to an acidic water such as dilute hydrochloric acid, or an acidic water such as dilute hydrochloric acid is added to the reaction solution, whereby the target azafluorene compound (II) is precipitated and isolated. After the reaction is completed, the target azafluorene compound (II) may be extracted by adding water and a solvent in which the target azafluorene compound (II) is soluble to the reaction solution. The target product extracted by the solvent is isolated by concentrating the solvent or adding a poor solvent. However, since the solubility of the azafluorene compound (II) in the solvent tends to be very low at room temperature, it is usually preferable to bring the reaction solution into contact with acidic water to precipitate the product.

[0124] The obtained azafluorene compound (II) can be used as it is as a raw material for step (ii), but it may be purified before use in step (ii). The purification method is not particularly limited, and a conventional purification method can be adopted. Specifically, purification is performed by recrystallization, reprecipitation, extraction purification, column chromatography, etc.

[0125] <Method for producing azafluorene monomer (1)> The method for producing the azafluorene monomer (1) in step (ii) shown in the following formula will be described below by dividing it into reaction modes.

[0126] [ka]

[0127] In the formula, A 1 ~A 8 , R 1 ~R 12 and n is A in formula (7) and formula (8). 1 ~A 8 , R 1 ~R 12 and similar to n.

[0128] <Step (iia): Production method by Michael addition> The azafluorene monomer represented by the following general formula (1a) is produced from an azafluorene compound (II) and an ester group-substituted olefin (V) in the presence of a base according to the reaction represented by the following step (iia).

[0129] [ka]

[0130] In the formula, A 1 ~A 8 , R 1 ~R 11 and n is A in formula (7) and formula (8). 1 ~A 8 , R 1 ~R 11 and n. R i , R ii and R iii represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms.

[0131] <Olefins substituted with electron-withdrawing groups> The electron-withdrawing group-substituted olefin as the reactant in step (iia) is represented by general formula (V), in which R i , R ii and R iii each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms which may be substituted, or an aralkyl group having 6 to 10 carbon atoms which may be substituted. Specific examples include alkyl groups which may be linear or branched, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclohexyl group; aryl groups such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 2-thienyl group; and aralkyl groups such as a benzyl group, a 2-phenylethyl group, and a p-methoxybenzyl group. These substituents may be further substituted with any substituent as long as it does not inhibit the reaction in step (iia).

[0132] Examples of the electron-withdrawing group-substituted olefin (V) include acrylic esters such as methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate; methacrylic esters such as methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, and 2-hydroxyethyl methacrylate; α-substituted unsaturated esters such as methyl 2-ethylacrylate and methyl 2-phenylacrylate; and β-substituted unsaturated esters such as methyl cinnamate, ethyl cinnamate, methyl crotonate, and ethyl crotonate. As the electron-withdrawing group-substituted olefin (V), an unsaturated carboxylic acid ester represented by the following general formula (V-1) is preferred, which allows direct introduction of a polymerization reactive group. From the viewpoint of reaction rate and reaction selectivity, acrylic acid esters, methacrylic acid esters, or α-substituted unsaturated esters contained in the unsaturated carboxylic acid ester represented by formula (V-1) are more preferred, and R iii acrylic acid esters in which R is a hydrogen atom or a methyl group; iiiMore preferred are methacrylic acid esters in which R is a hydrogen atom or a methyl group. 11 The smaller the molecular weight, the cheaper the production becomes on an industrial scale, the easier the purification by distillation is, and the higher the reactivity is. Therefore, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, or phenyl methacrylate is particularly preferred.

[0133] [ka]

[0134] In the formula, R 11 is R in equation (8). 11 Same as R iii represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or an optionally substituted aralkyl group having 6 to 10 carbon atoms.

[0135] The organic substituent of the ester group is preferably a hydroxyalkyl group. Specifically, the unsaturated carboxylic acid ester represented by formula (V-1) is preferably an ester having a hydroxyalkyl group such as 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, or 1,4-cyclohexanedimethanol monoacrylate. In this case, the raw material of polyester carbonate and polyester can be obtained in one step. Two or more different types of electron-withdrawing group-substituted olefins (V) may be used, but it is preferable to use one type of electron-withdrawing group-substituted olefin (V) from the viewpoint of ease of purification.

[0136] Since the electron-withdrawing group-substituted olefin (V) has high polymerization activity, when present at a high concentration, polymerization tends to proceed easily due to external stimuli such as light, heat, acid, and base. At that time, a large amount of heat is generated. Therefore, it is better not to use the electron-withdrawing group-substituted olefin (V) in an excessive amount from the viewpoint of safety. The amount of the electron-withdrawing group-substituted olefin (V) used is usually 10 times or less by mole, preferably 5 times or less by mole, and more preferably 3 times or less by mole, relative to the raw material azafluorene compound (II). Since the theoretical amount at the lower limit is 2 times by mole relative to the raw material, the amount of the electron-withdrawing group-substituted olefin (V) used is usually 2 times or more by mole relative to the raw material azafluorene compound (II). In order to accelerate the progress of the reaction and not leave raw materials or intermediates, the amount of the electron-withdrawing group-substituted olefin (V) used is preferably 2.2 times or more by mole, and more preferably 2.5 times or more by mole, relative to the raw material azafluorene compound (II).

[0137] <base> Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate, and potassium phosphate; organic lithium salts such as n-butyl lithium and tertiary butyl lithium; alkali metal alkoxide salts such as sodium methoxide, sodium ethoxide, and potassium tertiary butyl methoxide; alkali metal hydrides such as sodium hydride and potassium hydride; tertiary amines such as triethylamine and diazabicycloundecene; and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide. As the base, one kind of substance or two or more kinds of substances may be used.

[0138] The methylene group, which is the bridging group of the azafluorene compound (II), easily undergoes a decomposition reaction in a solvent in the presence of a base. Therefore, when the reaction is carried out in a two-layer system of an organic layer and an aqueous layer, it is preferable to use a water-soluble inorganic base, since side reactions such as decomposition reactions can be suppressed. Among them, from the viewpoints of cost and reactivity, alkali metal hydroxides are preferable, and sodium hydroxide or potassium hydroxide is more preferable.

[0139] Furthermore, when sodium hydroxide is used as the base, the reaction rate drops significantly if the concentration of the aqueous solution (specifically, the aqueous sodium hydroxide solution) is low. Therefore, the concentration of the aqueous solution is usually 5 wt / vol% or more, preferably 10 wt / vol% or more, and more preferably 25 wt / vol% or more. The upper limit of the amount of base used is not particularly limited, but if the amount of base used is too large relative to the raw material azafluorene compound (II), the stirring and purification load after the reaction may become large. Therefore, when a 25 wt / vol% or more aqueous sodium hydroxide solution is used as the base, the amount of base used is usually 20 times or less by volume relative to the azafluorene compound (II), preferably 10 times or less by volume, and more preferably 5 times or less by volume. If the amount of base is too small, the reaction rate drops significantly, so the amount of base used is usually 0.2 times or more by volume relative to the raw material azafluorene compound (II), preferably 0.5 times or more by volume, and more preferably 1 time or more by volume.

[0140] <1-4-2-2-3. Phase transfer catalyst> In the step (iia), when the reaction is carried out in a two-layer system of an organic layer and an aqueous layer, it is preferable to use a phase transfer catalyst in order to increase the reaction rate. Phase transfer catalysts include quaternary ammonium salt halides (excluding fluorides) such as tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium iodide, acetyltrimethylammonium bromide, and benzyltriethylammonium chloride; N,N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, and N-ethyl- Halides of quaternary pyrrolidinium salts such as N-methylpyrrolidinium bromide (excluding fluorides); halides of quaternary morpholinium salts such as N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, and N-allyl-N-methylmorpholinium bromide (excluding fluorides); halides of quaternary piperidinium salts such as N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N,N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidinium acetate, and N-methyl-N-ethylpiperidinium iodide (excluding fluorides); crown ethers, etc. These may be used alone or in combination of two or more.

[0141] The phase transfer catalyst is preferably a quaternary ammonium salt, more preferably benzyltrimethylammonium chloride or benzyltriethylammonium chloride. If the amount of phase transfer catalyst used is too large relative to the raw material azafluorene compound (II), side reactions such as ester hydrolysis and successive Michael reactions tend to progress significantly, and the cost also increases. From this perspective, the amount of phase transfer catalyst used is usually 5 times or less by mole, preferably 2 times or less by mole, and more preferably 1 time or less by mole, relative to the raw material azafluorene compound (II). If the amount of phase transfer catalyst used is too small, the effect of improving the reaction rate cannot be sufficiently obtained, and the reaction rate may be significantly reduced, so the amount of phase transfer catalyst used is usually 0.01 times or more by mole, preferably 0.1 times or more by mole, and more preferably 0.5 times or more by mole, relative to the raw material azafluorene compound.

[0142] <Solvent> Step (iib) is preferably carried out in a solvent. Specific examples of solvents that can be used include alkylnitrile solvents such as acetonitrile and propionitrile; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; linear esters such as methyl acetate, ethyl acetate, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl lactate, and ethyl lactate (straight-chain esters are a type of ester solvent); cyclic esters such as γ-butyrolactone and caprolactone (cyclic esters are a type of ester solvent); ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, and propylene glycol-1-monoethyl ether acetate (ether esters are a type of ester solvent); diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclohexane, methyl ... Ether solvents such as pentyl ether and tertiary butyl methyl ether; halogenated solvents such as 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide and sulfolane; monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane (monocyclic monocyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbons); derivatives of monocyclic aliphatic hydrocarbons such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc.;Polycyclic aliphatic hydrocarbons such as decalin (polycyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbon); acyclic aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane; aromatic hydrocarbons such as toluene, p-xylene, o-xylene, and m-xylene; aromatic heterocycles such as pyridine; and alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, tertiary butanol, hexanol, octanol, and cyclohexanol.

[0143] It has been found that by using a solvent that undergoes phase separation from water, side reactions such as the decomposition reaction of the methylene group, which is the crosslinking group of the azafluorene compound (II), tend to be suppressed. Furthermore, when a solvent that dissolves the raw material azafluorene compound (II) well is used, the reaction tends to proceed well, so it is preferable to use a solvent in which the solubility of the azafluorene compound (II) is 0.5% by mass or more at a temperature of 25°C. A solvent in which the solubility of the azafluorene compound (II) is 1.0% by mass or more at a temperature of 25°C is more preferable, and a solvent in which the solubility of the azafluorene compound (II) is 1.5% by mass or more is even more preferable. Specifically, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, aromatic hydrocarbons, or ether solvents are preferable, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, 1,4-dioxane, or methylcyclopentyl ether is more preferable.

[0144] These solvents may be used alone or in combination of two or more. The upper limit of the amount of the solvent used is not particularly limited, but in consideration of the production efficiency of the target product per reactor, it is 20 times, preferably 15 times, and more preferably 10 times the volume of the raw material azafluorene compound (II). On the other hand, if the amount of the solvent used is too small, the solubility of the reagents is deteriorated, making stirring difficult and slowing down the progress of the reaction, so the lower limit is usually 1 times, preferably 2 times, and more preferably 4 times the volume of the raw material azafluorene compound (II).

[0145] <Reaction format> When carrying out the step (iia), the reaction type is not particularly limited, and may be a batch reaction, a flow reaction, or a combination thereof. In the case of a batch type reaction, if the electron-withdrawing group-substituted olefin (V) is added all at once to the reactor at the start of the reaction, the electron-withdrawing group-substituted olefin (V) is present in a high concentration, and therefore the polymerization reaction as a side reaction is likely to proceed. From the viewpoint of suppressing the side reaction, it is preferable to add the raw material azafluorene compound (II), phase transfer catalyst, solvent and base to the reactor, and then gradually add the electron-withdrawing group-substituted olefin (V) little by little.

[0146] <Reaction conditions> In step (iia), if the temperature is too low, a sufficient reaction rate cannot be obtained, and conversely, if the temperature is too high, the hydrolysis reaction between the electron-withdrawing group-substituted olefin (V) and the product azafluorene monomer (1a) tends to proceed easily. Therefore, it is preferable to control the temperature. Specifically, the lower limit of the reaction temperature is usually -20°C, preferably -10°C, and more preferably -5°C. On the other hand, the upper limit of the reaction temperature is usually 40°C, preferably 30°C, more preferably 20°C, and particularly preferably 5°C.

[0147] The lower limit of the reaction time in step (iia) is generally 15 minutes, preferably 30 minutes, and more preferably 1 hour. The upper limit of the reaction time is not particularly limited, but is generally 20 hours, preferably 10 hours, and more preferably 5 hours.

[0148] <Isolation and purification of the target product> The target azafluorene monomer (1a) is separated and purified, for example, as follows. First, after the reaction is completed, the by-product metal halide and the remaining inorganic base are removed from the reaction solution by filtration. Then, the target azafluorene monomer (1a) is precipitated and isolated by concentrating the solvent or adding a poor solvent for the target product.

[0149] After the reaction is completed, the reaction solution may be extracted with acidic water and a solvent in which the target azafluorene monomer (1a) is soluble. The target product extracted with the solvent can be isolated by concentrating the solvent or by adding a poor solvent. The solvent that can be used during extraction is not particularly limited as long as it dissolves the target azafluorene monomer (1a). Specifically, aromatic hydrocarbon compounds such as toluene and xylene; halogen-based solvents such as dichloromethane and chloroform, etc., can be used. One or more types of solvents can be used.

[0150] The azafluorene monomer (1a) obtained here can be used as it is as a raw material monomer for polyester or polyestercarbonate, or as a precursor for a raw material monomer for polycarbonate, but it may be purified before use. The purification method is not particularly limited, and a normal purification method can be adopted. Specifically, purification is performed by recrystallization, reprecipitation, extraction purification, column chromatography, etc. In addition, the azafluorene monomer (1a) can be dissolved in a suitable solvent and treated with activated carbon (specifically, purification). The solvent that can be used in this case is the same as the solvent that can be used in the extraction.

[0151] When the azafluorene monomer (1a) obtained here has a carboxy group, the azafluorene monomer (1a) having a carboxy group can be used, for example, as a raw material monomer for polyester or polyestercarbonate, or as a precursor for a raw material monomer for polycarbonate. Also, it can be converted into an azafluorene monomer (1a) having an ester group by an esterification reaction.

[0152] <Step (iib): Method for producing azafluorene monomer (1b) by alkylation reaction> The azafluorene monomer (1b) can be produced by an alkylation reaction of the azafluorene compound (II) with an alkylating agent (VI-1) and an alkylating agent (VI-2) in the presence of a base.

[0153] [ka]

[0154] In the formula, A 1 ~A 8 , R 1 ~R 11 and n is A in formula (7) and formula (8). 1 ~A 8 , R 1 ~R 11 and n are the same as those for n. X represents a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine), a mesyl group, and a tosyl group. Alkylation reactions of fluorenes are widely known, and for example, 9,9-bis(haloalkyl)fluorenes such as 9,9-bis(bromohexyl)fluorene and 9,9-bis(iodohexyl)fluorene have been reported (Gunin Saikia, Parameswar K. Iyer. “Facile CH Alkylation in Water: Enabling Defect-Free Materials for Optoelectronic Devices.” The Journal of Organic Chemistry, 1155 Sixteenth Street NW Washington, DC 20036, ACS Publications. ,18 March 2010. ,75, 8, p.2714-2717). Based on these findings, it is possible to synthesize azafluorene monomer (1b) using azafluorene compound (II) as a raw material.

[0155] The alkylating agent used in step (iib) includes methyl chloroacetate, methyl bromoacetate, methyl iodoacetate, ethyl chloroacetate, ethyl bromoacetate, ethyl iodoacetate, propyl chloroacetate, n-butyl chloroacetate, tert-butyl chloroacetate, tert-butyl bromoacetate, tert-butyl iodoacetate, methyl 2-chloropropionate, methyl bromo-2-propionate, methyl 2-iodopropionate, ethyl 2-chloropropionate, tert-butyl 2-chloropropionate, tert-butyl 2-bromopropionate, ethyl 2-bromopropionate, ethyl 2-iodo ... alkyl haloalkanoates such as methyl 3-chlorobutyrate, methyl 3-bromobutyrate, methyl 3-iodobutyrate, ethyl 3-chlorobutyrate, ethyl 3-chlorobutyrate, ethyl 3-iodobutyrate, and tert-butyl 2-iodopropionate; aryl haloalkanoates such as phenyl chloroacetate, phenyl bromoacetate, and phenyl iodoacetate; and alkyl halobenzoates such as methyl 4-chloromethylbenzoate, methyl 4-bromomethylbenzoate, ethyl 4-chloromethylbenzoate, ethyl 4-bromomethylbenzoate, methyl 3-chloromethylbenzoate, and methyl 3-bromomethylbenzoate.

[0156] <Step (iic): In formula (8), R 11 , R 12 is a group having a hydroxy ester group (method for producing azafluorene dihydroxy ester (1c) by transesterification of azafluorene monomer (1))> The azafluorene dihydroxyester compound represented by the following general formula (1c) is produced from an azafluorene monomer (1) and a diol (VII) in the presence of a base according to the following step (iic).

[0157] [ka]

[0158] In the formula, A 1 ~A 8 , R 1 ~R 12and n is A in formula (7) and formula (8). 1 ~A 8 , R 1 ~R 12 and n. R iv represents an organic substituent having 1 to 10 carbon atoms.

[0159] <Diol> The diol (VII) used in step (iic) represents a diol having 1 to 10 carbon atoms. Specific examples include chain alkylene diols (which may be linear or branched) such as ethylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol; cyclic alkylene diols such as cyclohexanedimethanol; oligoethylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol; secondary diols such as isosorbide; and aromatic diols such as resorcinol. These diols may be substituted with any substituent within the range that does not inhibit the reaction.

[0160] Among these, alkylene glycols and oligoethylene glycols are preferred from the viewpoints of reaction rate and cost, and ethylene glycol is particularly preferred. In the step (iic), it is possible to use two or more different diols (VII). However, for the sake of simplicity in purification, one type of diol (VII) is usually used. The amount of diol (VII) used is such that the reaction proceeds faster because the alcohol generated from the organic substituent of the ester group of the raw material azafluorene monomer (1) tends to compete with the added diol (VII). In addition, the amount of diol (VII) used is larger, and the reaction can be suppressed by using a larger amount of diol (VII) to suppress the generation of a by-product in which azafluorene is crosslinked with diol, as shown in the following general formula (VIII). This self-transesterification product (VIII) itself acts as a polycarbonate raw material containing polyester carbonate, or a polyester raw material, so even if it is contained in the azafluorene dihydroxyester compound (1c), it is considered that there is no significant problem as a polycarbonate raw material, polyester raw material, or polyester carbonate raw material. However, from the viewpoint of the quality of polycarbonate, polyester, and polyester carbonate, the content of the self-transesterification product (VIII) is usually 0.1 times by mole or less, preferably 0.05 times by mole or less, more preferably 0.03 times by mole or less, based on the azafluorene dihydroxyester compound (1c) of the product. The amount of the diol (VII) used is usually 3 times by mole or more, preferably 10 times by mole or more, more preferably 50 times by mole or more, based on the azafluorene monomer (1).

[0161] [ka]

[0162] In the formula, A 1 ~A 8 , R 1 ~R 10 and n is A in the formula (7) and the formula (8). 1 ~A 8 , R 1 ~R 10 and n. R iv represents an organic substituent having 1 to 10 carbon atoms.

[0163] The diol (VII) may be added at once during the charging or may be added in portions as the reaction proceeds. The self-transesterification product represented by the general formula (VIII) can be converted to an azafluor dihydroxyester compound (1c) by the addition of the diol (VII). <base> Examples of the base used in step (iic) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.; alkaline earth metal hydroxides such as calcium hydroxide, barium hydroxide, etc.; alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.; alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate, etc.; alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate, potassium phosphate, etc.; organic lithium salts such as n-butyllithium, tert-butyllithium, etc.; alkali metal alkoxide salts such as sodium methoxide, sodium ethoxide, potassium tert-butyloxide, etc.; alkali metal hydrides such as sodium hydride and potassium hydride; and quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, etc.

[0164] These bases may be used alone or in combination of two or more. Among these bases, alkali metal alkoxides are preferred from the standpoint of cost and reactivity, and sodium methoxide or sodium ethoxide is particularly preferred. The upper limit of the amount of base used is not particularly limited, but if the amount of base used is too large, the burden of stirring and purification after the reaction tends to be large. Therefore, the amount of base used is 10 times or less by mole, preferably 5 times or less by mole, and more preferably 1 time or less by mole of the azafluorene monomer (1).

[0165] On the other hand, if the amount of base used is too small, the reaction tends to proceed slowly, so the amount of base used is usually 0.01 times by mole or more, preferably 0.05 times by mole or more, and more preferably 0.1 times by mole or more, based on the amount of the raw material azafluorene monomer (1).

[0166] <Solvent> The step (iic) may be carried out without a solvent. However, when the azafluorene monomer (1) as the raw material has low solubility in the diol (VII) as the reaction agent and low reactivity with the diol, the step (iic) may be carried out using a solvent.

[0167] Specific examples of solvents that can be used include alkylnitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tertiary butyl methyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; halogenated solvents such as 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide and sulfolane; and monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane (note that monocyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbon). Derivatives of monocyclic aliphatic hydrocarbons such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, and 1,3,5-trimethylcyclohexane; polycyclic aliphatic hydrocarbons such as decalin (polycyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbon); noncyclic aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane; and aromatic hydrocarbons such as toluene, p-xylene, o-xylene, and m-xylene. These solvents may be used alone or in combination of two or more.

[0168] Among these solvents, ether solvents are preferred because the reaction tends to proceed well when a solvent that is highly soluble in both the raw materials azafluorene monomer (1) and diol (VII) is used. Diethylene glycol dimethyl ether or triethylene glycol dimethyl ether is particularly preferred because it allows the reaction to proceed at high temperatures.

[0169] The upper limit of the amount of the solvent used is not particularly limited, but in consideration of the production efficiency of the target product per reactor, it is usually 20 times, preferably 15 times, and more preferably 10 times the volume of the raw material azafluorene monomer (1). On the other hand, if the amount of the solvent used is too small, the solubility of the reagents decreases, making stirring difficult and the reaction tends to proceed slowly, so the lower limit is usually 1 times, preferably 2 times, and more preferably 4 times the volume of the raw material azafluorene monomer (1).

[0170] <Reaction format> When carrying out the step (iic), the reaction type is not particularly limited, and may be a batch reaction, a flow reaction, or a combination thereof. <Reaction conditions> When the solvent or diol (VII) as a reaction agent contains water, hydrolysis of the ester proceeds, and dicarboxylic acid (IX) or hydroxycarboxylic acid (X) as shown below tends to be generated as a by-product. The amount of by-products tends to increase with an increase in the amount of water. In order to suppress the generation of by-products, it is preferable to use an anhydrous solvent or diol (VII) as a reaction agent, or to carry out azeotropic dehydration using a solvent such as toluene or xylene that is not involved in the reaction and forms an azeotrope with water before the reaction.

[0171] [ka]

[0172] In the formula, A 1 ~A 8 , R 1 ~R10 and n is A in the formula (7) and the formula (8). 1 ~A 8 , R 1 ~R 10 and n. R iv represents an organic substituent having 1 to 10 carbon atoms.

[0173] The dicarboxylic acid (IX) and the hydroxycarboxylic acid (X) can also be used as a raw material for polycarbonates including polyester carbonates, or as a raw material for polyesters. In step (iic), if the temperature is too low, a sufficient reaction rate tends not to be obtained. Therefore, the lower limit of the reaction temperature is usually 20°C, preferably 50°C, more preferably 80°C. On the other hand, the upper limit is usually 150°C, preferably 120°C, more preferably 100°C.

[0174] The lower limit of the reaction time in step (iic) is generally 1 hour, preferably 2 hours, more preferably 4 hours. The upper limit of the reaction time is not particularly limited, but is generally 30 hours, preferably 20 hours, more preferably 10 hours. <Isolation and purification of the target product> The target azafluor dienylene hydroxyester compound (1c) is separated and purified, for example, as follows. First, after the reaction is completed, the by-product metal halide and insoluble matters such as remaining inorganic base are removed from the reaction solution by filtration. Then, the target azafluor dienylene hydroxyester compound (1c) is precipitated and isolated by concentrating the solvent or adding a poor solvent for the target compound.

[0175] After the reaction is completed, the reaction solution may be extracted with acidic water and a solvent capable of dissolving the target azafluor dihydroxyester compound (1c). The target product extracted with the solvent can be isolated by concentrating the solvent or adding a poor solvent. The target product extracted with the solvent can be washed with an aqueous solution of sodium carbonate, potassium carbonate, or the like to remove the by-product carboxylic acid.

[0176] The solvent that can be used during extraction is not particularly limited as long as it dissolves the target azafluor dihydroxyester compound (1c). Specifically, ester solvents such as ethyl acetate, aromatic hydrocarbon compounds such as toluene and xylene, and halogen-based solvents such as dichloromethane and chloroform can be used. One or more solvents can be used.

[0177] The azafluor dioxy ester compound (1c) can be used as it is for polymerization as a raw material for polycarbonate containing polyester carbonate or as a raw material for polyester, or can be used after purification. The purification method is not particularly limited, and a conventional purification method can be adopted. Specifically, purification is performed by recrystallization, reprecipitation, extraction purification, etc. Also, the azafluor dioxy ester compound (1c) can be dissolved in a suitable solvent and treated with activated carbon (specifically, purification). The solvent that can be used in this case is the same as the solvent that can be used in the extraction.

[0178] <Production method of azafluorendi aryl ester compound of general formula (1d) (production method of azafluorendi aryl ester compound (1d) by transesterification after synthesis of azafluorendi ester compound (1))> The azafluorene diaryl ester compound (1d) can be produced by a method including steps (iia) and (iib) of synthesizing the azafluorene diaryl ester compound (1) and a subsequent transesterification reaction with a diaryl carbonate (XI) (step (iid)).

[0179] [ka]

[0180] In the formula, A 1 ~A 8 , R 1 ~R 12 and n is A in formula (7) and formula (8). 1 ~A 8 , R1 ~R 12 and n is the same as Ar. Ar represents an aryl group having 6 to 11 carbon atoms.

[0181] <Diaryl carbonates (XI)> Diaryl carbonates (XI) are reaction reagents. Examples of aryl carbonates (XI) include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, and bis(biphenyl) carbonate. Among these, diphenyl carbonate is preferred because it is inexpensive and industrially available. These diaryl carbonates may be used alone or in combination of two or more.

[0182] The upper limit of the amount of diaryl carbonates (XI) used is not particularly limited. However, if the amount used is too large relative to the raw material azafluorene monomer (1), the purification load after the reaction tends to be large. Therefore, the amount of diaryl carbonates (XI) used is usually 20 times the molar amount of the azafluorene monomer or less, preferably 10 times the molar amount, more preferably 5 times the molar amount. On the other hand, if the amount of diaryl carbonates (XI) used is too small, it may remain in the product of the raw material azafluorene monomer (1), or an azafluorene monoaryl ester compound (1e) as shown below may be generated as an intermediate and remain in the final product. In order to suppress this, the amount of diaryl carbonates (XI) used is usually 1 time the molar amount or more, preferably 1.5 times the molar amount or more, more preferably 2 times the molar amount of the raw material azafluorene monomer (1).

[0183] [ka]

[0184] In the formula, A 1 ~A 8 , R 1 ~R 11 and n is A in the formula (7) and the formula (8). 1 ~A8 , R 1 ~R 11 and n is the same as Ar. Ar represents an aryl group having 6 to 11 carbon atoms.

[0185] <Transesterification catalyst> Examples of the transesterification catalyst include titanium compounds such as tetrabutoxytitanium, tetraisobutoxytitanium, tetramethoxytitanium, tetraisopropoxytitanium, tetraethoxytitanium, tetrakis(2-ethylhexyloxy)titanium, tetrastearyloxytitanium, tetraphenoxytitanium, titanium(IV) acetylacetonate, and titanium(IV) diisopropoxide bis(acetylacetonate); alkali metal compounds such as lithium carbonate, dibutylaminolithium, lithium acetylacetonate, sodium phenoxide, and potassium phenoxide; cadmium compounds such as cadmium acetylacetonate and cadmium carbonate; zirconium compounds such as zirconium acetylacetonate and zirconocene; lead compounds such as lead sulfide, lead hydroxide, lead salts, zinc salts, lead carbonate, lead acetate, tetrabutyl lead, tetraphenyl lead, triphenyl lead, dimethoxy lead, and diphenoxy lead; copper acetate, copper bisacetylacetonate, and copper oleate. copper compounds such as butyl copper, dimethoxy copper, and copper chloride; iron compounds such as iron hydroxide, iron carbonate, triacetoxy iron, trimethoxy iron, and triphenoxy iron; zinc compounds such as zinc bisacetylacetonate, diacetoxy zinc, dimethoxy zinc, diethoxy zinc, and diphenoxy zinc; organic tin compounds such as di-n-butyltin oxide, diphenyltin oxide, di-n-ocrylyl tin oxide, di-n-butyltin dimethoxide, di-n-butyltin diacrylate, di-n-butyltin dimethacrylate, di-n-butyltin dilaurate, tetramethoxytin, tetraphenoxytin, and tetrabutyl-1,3-diacetoxydistannoxane; aluminum compounds such as aluminum acetate, aluminum methoxide, aluminum ethoxide, and aluminum phenoxide; vanadium compounds such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, and vanadium sulfate; and phosphonium salts such as tetraphenylphosphonium phenoxide. These may be used alone or in combination of two or more.

[0186] Among these, it is preferable to use phosphonium salts, lithium compounds, zirconium compounds, organotin compounds, titanium compounds, and the like, because they are industrially inexpensive and have advantages in terms of reaction operation, and among these, organotin compounds and titanium compounds are particularly preferable.

[0187] The upper limit of the amount of the transesterification reaction catalyst used is not particularly limited, but if the amount used is too large, the burden of purification after the reaction will increase. Therefore, the amount used is usually 20 mol % or less, preferably 10 mol % or less, and more preferably 5 mol % or less, based on the azafluorene monomer (1). On the other hand, if the amount of the transesterification catalyst used is too small, the reaction time may become too long, so the amount of the transesterification catalyst used is usually 0.1 mol % or more, preferably 0.5 mol % or more, and more preferably 1 mol % or more, based on the raw material azafluorene monomer.

[0188] <Solvent> In step (iid), a reaction solvent may be used, but it is preferable to carry out the reaction using only the raw materials azafluorene monomer (1), diaryl carbonates (XI), and the transesterification catalyst without using a reaction solvent. However, when the raw materials azafluorene monomer (1) and diaryl carbonates (XI) are solid at room temperature and difficult to stir, a reaction solvent may be used. When a reaction solvent is used, the type is not limited as long as it is a solvent that can suitably dissolve and / or disperse the raw materials azafluorene monomer (1), diaryl carbonates (XI), and the transesterification catalyst.

[0189] Specific examples of solvents that can be used include alkylnitrile solvents such as acetonitrile and propionitrile; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, and tertiary butyl methyl ether; halogenated solvents such as 1,2-dichloroethane, dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and 1,2-dichlorobenzene; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxide solvents such as dimethylsulfoxide and sulfolane; monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane (note that monocyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbon); methylcyclopentane, ethylcyclopentane, methylcyclohexane, and the like. Derivatives of monocyclic aliphatic hydrocarbons such as ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, and 1,3,5-trimethylcyclohexane; polycyclic aliphatic hydrocarbons such as decalin (note that polycyclic aliphatic hydrocarbons are a type of cyclic aliphatic hydrocarbon); acyclic aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane; aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, and 1,2,3,4-tetrahydronaphthalene; and aromatic heterocycles such as pyridine. These solvents may be used alone or in combination of two or more.

[0190] The reaction in step (iid) is preferably carried out at a high temperature of 100° C. or higher. Therefore, among the above-mentioned solvents, chlorobenzene, 1,2-dichlorobenzene, trichlorobenzene, toluene, p-xylene, o-xylene, m-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, or sulfolane, which are solvents having a boiling point of 100° C. or higher, are preferred. 1,2-dichlorobenzene, xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, or 1,2,3,4-tetrahydronaphthalene or decahydronaphthalene are particularly preferred because they can suitably dissolve the raw material azafluor diester compound (1), have a boiling point of 130° C. or higher, and therefore allow the reaction at a higher temperature.

[0191] The upper limit of the amount of the solvent used is not particularly limited, but from the viewpoint of improving the production efficiency of the target product per reactor, the upper limit of the amount of the solvent used is usually 15 times, preferably 10 times, more preferably 5 times the volume of the raw material azafluorene monomer (1). On the other hand, if the amount of the solvent used is too small, the solubility of the reagent is deteriorated, making stirring difficult and slowing down the progress of the reaction. Therefore, the lower limit of the amount of the solvent used is usually 0.5 times, preferably 1 time, more preferably 2 times the volume of the raw material azafluorene monomer (1).

[0192] <Reaction format> When carrying out the step (iid), the reaction type is not particularly limited, and may be a batch type reaction, a flow type reaction, or a combination thereof.

[0193] <Reaction conditions> In the reaction of step (iid), if the temperature is too low, a sufficient reaction rate tends not to be obtained. Therefore, the lower limit of the reaction temperature is usually 50°C, preferably 70°C, more preferably 100°C. On the other hand, the upper limit of the reaction temperature is usually 250°C, preferably 200°C, more preferably 180°C. The lower limit of the reaction time in step (iid) is usually 1 hour, preferably 2 hours, more preferably 3 hours. The upper limit of the reaction time is not particularly limited, but is usually 30 hours, preferably 20 hours, more preferably 10 hours. In step (iid), in order to shift the equilibrium to the product side, the reaction may be carried out while distilling off by-products under reduced pressure. When the pressure is reduced, the pressure is usually 20 kPa or less, preferably 10 kPa or less, more preferably 5 kPa or less. On the other hand, if the pressure is reduced too much, the diaryl carbonate used as a reagent may sublime. From the viewpoint of suppressing sublimation, the pressure is usually 0.1 kPa or more, preferably 0.5 kPa or more, more preferably 1.0 kPa or more.

[0194] <Isolation and purification of the target product> After the reaction is completed, a poor solvent is added to the reaction solution to precipitate and isolate the target azafluorene diaryl ester monomer (1d). After the reaction is completed, the target azafluorene diaryl ester monomer (1d) may be extracted by adding a solvent in which the target azafluorene diaryl ester monomer (1d) is soluble and water to the reaction solution. The target extracted by the solvent is isolated by concentrating the solvent or adding a poor solvent.

[0195] The obtained azafluorene diaryl ester monomer (1d) can be used as it is for polymerization as a polycarbonate raw material containing polyester carbonate or as a polyester raw material, or it can be used after purification. The purification method is not particularly limited, and a conventional purification method can be adopted. Specifically, purification is performed by recrystallization, reprecipitation, extraction purification, column chromatography, etc.

[0196] <Method for producing diol compound of general formula (7)> (Method for producing diol compound (7) by synthesis of diester compound (8) followed by reduction reaction) The method for producing the diol compound (7) is not particularly limited. For example, the diol compound (7) can be obtained by subjecting a diester compound (8) as a starting material to a reduction reaction. [ka]

[0197] The synthesis of diols by reduction of esters is well known, and in US Patent Application Publication No. 2012 / 0170118, diols are produced by reduction of esters using lithium aluminum hydride as a reducing agent. As metal hydrides, diisobutylaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc. can also be used. Reduction of esters by catalytic hydrogenation using ruthenium, rhodium, palladium, or platinum as a catalyst is also a widely known method.

[0198] (In the general formula (7), R 9 is a methylene group) R 9 The diol compound (7), in which R is a methylene group, can be produced from the azafluorene compound (II) and a formaldehyde in the presence of a base.

[0199] <Formaldehyde> The formaldehyde is not particularly limited as long as it is a substance capable of supplying formaldehyde to the reaction system.Specific examples include gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde polymerized from formaldehyde, trioxane, etc.It is preferable to use paraformaldehyde because it is industrially inexpensive and powdery, making it easy to operate and capable of being weighed accurately.

[0200] There is no particular upper limit on the amount of formaldehyde used, but if the amount used is too large, the purification load after the reaction tends to be large, so the amount of formaldehyde used is usually 20 times or less by mole, preferably 10 times or less by mole, and more preferably 5 times or less by mole, relative to the azafluorene compound (II). The lower limit is theoretically 2 times by mole relative to the raw material, so the amount of formaldehyde used is usually 2 times or more by mole. In order to speed up the reaction and not leave raw materials or intermediates, there is no problem in using a formaldehyde in a slightly excessive amount relative to the raw material azafluorene compound (II). From this viewpoint, the amount of formaldehyde used is preferably 2.1 times or more by mole, more preferably 2.2 times or more by mole, relative to the raw material oligofluorene compound (II). <base> Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide; carbonates of alkali metals such as sodium carbonate, sodium hydrogen carbonate, and potassium carbonate; carbonates of alkaline earth metals such as magnesium carbonate and calcium carbonate; alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate, and potassium phosphate; organic lithium salts such as n-butyl lithium and tertiary butyl lithium; alkoxide salts of alkali metals such as sodium methoxide, sodium ethoxide, and potassium tertiary butyl oxide; alkali metal hydrides such as sodium hydride and potassium hydride; tertiary amines such as triethylamine and diazabicycloundecene; and quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. These may be used alone or in combination of two or more.

[0201] From the viewpoint of exhibiting sufficient basicity in this reaction, the base is preferably an alkali metal alkoxide. Furthermore, from the viewpoint of being industrially inexpensive, the base is more preferably sodium methoxide or sodium ethoxide. The alkali metal alkoxide may be in the form of a powder or a liquid such as an alcohol solution. The alkoxide may also be prepared by reacting an alkali metal with an alcohol.

[0202] If an excess amount of base is used, the decomposition reaction of the diol compound (7) tends to proceed. Therefore, the amount of base used is usually 1 mole or less, preferably 0.5 mole or less, more preferably 0.2 mole or less, relative to the raw material azafluorene compound (II). On the other hand, if the amount of base used is too small, the reaction proceeds slowly, so the amount of base used is usually 0.01 mole or more, preferably 0.05 mole or more, relative to the raw material azafluorene compound (II).

[0203] It is preferable to use a solvent for the synthesis reaction. Examples of solvents that can be used are as follows. Specifically, acetonitrile, propionitrile, etc. are used as alkylnitrile solvents. Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are used as ketone solvents. As ester solvents, linear esters such as methyl acetate, ethyl acetate, propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl lactate, ethyl lactate, etc.; cyclic esters such as γ-butyrolactone, chaprolactone, etc.; ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol-1-monomethyl ether acetate, propylene glycol-1-monoethyl ether acetate, etc. are used. As the ether solvent, diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tertiary butyl methyl ether, etc. are used. As the halogen solvent, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc. are used. As the halogen aromatic hydrocarbon, chlorobenzene, 1,2-dichlorobenzene, etc. are used. As the amide solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. are used. As the sulfoxide solvent, dimethyl sulfoxide, sulfolane, etc. are used.Examples of cyclic aliphatic hydrocarbons include monocyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; derivatives of monocyclic aliphatic hydrocarbons such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, and 1,3,5-trimethylcyclohexane; polycyclic aliphatic hydrocarbons such as decalin; and noncyclic aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, and n-tetradecane. Examples of aromatic hydrocarbons include toluene, p-xylene, o-xylene, and m-xylene. As the alcohol solvent, methanol, ethanol, isopropanol, n-butanol, tertiary butanol, hexanol, octanol, cyclohexanol, etc. can be used.

[0204] Among the above-mentioned solvents, polar amide solvents or sulfoxide solvents are preferred, and N,N-dimethylformamide is particularly preferred, from the viewpoint that the solubility of anions generated from the azafluorene compound (II) is high and the reaction tends to proceed well. As the solvent, one type may be used, or two or more types may be used. The upper limit of the amount of the solvent used is not particularly limited, but from the viewpoint of the production efficiency of the target product per reactor, it is usually 10 times the volume of the raw material azafluorene compound (II), preferably 7 times the volume, and more preferably 4 times the volume. On the other hand, if the amount of the solvent used is too small, stirring becomes difficult and the reaction tends to proceed slowly. Therefore, the lower limit of the amount of the solvent used is usually 1 times the volume of the raw material azafluorene compound (II), preferably 2 times the volume, and more preferably 3 times the volume.

[0205] <Reaction format> The reaction may be carried out in a batch reaction, a flow reaction, or a combination of the two, and the reaction may be carried out in any manner without any particular limitation. In the case of a batch reaction, it is preferable to add the base little by little after adding the raw material azafluorene compound (II), formaldehyde, and a solvent, since it is known that the decomposition reaction is likely to proceed if the base is added all at once at the start of the reaction.

[0206] <Reaction conditions> If the temperature is too low, a sufficient reaction rate cannot be obtained, and conversely, if the temperature is too high, the decomposition reaction tends to proceed, so it is preferable to control the reaction temperature. When using the optimal solvent, N,N-dimethylformamide, and the optimal base, sodium ethoxide, the lower limit of the reaction temperature is usually -50°C and the upper limit is usually 30°C. Specifically, R 10 When R is a methylene group and n=1, the upper limit of the reaction temperature is preferably 20° C., more preferably 10° C. On the other hand, the lower limit is preferably −20° C., more preferably 0° C. or higher. 3 When R is an ethylene group and n=1, the upper limit of the reaction temperature is preferably 25° C., more preferably 20° C. On the other hand, the lower limit is preferably 0° C., more preferably 10° C. 10 When is a methylene group and n=2, the upper limit of the reaction temperature is preferably 25° C., more preferably 20° C. On the other hand, the lower limit is preferably 0° C., more preferably 10° C.

[0207] <Isolation and purification of the target product> After the reaction is completed, the target diol compound (7) can be isolated by adding the reaction solution to an acidic water such as dilute hydrochloric acid, or by adding an acidic water such as dilute hydrochloric acid to the reaction solution and precipitating it. Alternatively, after the reaction is completed, a solvent in which the target diol compound (7) is soluble and water can be added to the reaction solution to extract it. The target product extracted with the solvent can be isolated by concentrating the solvent or adding a poor solvent.

[0208] The obtained diol compound (7) can be used as it is for polymerization as a polymer raw material, but it may be polymerized after purification. The purification method is not particularly limited, and a conventional purification method can be adopted, specifically, recrystallization, reprecipitation, extraction purification, column chromatography, etc. can be adopted.

[0209] The presence of metal components often has an adverse effect on the polymerization reaction. The content ratio of metals of Group 1 and Group 2 of the long periodic table in the monomer is preferably 500 mass ppm or less, more preferably 200 mass ppm or less, further preferably 50 mass ppm or less, and particularly preferably 10 mass ppm or less. In order to remove metal components, a liquid separation operation is generally very effective, but since the target diol compound (7) dissolves in highly polar solvents such as N,N-dimethylformamide and tetrahydrofuran, a liquid separation operation performed in a two-layer system is very difficult. On the other hand, even if a normal purification treatment is performed in which the precipitate after the reaction is stopped is washed with water or an arbitrary solvent (liquid) is added to the precipitate, heated, suspended, and washed, it is difficult to sufficiently remove the contaminated metal components, and metal components of the order of several hundreds of mass ppm may remain in the precipitate. Therefore, a method in which the reaction precipitate containing impurities is dissolved in a highly polar solvent such as N,N-dimethylformamide or tetrahydrofuran, and then water is added to the solution to cause precipitation is preferable as a simple and effective method for removing inorganic salts (i.e., a purification method).

[0210] <Specific examples of azafluorene monomers> In the formula (7), specific examples of the azafluorene monomer where n=0 include those shown in the following group [N].

[0211] [ka]

[0212] [ka]

[0213] Specific examples of preferred azafluorene diaryl ester monomers include those shown in the following group "O".

[0214] [ka]

[0215] The resin of the present disclosure can exhibit desired optical properties by adjusting the content ratio of the structural unit (a) in the resin to a specific range. The content of the structural unit (a) in the resin is preferably 1% by weight or more and 70% by weight or less with respect to the weight of the entire resin. Methods for adjusting the ratio of the structural unit (a) in the resin include, for example, a method of copolymerizing a monomer having the structural unit (a) with another monomer, and a method of blending a resin containing the structural unit (a) with another resin. The method of copolymerizing a monomer having the structural unit (a) with another monomer is preferred because it allows precise control of the content of the structural unit (a), high transparency is obtained, and uniform properties are obtained over the entire surface of the film.

[0216] In order to obtain a positive refractive index anisotropy and sufficient reverse wavelength dispersion, the content ratio of the structural unit (a) is preferably 40% by weight or less, more preferably 25% by weight or less, and particularly preferably 20% by weight or less. In this case, the photoelastic coefficient and its stability are good, and a sufficiently high birefringence can be obtained by stretching. In addition, in this case, the proportion of the structural unit (a) in the resin is small, so the range of molecular design is widened, and when modification of the resin is required, improvement is easy. In addition, the content ratio of the structural unit (a) is preferably 5% by weight or more, more preferably 10% by weight or more. In this case, the optical properties do not change sensitively according to a slight variation in the content of the structural unit (a), and it is easy to manufacture the resin so that the various properties fall within a certain range.

[0217] In addition, the structural unit (a) is a structural unit having a high refractive index, and by using the structural unit (a), the resin becomes suitable for high refractive index lens applications. In this case, from the viewpoint of imparting the resin with a high refractive index as well as appropriate heat resistance and fluidity, the content ratio of the structural unit (a) in the resin is preferably 65% ​​by weight or less, more preferably 60% by weight or less. In this case, the content ratio of the structural unit (a) in the resin is preferably 20% by weight or more, more preferably 30% by weight or more.

[0218] The resin of the present disclosure is preferably obtained by copolymerizing a monomer that is a raw material of the structural unit (a) with another monomer. Examples of the other monomers to be copolymerized include dihydroxy compounds and diester compounds. In order to develop the desired reverse wavelength dispersion, it is preferable to incorporate a structural unit having positive birefringence into the polymer structure together with the structural unit (a) having negative birefringence. Therefore, the other monomers to be copolymerized are preferably dihydroxy compounds or diester compounds that are raw materials of the structural unit having positive birefringence.

[0219] The copolymerizable monomer may be a compound capable of introducing a structural unit containing an aromatic ring, or a compound not capable of introducing a structural unit containing an aromatic ring, i.e., a compound composed of an aliphatic structure. Specific examples of the compound composed of the aliphatic structure are given below. Dihydroxy compounds of linear aliphatic hydrocarbons such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; dihydroxy compounds of branched aliphatic hydrocarbons such as neopentyl glycol and hexylene glycol; dihydroxy compounds of secondary and tertiary alcohols of alicyclic hydrocarbons such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol; 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, and the like. Dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons such as candimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and limonene; oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol; dihydroxy compounds having a cyclic ether structure such as isosorbide; dihydroxy compounds having a cyclic acetal structure such as spiroglycol and dioxane glycol; alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Examples of primary alcohols of alicyclic hydrocarbons include dihydroxy compounds derived from terpene compounds.

[0220] Specific examples of compounds into which the structural unit containing an aromatic ring can be introduced are given below: 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)propane, )methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3-bis(4-hydroxyphenyl)pentane, Bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4, Aromatic bisphenol compounds such as 4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; dihydroxy compounds having an ether group bonded to an aromatic group such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone;Aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc.;

[0221] The aliphatic dicarboxylic acid and aromatic dicarboxylic acid components can be used as the raw materials for the polyester carbonate as dicarboxylic acids themselves, but depending on the production method, dicarboxylic acid esters such as methyl esters and phenyl esters, and dicarboxylic acid derivatives such as dicarboxylic acid halides can also be used as raw materials. In addition, as copolymerization monomers, dihydroxy compounds having a fluorene ring, such as 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, which are conventionally known as compounds having a structural unit with negative birefringence, and dicarboxylic acid compounds having a fluorene ring can also be used in combination with a monomer having the structural unit (a).

[0222] From the viewpoint of optical properties, the resin of the present disclosure preferably contains a structural unit that does not contain an aromatic component as a structural unit other than the structural unit (a). That is, it is preferable to use a compound composed of an aliphatic structure as a copolymerization monomer. Among the compounds composed of an aliphatic structure, a compound having an alicyclic structure is more preferable from the viewpoint of excellent mechanical properties and heat resistance. If an aromatic component is contained in the main chain of the polymer, as described above, the reverse wavelength dispersion of the azafluorene ring is offset, so that the content of the structural unit (a) must be increased, which may cause deterioration of the photoelastic coefficient and mechanical properties. By adopting a structural unit that does not contain an aromatic component as a structural unit other than the structural unit (a), it is possible to prevent the aromatic component from being incorporated into the main chain.

[0223] On the other hand, in order to ensure optical properties while balancing heat resistance, mechanical properties, etc., it may be effective to incorporate aromatic components into the main chain or side chain of the polymer. From the viewpoint of balancing various properties, it is preferable that the content of structural units containing aromatic groups (excluding structural unit (a)) in the resin is 5% by weight or less. Among the structural units that can be introduced by the compound having an alicyclic structure, the resin of the present disclosure particularly preferably contains at least one of a structural unit represented by the following formula (10) and a structural unit represented by the following formula (11) as a copolymerization component, from the viewpoints of optical properties, mechanical properties, heat resistance, etc. The structure represented by formula (10) and the structure represented by formula (11) are sometimes referred to as "structural unit (b)".

[0224] [ka]

[0225] [ka]

[0226] The dihydroxy compound capable of introducing the structural unit represented by the formula (10) includes isosorbide (ISB), isomannide, and isoidet, which are stereoisomers. These may be used alone or in combination of two or more. Among these, it is preferable to use ISB from the viewpoint of availability and polymerization reactivity. As a dihydroxy compound capable of introducing the structural unit of the above formula (11), spiroglycol can be used.

[0227] The resin of the present disclosure may contain either one of the structural units represented by the formula (10) and the structural units represented by the formula (11), or may contain both. In the resin of the present disclosure, the structural unit (b) is preferably contained in an amount of 10% by weight or more and 90% by weight or less. The content of the structural unit (b) in the resin is more preferably 85% by weight or less, and even more preferably 80% by weight or less. The content of the structural unit (b) in the resin is more preferably 50% by weight or more, even more preferably 60% by weight or more, and particularly preferably 70% by weight or more. If the content of the structural unit (b) is equal to or more than the lower limit, sufficient mechanical properties, flowability, and a low photoelastic coefficient can be obtained. On the other hand, if the content of the structural unit (b) is equal to or less than the upper limit, the reverse wavelength dispersion exhibited by the structural unit (a) is sufficient.

[0228] The resin of the present disclosure may contain a structural unit other than the structural unit (a) and the structural unit (b). Such a structural unit may be referred to as a "structural unit (c)". The resin contains at least the structural unit (a) and may further contain at least one of the structural unit (b) and the structural unit (c). As a monomer having the structural unit (c) (i.e., a monomer capable of introducing the structural unit (c) into a resin), it is preferable to use 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 1,4-cyclohexanedicarboxylic acid, or a derivative thereof, and more preferably 1,4-cyclohexanedimethanol or tricyclodecane dimethanol. Resins containing structural units derived from these monomers have an excellent balance of optical properties, heat resistance, mechanical properties, and the like. In addition, since the polymerization reactivity of diester compounds is relatively low, it is preferable not to use diester compounds other than those containing the structural unit (a) from the viewpoint of increasing the reaction efficiency.

[0229] The dihydroxy compound or diester compound for introducing the structural unit (c) is used alone or in combination of two or more depending on the required performance of the resin to be obtained. The content of the structural unit (c) in the resin is preferably 1% by weight or more and 50% by weight or less, more preferably 5% by weight or more and 40% by weight or less, and even more preferably 10% by weight or more and 30% by weight or less. The structural unit (c) plays a role in adjusting the heat resistance of the resin and imparting flexibility and toughness. Therefore, if the content of the structural unit (c) is too small, the mechanical properties and melt processability of the resin may be reduced. On the other hand, if the content of the structural unit (c) is too high, the heat resistance and optical properties may be reduced. In other words, by adjusting the content of the structural unit (c) to the above range, the mechanical properties and melt processability of the resin are improved, and further, the heat resistance and optical properties are improved.

[0230] [Method of producing resin of the present disclosure] The polycarbonate, polyester, and polyester carbonate that are preferably used as the resin of the present disclosure are produced, for example, by a commonly used polymerization method. That is, for example, the resin can be produced by a solution polymerization method or an interfacial polymerization method using phosgene or a carboxylic acid halide, or a melt polymerization method in which a reaction is carried out without using a solvent. Among these production methods, it is preferable to produce the resin by the melt polymerization method from the viewpoint of being able to produce the resin without using a solvent or a highly toxic compound, reducing the environmental load, and also from the viewpoint of excellent productivity.

[0231] When a solvent is used for polymerization, the glass transition temperature of the resin may be lowered due to the plasticizing effect of the remaining solvent in the resin. Therefore, it becomes difficult to control the molecular orientation to a constant level in the stretching process described below. In addition, when a halogen-based organic solvent such as methylene chloride remains in the resin, the resin may cause corrosion, and for example, corrosion may occur when a molded body of the resin is incorporated in an electronic device. Since the resin obtained by the melt polymerization method does not contain a solvent, it is advantageous for stabilizing the processing process and product quality.

[0232] When the resin is produced by the melt polymerization method, for example, a monomer having the structural unit (a), a copolymerization monomer such as a diol or diester, and a polymerization catalyst are mixed, and an ester exchange reaction is carried out under molten condition, and the reaction rate is increased while removing the elimination component from the system. At the end of the polymerization, the reaction is carried out under high temperature and high vacuum conditions until the desired molecular weight is reached. When the reaction is completed, the molten resin is extracted from the reactor. The resin obtained in this manner is used as a raw material for molded products such as retardation films.

[0233] In the present disclosure, the polycarbonate or polyester carbonate is obtained by polycondensing a monomer containing at least the structural unit (a), one or more dihydroxy compounds, and a carbonic acid diester as raw materials. The carbonic acid diester used in the polycondensation reaction is usually one represented by the general formula (6). These carbonic acid diesters may be used alone or in combination of two or more.

[0234] [ka]

[0235] In the formula (6), R 13 and R 14 R is an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms. 13 and R 14 may be the same or different. 13 and R 14 is preferably an optionally substituted aryl group, more preferably an unsubstituted aryl group. Examples of the substituent include an alkyl group, an ester group, an ether group, a carboxylic acid, an amide group, and a halogen atom.

[0236] Examples of the carbonic acid diester represented by the formula (6) include diphenyl carbonate (i.e., DPC) and substituted diphenyl carbonates such as ditolyl carbonate. Examples of the carbonic acid diester include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, and the like. The carbonic acid diester is preferably diphenyl carbonate or a substituted diphenyl carbonate, and more preferably diphenyl carbonate. The carbonic acid diester may contain impurities such as chloride ions. Such impurities may inhibit the polymerization reaction or deteriorate the hue of the polycarbonate, so it is preferable to use a carbonic acid diester that has been purified by distillation or the like, as necessary.

[0237] In the polycondensation reaction, the molar ratio of the total dihydroxy compounds and the diester compounds used in the reaction can be strictly adjusted to control the reaction rate and the molecular weight of the resulting resin. In the case of polycarbonate, the molar ratio of the carbonic acid diester to the total dihydroxy compounds is preferably adjusted to 0.90 to 1.10, more preferably adjusted to 0.95 to 1.07, and particularly preferably adjusted to 0.98 to 1.05. In the case of polyester, the molar ratio of the total diester compounds to the total dihydroxy compounds is preferably adjusted to 0.70 to 1.10, more preferably adjusted to 0.80 to 1.05, and particularly preferably adjusted to 0.85 to 1.00. In the case of polyester carbonate, the molar ratio of the total amount of the carbonic acid diester and the total diester compounds to the total dihydroxy compounds is preferably adjusted to 0.90 to 1.10, more preferably adjusted to 0.95 to 1.05, and particularly preferably adjusted to 0.97 to 1.02.

[0238] If the molar ratio is too far above or below the range, it may be impossible to produce a resin with the desired molecular weight. If the molar ratio is too small, the number of hydroxyl group terminals in the produced resin may increase, resulting in a decrease in the thermal stability of the resin. If the molar ratio is too large, the rate of the transesterification reaction may decrease under the same conditions, or the amount of residual carbonic acid diester or diester compound in the produced resin may increase. The residual low molecular weight components may volatilize during film formation or stretching of the resin, resulting in defects in the film.

[0239] The melt polymerization method is usually carried out in a multi-stage process of two or more stages. The polycondensation reaction may be carried out in two or more stages using one polymerization reactor by sequentially changing the conditions, or may be carried out in two or more stages using two or more reactors by changing the conditions for each stage, but from the viewpoint of production efficiency, it is usually carried out using two or more reactors, preferably three or more reactors. The polycondensation reaction may be carried out in a batch system, a continuous system, or a combination of a batch system and a continuous system, but from the viewpoint of production efficiency and stability of quality, a continuous system is preferred.

[0240] In the polycondensation reaction, it is preferable to appropriately control the balance between temperature and pressure in the reaction system. If either the temperature or pressure is changed too quickly, unreacted monomers may be distilled out of the reaction system. As a result, the molar ratio of the dihydroxy compound and the diester compound may change, and a resin with the desired molecular weight may not be obtained. The polymerization rate of the polycondensation reaction is controlled by the balance between the hydroxyl group terminal and the ester group terminal or carbonate group terminal. Therefore, particularly when polymerization is performed in a continuous manner, if the balance of the terminal groups fluctuates due to the distillation of unreacted monomers, it becomes difficult to control the polymerization rate at a constant rate, and the molecular weight of the resulting resin may fluctuate greatly. Since the molecular weight of the resin correlates with the melt viscosity, when the resulting resin is melt-formed into a film, the melt viscosity fluctuates, making it difficult to maintain the quality of the film, such as the film thickness, constant, which may lead to a decrease in the quality and productivity of the film.

[0241] Furthermore, when unreacted monomers are distilled off, not only the balance of the terminal groups but also the copolymerization composition of the resin deviates from the desired composition, which may affect the optical quality of the retardation film. In the retardation film of the present disclosure, the wavelength dispersion of the retardation described below is controlled by the ratio of the structural unit (a) and the copolymerization component in the resin, so if the ratio is disturbed during polymerization, the optical characteristics as designed may not be obtained, or when a long film is obtained, the optical characteristics may change depending on the position of the film, making it impossible to manufacture a polarizing plate of a certain quality.

[0242] Specifically, the following conditions can be adopted as the reaction conditions in the first stage reaction. That is, the maximum temperature of the inside of the polymerization reactor is usually set to 150°C or more, preferably 170°C or more, more preferably 190°C or more. The maximum temperature of the inside of the polymerization reactor is usually set to 250°C or less, preferably 240°C or less, more preferably 230°C or less. The pressure of the polymerization reactor is usually set to 70 kPa or less, preferably 50 kPa or less, more preferably 30 kPa or less. The pressure of the polymerization reactor is usually set to 1 kPa or more, preferably 3 kPa or more, more preferably 5 kPa or more. The pressure is absolute pressure. The reaction time is usually set to 0.1 hours or more, preferably 0.5 hours or more. The reaction time is usually set to 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less. The first stage reaction is carried out while distilling off the monohydroxy compound derived from the diester compound generated outside the reaction system. For example, when diphenyl carbonate is used as the carbonic acid diester, the monohydroxy compound distilled off from the reaction system in the first reaction step is phenol.

[0243] In the first stage reaction, the lower the reaction pressure, the more the polymerization reaction can be accelerated, but on the other hand, if the pressure is too low, a large amount of unreacted monomer will be distilled off. In order to suppress the distillation of unreacted monomer and accelerate the reaction by reducing the pressure, it is effective to use a reactor equipped with a reflux condenser. It is especially good to use a reflux condenser in the early stages of the reaction when there is a large amount of unreacted monomer.

[0244] In the second and subsequent reactions, the pressure of the reaction system is gradually lowered from the pressure of the first stage, and the monohydroxy compound generated is removed from the reaction system, and the pressure of the reaction system is finally set to 5 kPa or less, preferably 3 kPa or less, and more preferably 1 kPa or less. The maximum internal temperature is usually set to 210°C or more, preferably 220°C or more. The maximum internal temperature is usually set to 260°C or less, preferably 250°C or less, and particularly preferably 240°C or less. The reaction time is usually set to 0.1 hours or more, preferably 0.5 hours or more, and more preferably 1 hour or more. The reaction time is usually set to 10 hours or less, preferably 5 hours or less, and more preferably 3 hours or less. In order to suppress coloration and thermal deterioration and obtain a resin with good hue and thermal stability, the maximum internal temperature in all reaction stages is usually 260°C or less, preferably 250°C or less, and more preferably 240°C or less.

[0245] The transesterification catalyst (hereinafter, the "transesterification catalyst" may be referred to as the "catalyst" or "polymerization catalyst") that can be used during polymerization can have a very large effect on the reaction rate and the color tone and thermal stability of the resin obtained by polycondensation. The catalyst used is not limited as long as it can satisfy the transparency, hue, heat resistance, thermal stability, and mechanical strength of the produced resin, and examples of the catalyst include metal compounds of Group 1 or Group 2 of the long periodic table (hereinafter, Group 1 of the long periodic table will be referred to as "Group 1" and Group 2 of the long periodic table will be referred to as "Group 2"). Basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are included. Preferably, a compound of at least one metal selected from the group consisting of metals of Group 2 of the long periodic table and lithium is used.

[0246] As the Group 1 metal compound, for example, the following compounds can be used, but other Group 1 metal compounds can also be used: sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium tetraphenylborate, tetraphenylborate, potassium tetraphenylborate, lithium tetraphenylborate, cesium tetraphenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates and phenolates of sodium, potassium, lithium and cesium, and disodium, dipotassium, dilithium and dicesium salts of bisphenol A. Of these, it is preferable to use lithium compounds from the viewpoints of polymerization activity and the hue of the resulting polycarbonate.

[0247] As the Group 2 metal compound, for example, the following compounds can be used, but other Group 2 metal compounds can also be used: calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate. Of these, magnesium compounds, calcium compounds, and barium compounds are preferably used, and from the viewpoint of polymerization activity and the hue of the resulting polycarbonate, magnesium compounds and / or calcium compounds are more preferably used, and calcium compounds are particularly preferably used.

[0248] It is possible to use, in combination with the Group 1 metal compound and / or Group 2 metal compound, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound as an auxiliary, but it is particularly preferable to use at least one metal compound selected from the group consisting of metals in Group 2 of the long form periodic table and lithium. As the basic phosphorus compound, for example, the following compounds can be used, but other basic phosphorus compounds can also be used: triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, or a quaternary phosphonium salt.

[0249] As the basic ammonium compound, for example, the following compounds can be used, but other basic ammonium compounds can also be used: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N,N,N-trimethylethanolamine (choline), trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0250] As the amine compound, for example, the following compounds can be used, but other amine compounds can also be used: 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, and guanidine.

[0251] The amount of the polymerization catalyst used is usually 0.1 μmol to 300 μmol, preferably 0.5 μmol to 100 μmol, more preferably 1 μmol to 50 μmol per mol of the total dihydroxy compounds used in the polymerization. When at least one metal compound selected from the group consisting of metals of Group 2 of the long periodic table and lithium is used as the polymerization catalyst, particularly when a magnesium compound and / or a calcium compound is used, the amount of the polymerization catalyst used is usually 0.1 μmol or more, preferably 0.3 μmol or more, more preferably 0.5 μmol or more, per mol of the total dihydroxy compounds, in terms of the amount of metal. The amount of the polymerization catalyst used is usually 30 μmol or less, preferably 20 μmol or less, more preferably 10 μmol or less.

[0252] When a diester compound is used as a monomer to produce a polyester or polyester carbonate, a transesterification catalyst such as a titanium compound, a tin compound, a germanium compound, an antimony compound, a zirconium compound, a lead compound, an osmium compound, a zinc compound, or a manganese compound can be used in combination with or without the basic compound. The amount of these transesterification catalysts used is usually within the range of 1 μmol to 1 mmol, preferably within the range of 5 μmol to 800 μmol, and more preferably within the range of 10 μmol to 500 μmol, in terms of the amount of metal, relative to 1 mol of all dihydroxy compounds used in the reaction.

[0253] If the amount of catalyst is too small, the polymerization rate will be slow, and the polymerization temperature will have to be increased accordingly to obtain a resin with the desired molecular weight. As a result, the color of the resulting resin will likely deteriorate, and the unreacted raw materials will volatilize during polymerization, causing the molar ratio of the dihydroxy compound and the diester compound to be lost, and the resin may not reach the desired molecular weight. On the other hand, if the amount of polymerization catalyst used is too large, undesirable side reactions will occur, which may cause the color of the resulting resin to deteriorate or the resin to become discolored during molding.

[0254] Among the group 1 metals, sodium, potassium, and cesium may adversely affect the color if contained in a large amount in the resin. These metals may be mixed not only from the catalyst used, but also from the raw materials and reaction equipment. Regardless of the source, the total amount of compounds of these metals in the resin is usually 2 μmol or less, preferably 1 μmol or less, and more preferably 0.5 μmol or less per 1 mol of the total dihydroxy compounds.

[0255] The resin of the present disclosure can be polymerized as described above, and then cooled and solidified, and pelletized with a rotary cutter or the like. The pelletization method is not limited, but may be a method of extracting the resin in a molten state from the final polymerization reactor, cooling and solidifying it in the form of a strand, and pelletizing it. Alternatively, the resin may be supplied in a molten state from the final polymerization reactor to a single-screw or twin-screw extruder, melt-extruded, cooled and solidified, and pelletized. Alternatively, the resin may be extracted in a molten state from the final polymerization reactor, cooled and solidified in the form of a strand, pelletized once, and then supplied to a single-screw or twin-screw extruder again, melt-extruded, cooled and solidified, and pelletized.

[0256] The molecular weight of the resin thus obtained can be expressed by the reduced viscosity. If the reduced viscosity of the resin is too low, the mechanical strength of the molded product may be reduced. Therefore, the reduced viscosity is usually 0.20 dL / g or more, and preferably 0.30 dL / g or more. On the other hand, if the reduced viscosity of the resin is too high, the fluidity during molding decreases, and the productivity and moldability tend to decrease. Therefore, the reduced viscosity is usually 1.20 dL / g or less, preferably 1.00 dL / g or less, more preferably 0.80 dL / g or less, and particularly preferably 0.60 dL / g or less. The reduced viscosity is measured using methylene chloride as a solvent, precisely adjusting the polycarbonate concentration to 0.6 g / dL, and using an Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C.

[0257] When resins have the same composition, there is a correlation between the reduced viscosity and the melt viscosity of the resin, so that the stirring power of the polymerization reactor, the discharge pressure of the gear pump that transports the molten resin, etc. can usually be used as indicators for operation management. That is, when the indicated values ​​of the above-mentioned operating devices reach the target values, the polymerization reaction is stopped by returning the pressure of the reactor to normal pressure or by withdrawing the resin from the reactor. The melt viscosity of the resin of the present disclosure is 240°C at a shear rate of 91.2 sec -1 Under the measurement conditions, the melt viscosity of the resin is preferably 700 Pa·s or more and 5000 Pa·s or less, more preferably 4000 Pa·s or less, even more preferably 3000 Pa·s or less, and particularly preferably 2700 Pa·s or less. The melt viscosity of the resin is more preferably 1000 Pa·s or more, even more preferably 1500 Pa·s or more, and particularly preferably 2000 Pa·s or more. The melt viscosity is measured, for example, using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.).

[0258] The glass transition temperature of the resin of the present disclosure is preferably 110°C or more and 160°C or less. The glass transition temperature is more preferably 155°C or less, even more preferably 150°C or less, and particularly preferably 145°C or less. The glass transition temperature is more preferably 120°C or more, and even more preferably 130°C or more. When the glass transition temperature is above the lower limit, the heat resistance of the resin tends to be good, and for example, the dimensional change of the film after molding and the quality loss under the use conditions of the retardation film can be prevented. On the other hand, when the glass transition temperature is below the upper limit, the thickness unevenness of the film during film molding and the film becoming brittle are suppressed, and the stretchability is improved. Furthermore, the transparency of the film is good.

[0259] When a diester compound is used in the polycondensation reaction, the by-produced monohydroxy compound remains in the resin and volatilizes during film formation or stretching, causing odors that can worsen the working environment, contaminate the transport roll, etc., and may impair the appearance of the film. When diphenyl carbonate (DPC), a particularly useful carbonic acid diester, is used, the by-produced phenol has a relatively high boiling point and is not sufficiently removed even by reaction under reduced pressure, and is likely to remain in the resin. Therefore, the monohydroxy compound derived from the carbonic acid diester contained in the resin of the present disclosure is preferably 1500 ppm by weight or less, more preferably 1000 ppm by weight or less, and even more preferably 700 ppm by weight or less. In order to solve the above problem, the lower the content of the monohydroxy compound, the better, but it is difficult to reduce the monohydroxy compound remaining in the polymer to zero in the melt polymerization method, and excessive effort is required for removal. Usually, the above problem can be sufficiently suppressed by reducing the content of the monohydroxy compound to 1 ppm by weight.

[0260] In order to reduce low molecular weight components, including monohydroxy compounds derived from carbonic acid diesters, remaining in the resin of the present disclosure, it is effective to degas the resin in an extruder as described above and to reduce the pressure at the end of the polymerization to 3 kPa or less, preferably 2 kPa or less, and more preferably 1 kPa or less. When the pressure at the end of the polymerization is reduced, if the reaction pressure is reduced too much, the molecular weight may rise rapidly and the reaction may become difficult to control, so it is preferable to produce the resin with an excess of hydroxyl groups or excess of ester groups to bias the end group balance. When a diester compound is used as a monomer having structural unit (a) to synthesize polyester carbonate, the diester monomer having structural unit (a) is relatively low in reactivity, so that unreacted material is likely to remain. Therefore, by polymerizing the resin with an excess of hydroxyl groups, it is possible to increase the reaction rate of the diester monomer. That is, it is preferable to set the amount of ester terminals in the final polymer to 1 mol / ton or more and 70 mol / ton or less. The amount of ester terminals in the polymer is more preferably 50 mol / ton or less, and particularly preferably 30 mol / ton or less. The amount of ester terminals in the polymer is more preferably 5 mol / ton or more, and particularly preferably 10 mol / ton or more.

[0261] If necessary, a heat stabilizer can be blended into the resin of the present disclosure in order to prevent a decrease in molecular weight or deterioration in color during molding, etc. Examples of such heat stabilizers include commonly known hindered phenol-based heat stabilizers and / or phosphorus-based heat stabilizers. Examples of the hindered phenol compound that can be used include the following compounds: 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,5-di-tert-butylhydroquinone, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxyphenyl)propionate, and 2-tert-butyl-5-methyl-2'-hydroxyphenyl. dibenzyl)-4-methylphenyl acrylate, 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis-(6-cyclohexyl-4-methylphenol), 2,2'-ethylidene-bis-(2,4-di-tert-butylphenol), tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]-methane, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and the like. Among them, tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]-methane, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

[0262] As the phosphorus-based compound, for example, the following phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof can be used, but it is also possible to use phosphorus-based compounds other than these compounds: triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), benzene phosphonic acid dimethyl, benzene phosphonic acid diethyl, benzene phosphonic acid dipropyl. These heat stabilizers may be used alone or in combination of two or more.

[0263] The heat stabilizer may be added to the reaction liquid during melt polymerization, or may be added to the resin using an extruder and kneaded with the resin. When forming a film by melt extrusion, the heat stabilizer may be added to the extruder to form a film, or the heat stabilizer may be added to the resin in advance using an extruder and formed into pellets or the like. The amount of these heat stabilizers is, relative to 100 parts by weight of the resin used in the present disclosure, preferably 0.0001 parts by weight or more, more preferably 0.0005 parts by weight or more, even more preferably 0.001 parts by weight or more, and is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, and even more preferably 0.2 parts by weight or less.

[0264] The resin of the present disclosure may be blended with a commonly known antioxidant for the purpose of preventing oxidation, if necessary. As such an antioxidant, for example, the following compounds may be used, but other compounds may also be used. Pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl -2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane. The antioxidants may be used alone or in combination of two or more. The amount of these antioxidants to be added is preferably 0.0001 part by weight or more, and more preferably 0.5 part by weight or more, based on 100 parts by weight of the resin.

[0265] In addition to the heat stabilizer and antioxidant, the resin of the present disclosure may contain additives such as commonly used ultraviolet absorbers, release agents, antistatic agents, slip agents, lubricants, plasticizers, compatibilizers, nucleating agents, flame retardants, inorganic fillers, impact modifiers, foaming agents, and dyes and pigments, as long as the additives do not impair the object of the present disclosure. For the purpose of modifying the mechanical properties and solvent resistance of the resin, the resin of the present disclosure can be kneaded with synthetic resins such as aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS, polylactic acid, polybutylene succinate, and rubber to prepare a polymer alloy. That is, the resin of the present disclosure can be used as a polymer alloy. As the synthetic resin and rubber, one or more types can be used. These synthetic resins and rubbers are added to the resin, for example, as modifiers.

[0266] The timing of mixing and kneading the additives and modifiers with the resin is not particularly limited. For example, the additives and modifiers are added to the resin at once or in any order. For mixing and kneading, a tumbler, a V-type blender, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder, etc. are used. Among these, it is preferable to use an extruder, especially a twin-screw extruder, from the viewpoint of improving dispersibility.

[0267] [Examples of uses of the resin disclosed herein] The resin has excellent optical properties, heat resistance, moldability, and high transparency, and can be used for optical films, optical disks, optical prisms, lenses, etc. When the resin is given reverse wavelength dispersion, the resin is particularly suitable for use as a retardation film. When the resin is given high refractive index properties, the resin is particularly suitable for use as a high refractive index lens.

[0268] [Optical film made of the resin of the present disclosure] As a method for producing an unstretched film using the resin of the present disclosure, for example, the following method can be adopted. Specifically, a casting method can be adopted in which the resin is dissolved in a solvent, the resulting solution is cast, and then the solvent is removed (solution casting method). Here, "casting" means spreading the solution thinly, for example, to a certain film thickness. Also, a melt film-forming method can be adopted in which the resin is melted without using a solvent to form a film.Specific examples of the melt film-forming method include melt extrusion using a T-die, calendar molding, heat pressing, co-extrusion, co-melting, multi-layer extrusion, and inflation molding.The film-forming method of the unstretched film is not particularly limited, but is preferably a melt film-forming method from the viewpoint of avoiding problems caused by residual solvent in the casting method.Among the melt film-forming methods, the melt extrusion method using a T-die is more preferable from the viewpoint of ease of stretching treatment performed in the subsequent process.

[0269] When forming an unstretched film by the melt film-forming method, the forming temperature is preferably 270°C or less, more preferably 265°C or less, and particularly preferably 260°C or less. If the forming temperature is too high, defects due to the generation of foreign matter or bubbles in the obtained film may increase, or the film may become discolored. However, if the forming temperature is too low, the melt viscosity of the resin becomes too high, making it difficult to form, and it may be difficult to produce an unstretched film with a uniform thickness. Therefore, the forming temperature is usually 200°C or more, preferably 210°C or more, and more preferably 220°C or more. The forming temperature of the unstretched film is the temperature during forming in the melt film-forming method, etc., and is usually the temperature at the outlet of the die that extrudes the molten resin. In other words, the forming temperature is obtained by measuring the temperature at the outlet of the die.

[0270] In addition, if foreign matter is present in the film, it is recognized as a defect such as light leakage in the application of a polarizing plate. In order to remove foreign matter in the resin, a method is preferred in which a polymer filter is attached after the extruder, and the resin is filtered and then extruded through a die to form a film. In this case, it is necessary to connect the extruder, the polymer filter, and the die with piping to transport the molten resin. In order to minimize thermal deterioration in the piping, it is preferable to arrange each facility so that the residence time is as short as possible. In addition, it is preferable to carry out the process of transporting and winding the film after extrusion in a clean room, and to take care not to allow foreign matter to adhere to the film.

[0271] The thickness of the unstretched film is determined according to the stretching conditions such as the thickness of the retardation film after stretching and the stretching ratio designed in advance, but if it is too thick, thickness unevenness is likely to occur, and if it is too thin, it may cause breakage during stretching. From the viewpoint of preventing breakage, the thickness of the unstretched film is usually 30 μm or more, preferably 40 μm or more, and more preferably 50 μm or more. In addition, from the viewpoint of preventing the occurrence of unevenness, the thickness of the unstretched film is usually 200 μm or less, preferably 160 μm or less, and more preferably 120 μm or less. In addition, if the unstretched film has a thickness unevenness, it will cause retardation unevenness of the retardation film, so the thickness of the part used as the retardation film is preferably the set thickness ± 3 μm or less, more preferably the set thickness ± 2 μm or less, and particularly preferably the set thickness ± 1 μm or less.

[0272] The length of the unstretched film in the longitudinal direction (for example, in the stretching direction) is preferably 500 m or more, more preferably 1000 m or more, and particularly preferably 1500 m or more. From the viewpoint of productivity and quality, it is preferable to perform continuous stretching when producing a retardation film. Since conditions are usually adjusted to match a predetermined retardation at the start of stretching, if the length of the film is too short, the amount of products that can be obtained after the condition adjustment is reduced.

[0273] The unstretched film preferably has an internal haze of 3% or less, more preferably 2% or less, and particularly preferably 1% or less. If the internal haze of the unstretched film is greater than the upper limit, light scattering occurs, which may cause depolarization when laminated with a polarizer, for example. The lower limit of the internal haze is not particularly set, but is usually 0.1% or more. To measure the internal haze, a transparent film with adhesive, whose haze has been measured in advance, is attached to both sides of the unstretched film to obtain a sample in a state in which the influence of external haze has been removed, and the haze value of the transparent film with adhesive is subtracted from the measured value of the sample to obtain the internal haze value.

[0274] b of unstretched film *The value is preferably 3 or less. In this case, the occurrence of coloring and the like can be further prevented. * The value is more preferably 2 or less, and particularly preferably 1 or less. Regardless of the thickness, the unstretched film has a total light transmittance of preferably 85% or more, more preferably 90% or more, and particularly preferably 91% or more. If the transmittance is equal to or greater than the lower limit, a film with little coloring can be obtained. As a result, when the film is laminated with, for example, a polarizing plate, a circular polarizing plate with high polarization degree and transmittance can be obtained. When such a circular polarizing plate is used in an image display device, it can exhibit high display quality. The upper limit of the total light transmittance of the film of the present disclosure is not particularly limited, but the total light transmittance is usually 99% or less.

[0275] The aforementioned haze and b * In addition to lowering the value, lowering the refractive index of the resin can also suppress reflection on the surface of the film and improve the total light transmittance. The refractive index of the resin used in the present disclosure at sodium d line (589 nm) is preferably 1.49 to 1.56. The refractive index is more preferably 1.50 to 1.55, and even more preferably 1.51 to 1.54. The resin of the present disclosure partially contains an aromatic structure. Therefore, the refractive index of the resin is higher than that of an aliphatic polymer that does not have an aromatic structure, but the refractive index can be kept within the above range by not using an aromatic compound as a copolymerization component of the resin, for example.

[0276] The resin of the present disclosure has an absolute value of the photoelastic coefficient of 20×10 -12 Pa -1 It is preferable that the value is less than 15×10 -12 Pa -1 More preferably, it is 12×10 -12 Pa -1It is particularly preferable that the photoelastic coefficient is not more than 100%. If the photoelastic coefficient is excessively large, when the retardation film is laminated with a polarizing plate, there is a possibility that the image quality may be deteriorated, such as the periphery of the screen becoming white and blurred. This problem is particularly noticeable when the retardation film is used in a large display device or a foldable (specifically, bendable, rollable, or foldable) display device.

[0277] It is preferable that the unstretched film does not undergo brittle fracture in the folding test described below. In a film in which brittle fracture occurs, the film is likely to break during film formation or stretching, which may deteriorate the production yield. In order to obtain a film that does not undergo brittle fracture, it is important to design the molecular weight, melt viscosity, and glass transition temperature of the resin used in the present disclosure to be within the above-mentioned preferred range. In addition, a method of adjusting the film properties by copolymerizing or blending a component that can impart flexibility is also effective.

[0278] The unstretched film is stretched to obtain a retardation film. As the stretching method, a known method such as longitudinal uniaxial stretching, transverse uniaxial stretching using a tenter or the like, or a combination of these, simultaneous biaxial stretching, sequential biaxial stretching, etc. can be used. Stretching may be performed in a batch manner, but continuous stretching is preferable in terms of productivity. Furthermore, compared with the batch manner, continuous stretching can obtain a retardation film with less variation in the phase difference in the film plane.

[0279] The stretching temperature is usually in the range of (Tg-20°C) to (Tg+30°C), preferably in the range of (Tg-10°C) to (Tg+20°C), and more preferably in the range of (Tg-5°C) to (Tg+15°C). Tg is the glass transition temperature of the resin used as the raw material. The stretching ratio is determined depending on the desired retardation value, and is 1.2 times to 4 times, more preferably 1.5 times to 3.5 times, and even more preferably 2 times to 3 times in each of the longitudinal and transverse directions. If the stretching ratio is too small, the effective range in which the desired orientation degree and orientation angle can be obtained becomes narrow. On the other hand, if the stretching ratio is too large, the film may break or wrinkles may occur during stretching.

[0280] The stretching speed is appropriately selected depending on the purpose. The stretching speed and the strain rate have a relationship represented by the following formula. The strain rate is usually 30% / min to 2000% / min, preferably 50% / min to 1000% / min, more preferably 70% / min to 500% / min, and particularly preferably 100% / min to 400% / min. If the stretching speed is too high, breakage during stretching may occur, or the optical properties may vary greatly due to long-term use under high temperature conditions. If the stretching speed is too low, not only will the productivity decrease, but the orientation of the polymer molecular chains may be relaxed during stretching, making it difficult to obtain the desired orientation.

[0281] Strain rate (% / min) = {stretching rate (mm / min) / length of unstretched film (mm)} x 100

[0282] After the film is stretched, a heat setting process may be performed in a heating furnace as necessary, or a relaxation process may be performed by controlling the width of the tenter or adjusting the roll peripheral speed. The heat setting process is usually performed in a temperature range of 60°C to (Tg), preferably 70°C to (Tg-5°C). Tg is the glass transition temperature of the resin used in the unstretched film. If the heat treatment temperature is too high, the molecular orientation obtained by stretching may be disturbed, and the retardation may be significantly reduced from the desired value. In addition, when a relaxation process is provided, the stress generated in the stretched film can be removed by shrinking the film to 95% to 100% of the width of the film expanded by stretching. The treatment temperature applied to the film at this time is the same as the heat setting treatment temperature. By performing the heat setting treatment and relaxation process as described above, it is possible to suppress the fluctuation of optical properties due to long-term use under high temperature conditions.

[0283] The retardation film using the resin of the present disclosure preferably has an in-plane birefringence (Δn) at a wavelength of 590 nm of 0.0030 or more, more preferably 0.0035 or more, even more preferably 0.0040 or more, and particularly preferably 0.0045 or more. Since the retardation is proportional to the thickness (d) and birefringence (Δn) of the film, by setting the birefringence within the above-mentioned specific range, it is possible to express the retardation as designed with a thin film, and a retardation film that can be adapted to a thin device can be obtained. In order to express a high birefringence, the orientation degree of the polymer molecules must be increased by lowering the stretching temperature, increasing the stretching ratio, etc., but since the film is prone to breakage under such stretching conditions, it is advantageous for the resin used to have excellent toughness. In addition, the higher the birefringence, the more preferable it is, but if the birefringence is excessively high, it may be difficult to precisely control the retardation by stretching, so 0.1 or less is preferable. It is more preferably 0.08 or less, and particularly preferably 0.05 or less.

[0284] The thickness of the retardation film using the resin of the present disclosure is preferably 50 μm or less, depending on the required retardation design value. More preferably 45 μm or less, even more preferably 40 μm or less, and particularly preferably 35 μm or less. On the other hand, if the thickness is too thin, the film becomes difficult to handle, and wrinkles or breakage occurs during production, so the thickness of the retardation film of the present disclosure is preferably 5 μm or more, more preferably 10 μm or more.

[0285] The retardation film using the resin of the present disclosure preferably has a wavelength dispersion value, which is the ratio (R450 / R550) of the retardation at a wavelength of 450 nm (R450) to the retardation at a wavelength of 550 nm (R550), of 0.50 or more and 1.02 or less. The wavelength dispersion value (i.e., R450 / R550) is more preferably 1.00 or less, more preferably 0.95 or less, even more preferably 0.90 or less, and particularly preferably 0.87 or less. The wavelength dispersion value is more preferably 0.70 or more, even more preferably 0.75 or more, and even more preferably 0.80 or more. If the wavelength dispersion value is within the above-mentioned range, ideal retardation characteristics can be obtained in a wide wavelength range of the visible region. For example, a retardation film having wavelength dependency as a quarter wave plate is produced, and this retardation film is laminated with a polarizing plate to produce a circular polarizing plate or the like. This makes it possible to realize a polarizing plate and a display device with little wavelength dependency of hue.

[0286] A circular polarizing plate is obtained by laminating the retardation film and a known polarizing film and cutting them to a desired size. Such a circular polarizing plate can be used for, for example, compensating the viewing angle of various displays (liquid crystal display device, organic EL display device, plasma display device, FED field emission display device, SED surface electric field display device), preventing reflection of external light, compensating for color, converting linearly polarized light into circularly polarized light, etc. In particular, when used as a circular polarizing plate for preventing reflection of external light in an organic EL display, it enables a clean black display and has excellent quality reliability. Furthermore, it has a performance that can accommodate the thinning of future devices.

[0287] The polarizing film may be a polarizing film having an absorption axis in either the width direction or the length direction. Specific examples include films obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or a partially saponified ethylene-vinyl acetate copolymer film, after adsorbing a dichroic substance such as iodine or a dichroic dye, and a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among these, a long polarizing film obtained by adsorbing a dichroic substance such as iodine to a polyvinyl alcohol film and uniaxially stretching the film is particularly preferred because it has a high polarized dichroic ratio.

[0288] In the circular polarizing plate, the angle between the slow axis of the retardation film and the width direction of the polarizing film is preferably 38° or more and 52° or less, more preferably 40° or more and 50° or less, and particularly preferably 42° or more and 48° or less. By adjusting the angle within these ranges, it is possible to prevent an increase in the reflection of external light and prevent the reflected light from being colored. Therefore, the display quality of the image is further improved.

[0289] The retardation film and the polarizing film may be laminated via a pressure-sensitive adhesive. As the pressure-sensitive adhesive, any known pressure-sensitive adhesive may be used as long as it does not impair the optical properties of the laminated film. As described above, the circular polarizing plate has sufficient optical properties and is configured to be suitable for use in devices that require precision, thinness, and uniformity. Therefore, the circular polarizing plate can be suitable for use in, for example, liquid crystal panels used in liquid crystal displays and organic EL panels used in organic EL displays. In particular, organic EL panels have a metal layer that easily reflects external light, so they are prone to problems such as external light reflection and background reflection. In order to prevent such external light reflection, it is effective to provide the circular polarizing plate on the light-emitting surface. EXAMPLES

[0290] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure. The properties of the resin of the present disclosure and the optical film using the same were evaluated by the following methods. The property evaluation method is not limited to the following methods, and can be appropriately selected by a person skilled in the art.

[0291] Reduced viscosity of resin The resin was dissolved in methylene chloride to prepare a resin solution with a concentration of 0.6 g / dL. Measurements were performed at a temperature of 20.0°C ± 0.1°C using an Ubbelohde viscometer manufactured by Moritomo Rika Kogyo Co., Ltd., to measure the solvent transit time t0 and the solution transit time t. The relative viscosity η was calculated using the obtained t0 and t values ​​according to the following formula (i). rel The relative viscosity η rel Using the following formula (ii), the specific viscosity η sp asked for.

[0292] η rel =t / t0 (i) η sp =(η-η0) / η0=η rel -1 (ii)

[0293] Then, the obtained specific viscosity η sp Divide by the concentration c (g / dL) to get the reduced viscosity η sp The higher this value, the larger the molecular weight.

[0294] Resin melt viscosity The pellet-shaped resin was placed in a hot air dryer at 100°C for more than 6 hours to dry. Using the dried pellets, measurements were performed using a capillary rheometer manufactured by Toyo Seiki Co., Ltd. The measurement temperature was 240°C, and the shear rate was 6.08 to 1824 sec -1 The melt viscosity was measured at 91.2 sec -1 The melt viscosity value at was used. The orifice used had a die diameter of 1 mmφ×10 mmL.

[0295] · Glass transition temperature (Tg) of resin The glass transition temperature of the resin was measured using a differential scanning calorimeter DSC6220 manufactured by SII NanoTechnology. Approximately 10 mg of the resin was placed in an aluminum pan manufactured by the same company and sealed, and the temperature was raised from 30°C to 200°C at a heating rate of 20°C / min under a nitrogen gas flow of 50 mL / min. After holding the temperature for 3 minutes, the resin was cooled to 30°C at a rate of 20°C / min. The resin was held at 30°C for 3 minutes and then heated again to 200°C at a rate of 20°C / min. From the DSC data obtained in the second heating, the extrapolated glass transition onset temperature, which is the temperature at the intersection of a straight line extending the low-temperature baseline to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change part of the glass transition is maximum, was obtained, and this was taken as the glass transition temperature.

[0296] Film forming Approximately 4 g of resin pellets were dried in a hot air dryer at 100°C for more than 6 hours, and then polyimide films were placed on the top and bottom of the sample using a spacer measuring 14 cm in length, 14 cm in width, and 0.1 mm in thickness. The sample was preheated at a temperature of 200 to 230°C for 3 minutes, pressurized at a pressure of 7 MPa for 5 minutes, then removed together with the spacer and cooled to produce a film.

[0297] Photoelastic coefficient The measurements were performed using a combination of a birefringence measuring device consisting of a He-Ne laser, a polarizer, a compensator, an analyzer, and a photodetector, and a vibration type viscoelasticity measuring device (DVE-3 manufactured by Rheology Co., Ltd.) (for details, see Journal of the Society of Rheology of Japan, Vol. 19, p. 93-97 (1991)). The specific method is as follows. First, a sample with a width of 5 mm and a length of 20 mm was cut out from the film prepared by the above-mentioned method. This sample was fixed to the viscoelasticity measuring device, and the storage modulus E' of the sample was measured at a frequency of 96 Hz at room temperature (specifically, 25°C). While measuring the storage modulus E', the laser light emitted from the He-Ne laser was passed through the polarizer, the sample, the compensator, and the analyzer in that order. Next, the laser light was picked up by a detector (photodiode), and the signal was passed through a lock-in amplifier to determine the amplitude and phase difference relative to the strain from the waveform of the angular frequency ω or 2ω, and the strain optical coefficient O' was obtained. At this time, the direction of the absorption axis of the polarizer (axis) and the direction of the absorption axis of the analyzer were adjusted to be perpendicular to each other and to form an angle of π / 4 with respect to the stretching direction of the sample. The photoelastic coefficient C was calculated from the storage modulus E' and the strain optical coefficient O' by the following formula.

[0298] C=O' / E'

[0299] ·Film stretching From the film produced by the above-mentioned method, a film piece of 70 mm length and 100 mm width was cut out, and free end uniaxial stretching was performed using a batch-type biaxial stretching device (Island Industrial Co., Ltd. BIX-277-AL) to obtain a stretched film. The stretching conditions were as follows: the oven temperature was set to the glass transition temperature of the resin + 10°C, the stretching speed was 250% / min, and the stretching ratio was 2 times. If stretching was successful under these conditions, the stretching ratio was gradually increased to 2.1 times, 2.2 times, and so on, and stretching was repeated until the stretching ratio at which the film broke was reached.

[0300] -Measurement of the refractive index and Abbe number of monomers Using 1-methyl-2-pyrrolidone (NMP) as a solvent, sample solutions with sample concentrations ranging from 5% by weight to 20% by weight were prepared and used as measurement samples. The refractive indexes (i.e., nC, nd, and nF) of the measurement sample were measured at wavelengths of 656 nm (C-line), 587 nm (d-line), and 486 nm (F-line) using a Kalnew precision refractometer KPR-2000 manufactured by Shimadzu Device Manufacturing Co., Ltd. The measurements were performed at 23°C. A graph was prepared by plotting the concentration and the refractive index as a linear function, and the refractive index was obtained by extrapolating the 100% concentration. The Abbe number νd was calculated using the following formula: νd=(1-nd) / (nC-nF) A larger Abbe number indicates that the refractive index has a smaller wavelength dependency.

[0301] -Retardation, wavelength dispersion, and birefringence of stretched films A test piece 4 cm wide and 4 cm long was cut out from the center of the stretched film at the maximum stretch ratio, which was stretched by the above method. The retardation of the test piece was measured at wavelengths of 446.3 nm, 498.0 nm, 547.9 nm, 585.9 nm, 629.6 nm, and 747.1 nm using a retardation measuring device (specifically, KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd.), and the wavelength dispersion was examined from the measurement results. The wavelength dispersion was expressed as the ratio (R450 / R550) of the retardation at a wavelength of 450 nm (specifically, a wavelength of 446.3 nm) to the retardation at a wavelength of 550 nm (specifically, a wavelength of 547.9 nm). If R450 / R550 is greater than 1, the wavelength dispersion is positive, and if it is less than 1, the wavelength dispersion is reversed. When used as a quarter wave plate, the ideal value of R450 / R550 is 0.818 (more precisely, 450 / 550=0.818).

[0302] The birefringence (Δn) was calculated from the retardation (R590) at a wavelength of 590 nm (specifically, a wavelength of 585.9 nm) and the thickness of the stretched film according to the following formula. Birefringence (Δn) = R590 [nm] / (film thickness [mm] × 10 6 ) As described above, the maximum value among the values ​​obtained by repeatedly stretching the sample at different stretch ratios was used as the birefringence (Δn) of each evaluation sample. The higher the birefringence value, the higher the degree of orientation of the polymer. Also, the higher the birefringence value, the thinner the film can be to obtain the desired retardation value. The ideal retardation of a quarter-wave plate at a wavelength of 590 nm is 147.5 nm. When the birefringence (Δn) obtained by the above method was expressed, the film thickness when the retardation is 1 / 4 wavelength was calculated from the following formula.

[0303] 1 / 4 wavelength film thickness [μm] = (147.5 [nm] / 1000) / Δn [Monomer synthesis example] The synthesis method of the monomer used in the production of the resin will be described below. [Monomer synthesis example] [Synthesis Example 1] Synthesis of 11H-indano[1,2-b]quinoline (Compound 1)

[0304] [ka]

[0305] In a nitrogen atmosphere, 73.9g (1324mmol) of iron powder, 276g of ethanol, 16.9g (16.5mmol) of 1N hydrochloric acid, and 300g of demineralized water were added to a 1L four-neck flask, heated to an internal temperature of 70-75°C, and stirred. 50.0g (331mmol) of 2-nitrobenzaldehyde dissolved in 197g of ethanol was dropped into the flask over 1 hour, aged for 30 minutes, cooled to an internal temperature of 50°C or less, and 5.2g of 52% by weight potassium carbonate aqueous solution was added. The iron powder was filtered using a Kiriyama funnel, and the filtered iron powder residue was washed with 233g of ethanol. The filtrate was analyzed by HPLC and found to contain 32.6g (269mmol, 82% yield) of 2-aminobenzaldehyde. This solution was concentrated under reduced pressure, and 233 g of ethanol was removed. To the solution, 39.4 g (298 mmol) of 1-indanone and 101.2 g of 19% by weight potassium hydroxide-ethanol solution were added, and the mixture was stirred under reflux for 1 hour. The internal temperature was cooled to below 50°C, and 344 g of 1N hydrochloric acid was added to adjust the pH to 7-8. The precipitated solid was filtered with a Kiriyama separatory funnel and dried under reduced pressure at 80°C until a constant weight was reached, yielding 60.8 g (79% yield) of 11H-indano[1,2-b]quinoline (compound 1) as a milky white solid.

[0306] [Synthesis Example 2] Synthesis of bis(11H-indeno[1,2-b]quinolin-11-yl)methane (Compound 2)

[0307] [ka]

[0308] In a nitrogen atmosphere, 1.2 L of dimethylformamide, 100 g (460 mmol) of compound 1, 1.84 g (23.01 mmol) of 50 wt% aqueous potassium hydroxide solution, and 18.7 g (230 mmol) of 37% aqueous formalin solution were added to a 2 L flask, and the mixture was stirred for 2 hours at an internal temperature of 25° C. The reaction solution was poured into 1 L of demineralized water, and the precipitated solid was filtered off and dried under reduced pressure at 40° C. until a constant weight was reached, to obtain 45 g (101 mmol, 44% yield) of bis(11H-indeno[1,2-b]quinolin-11-yl)methane (compound 2) as a light brown solid.

[0309] [Synthesis Example 3] Synthesis of diethyl 3,3'-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (Compound 3)

[0310] [ka]

[0311] Into a 500 mL four-neck flask, 10 g (22 mmol) of bis(11H-indeno[1,2-b]quinolin-11-yl)methane (compound 2) obtained in Synthesis Example 2, 1 g (4.4 mmol) of N-benzyl-N,N,N-triethylammonium chloride, and 100 mL of tetrahydrofuran were placed, and after nitrogen replacement, the internal temperature was controlled to 15 to 18° C., 6.0 g of a 48 wt % aqueous sodium hydroxide solution was added, and then 4.9 g (49 mmol) of ethyl acrylate was added dropwise over 30 minutes, and the mixture was aged at room temperature for 3 hours. 200 mL of toluene and saturated aqueous sodium bicarbonate were added, and the mixture was extracted and separated. The organic layer was then concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 5.0 g of diethyl 3,3'-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 3). Compound 3 was confirmed to be a diastereomer by NMR analysis of a portion of the effluent fraction. The refractive index of compound 3 was 1.63, and the Abbe number was 19. The refractive index of compound 3 was measured at a wavelength of 587 nm. The same applies to the refractive index of each of the following compounds.

[0312] [Synthesis Example 4] Synthesis of diphenyl 3,3'-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 4)

[0313] [ka]

[0314] In a 500 mL separable flask, 41 g (63.4 mmol) of diethyl 3,3'-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 3) obtained in Synthesis Example 3, 67.9 g (317 mmol) of diphenyl carbonate, and 0.45 g (1.6 mmol) of tetraisopropyl orthotitanate were placed, the degree of vacuum was adjusted to 3.0 kPa, and the mixture was stirred for 5 hours until the internal temperature reached 185° C. while distilling off by-products. After pressurizing to normal pressure with nitrogen, the mixture was cooled to 90° C., and 203 g of orthoxylene was added. The resulting solution was purified by silica gel column chromatography to obtain 14.8 g (31% yield) of diphenyl 3,3'-[methylenebis(11H-indano[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 4) as a white solid. NMR measurements of the initial and final fractions confirmed that compound 4 was a diastereomer. The refractive index of compound 4 was 1.64 and the Abbe number was 18.

[0315] [Synthesis Example 5] Synthesis of 2,3-dihydro-1H-benz[e]inden-1-one (Compound 5)

[0316] [ka]

[0317] Under nitrogen, 33g (244mmol) of aluminum chloride and 300mL of anhydrous dichloromethane were added to a 1L four-neck flask and stirred at room temperature. A mixed solution of 25g (195mmol) of 3-chloropropanoyl chloride, 25g (195mmol) of naphthalene, and 200mL of anhydrous dichloromethane, which had been separately prepared, was added dropwise to this solution over 1 hour, and then stirred at room temperature for 2 hours. The reaction solution was concentrated under reduced pressure to remove dichloromethane, and 80g of compound 5 was obtained as a brown solid. 28g (483mmol) of sodium chloride was added to this compound 5, and the mixture was stirred at 140°C for 2 hours, and then cooled to room temperature. The resulting reaction solution was poured into 300mL of ice water, stirred for 30 minutes, and then 300mL of water and 300mL of dichloromethane were added to separate and extract the mixture. The separated aqueous layer was extracted twice with 300mL of dichloromethane. The combined organic layer was washed with 300 mL of saturated saline and then dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 24 g (132 mmol, 68% yield) of compound 5 as a yellow solid.

[0318] [Synthesis Example 6] Synthesis of 7H-benz[6,7]indeno[1,2-b]quinoline (Compound 6)

[0319] [ka]

[0320] To 1.5L of an ethanol solution containing 64g (527mmol) of 2-aminobenzaldehyde synthesized in the same manner as in Synthesis Example 1, 305g (3.95mol) of ammonium acetate and 48g (263mmol) of 2,3-dihydro-1H-benz[e]inden-1-one obtained in Synthesis Example 5 were added, and the mixture was stirred at 85°C for 16 hours. 750mL of an ethanol solution containing 32g of 2-aminobenzaldehyde was added, and the mixture was stirred at 85°C for 24 hours. The reaction solution was concentrated under reduced pressure, and 2L of water and 1.5L of dichloromethane were added to the residue, followed by separation and extraction. The aqueous layer was extracted twice with 1.5L of dichloromethane. The obtained organic layer was washed with 2L of saturated saline. The obtained organic layer was purified by silica gel column chromatography to obtain compound 6 in an amount of 85g (318mmol, 40% yield).

[0321] [Synthesis Example 7] Synthesis of diethyl 3,3'-[methylenebis(7H-benz[6,7]indeno[1,2-b]quinolone-7,7-diyl)]dipropionate (Compound 7)

[0322] [ka]

[0323] Except for using compound 6 obtained in Synthesis Example 6 as a raw material, diethyl 3,3'-[methylenebis(7H-benz[6,7]indeno[1,2-b]quinolone-7,7-diyl)]dipropionate (compound 7) was obtained in the same manner as in Synthesis Examples 2 and 3. The refractive index of compound 7 was 1.67 and the Abbe number was 14.

[0324] [Synthesis Example 8] Synthesis of diphenyl 3,3'-[methylenebis(7H-benz[6,7]indeno[1,2-b]quinoline-7,7-diyl)]dipropionate (Compound 8)

[0325] [ka]

[0326] Compound 8 was obtained in the same manner as in Synthesis Example 4, except that Compound 7 was used as a raw material.

[0327] [Resin synthesis example and characteristic evaluation] The abbreviations of the compounds used in the following Examples and Comparative Examples are as follows. Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (compound 9)

[0328] [ka]

[0329] Compound 9 was synthesized by the method described in JP 2015-25111 A.

[0330] DPC: Diphenyl carbonate (Mitsubishi Chemical) BHEPF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]-fluorene (Osaka Gas Chemicals) BCF: 9,9-bis(4-hydroxy-3-methylphenyl)-fluorene (Osaka Gas Chemicals) ISB: Isosorbide (manufactured by Rocket Fleuret, product name: POLYSORB) SPG: Spiroglycol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) CHDM: 1,4-cyclohexanedimethanol (SK Chemicals)

[0331] [Example 1] Diphenyl 3,3′-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 4) 24.42 parts by weight (0.033 mol), ISB 23.76 parts by weight (0.163 mol), SPG 50.33 parts by weight (0.165 mol), DPC 63.21 parts by weight (0.295 mol), and calcium acetate monohydrate 1.73×10 -3 Weight part (9.84×10 -6mol) was put into the reaction vessel, and the inside of the reaction vessel was replaced with reduced pressure nitrogen. The raw materials were dissolved under stirring at 150 ° C for about 10 minutes under a nitrogen atmosphere. In the first reaction step, the pressure was adjusted to 53.3 kPa, and then the temperature was raised to 220 ° C over 30 minutes. 30 minutes after reaching 220 ° C, the pressure was reduced from 53 kPa to 13.3 kPa over 60 minutes. The generated phenol was extracted outside the reaction system. Next, in the second reaction step, the pressure was kept at 13.3 kPa while the heat medium temperature was raised to 245 ° C over 15 minutes, and then the pressure was reduced to 0.10 kPa or less over 30 minutes. After reaching a predetermined stirring torque, the pressure was restored to normal pressure with nitrogen to stop the reaction, and the produced polyester carbonate was extruded into water, and the strands were cut to obtain pellets. The obtained polyester carbonate pellets were used for the various evaluations described above. The evaluation results are shown in Table 1.

[0332] [Example 2] Diphenyl 3,3′-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 4) 25.49 parts by weight (0.034 mol), ISB 23.12 parts by weight (0.158 mol), SPG 50.33 parts by weight (0.165 mol), DPC 61.96 parts by weight (0.289 mol), and calcium acetate monohydrate 1.71×10 -3 Weight part (9.71×10 -6 The same procedure as in Example 1 was repeated except that the amount of the amine was changed to 1.5 mol.

[0333] [Example 3] Diphenyl 3,3′-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 4) 21.49 parts by weight (0.029 mol), ISB 25.54 parts by weight (0.175 mol), SPG 50.33 parts by weight (0.165 mol), DPC 66.66 parts by weight (0.311 mol), and calcium acetate monohydrate 1.80×10 -3 Part by weight (1.02×10 -5 The procedure was the same as in Example 1, except that the amount of the amine was changed to 1.0 mol.

[0334] [Example 4] Diphenyl 3,3′-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 4) 26.02 parts by weight (0.035 mol), ISB 41.35 parts by weight (0.283 mol), SPG 30.20 parts by weight (0.099 mol), DPC 74.36 parts by weight (0.347 mol), and calcium acetate monohydrate 1.35×10 -3 Weight part (7.64×10 -6 The procedure was the same as in Example 1, except that the amount of the amine was changed to 1.0 mol.

[0335] [Example 5] Diphenyl 3,3′-[methylenebis(11H-indeno[1,2-b]quinoline-11,11-diyl)]dipropionate (compound 4) 30.03 parts by weight (0.040 mol), ISB 46.43 parts by weight (0.318 mol), CHDM 20.28 parts by weight (0.141 mol), DPC 89.53 parts by weight (0.418 mol), and calcium acetate monohydrate 1.21×10 -3 Weight part (6.88×10 -6 The procedure was the same as in Example 1, except that the amount of the amine was changed to 1.0 mol.

[0336] [Example 6] Diphenyl 3,3′-[methylenebis(7H-benz[6,7]indeno[1,2-b]quinoline-7,7-diyl)]dipropionate (compound 8) 18.10 parts by weight (0.021 mol), ISB 27.06 parts by weight (0.185 mol), SPG 50.33 parts by weight (0.165 mol), DPC 70.49 parts by weight (0.329 mol), and calcium acetate monohydrate 1.85×10 as a catalyst -3 Part by weight (1.05×10 -5 The procedure was the same as in Example 1, except that the amount of the amine was changed to 1.0 mol.

[0337] [Comparative Example 1] BHEPF 65.60 parts by weight (0.150 mol), ISB 25.90 parts by weight (0.177 mol), DPC 70.02 parts by weight (0.327 mol), and calcium acetate monohydrate 4.61 × 10 -4 Weight part (2.61×10 -6 The procedure of Example 1 was repeated except that 1,2-dichlorophenyl ether (mol) was used.

[0338] [Comparative Example 2] 38.90 parts by weight (0.103 mol) of BCF, 53.83 parts by weight (0.177 mol) of SPG, 59.90 parts by weight (0.280 mol) of DPC, and 4.93×10 calcium acetate monohydrate as a catalyst. -3 Weight part (2.80×10 -5 The same procedure as in Example 1 was repeated except that a 1,000 mol) dimethylformamide was used and the final reaction temperature was 260°C.

[0339] [Comparative Example 3] Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (compound 9) 30.31 parts by weight (0.047 mol), ISB 39.94 parts by weight (0.273 mol), SPG 30.20 parts by weight (0.099 mol), DPC 69.67 parts by weight (0.325 mol), and calcium acetate monohydrate 7.88×10 -4 Weight part (4.47×10 -6 The procedure was the same as in Example 1, except that the amount of the amine was changed to 1.0 mol.

[0340] [Comparative Example 4] Bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (compound 9) 31.58 parts by weight (0.049 mol), ISB 39.22 parts by weight (0.268 mol), SPG 30.20 parts by weight (0.099 mol), DPC 68.19 parts by weight (0.318 mol), and calcium acetate monohydrate 7.77 × 10 -4 Weight part (4.41×10 -6 The procedure was the same as in Example 1, except that the amount of the amine was changed to 1.0 mol.

[0341] [Table 1]

[0342] As shown in Table 1, all of Examples 1 to 6 have reverse wavelength dispersion, yet exhibit very high birefringence (Δn 590 nm), and can reduce the thickness of the film when used as a quarter-wave plate. In particular, Examples 1 to 4 and Example 6 have sufficiently low photoelastic coefficients, so that excellent performance and reliability can be obtained when used as a retardation film. Examples 1 to 6 also have sufficiently high glass transition temperatures and excellent heat resistance.

Claims

1. A thermoplastic resin having a structural unit represented by the following formula (1): [Formula 1] (1) In the formula, A １ ~A ８ Each independently represents ═CH— or ═N—. １ ~A ８ At least one of R contains =N-. １ ~R ８ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl or ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. １ ~R ８ At least two adjacent groups among R may be bonded to each other to form a ring. ９ and R １０ each independently represents a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. X is an oxygen atom, a carbonyl group, or an amino group which may be substituted, and n is an integer of 0 to 1.

2. The thermoplastic resin according to claim 1, wherein R 10 in said general formula (1) is a methylene group.

3. The thermoplastic resin according to claim 1, wherein R 9 in the general formula (1) is an ethylene group.

4. A thermoplastic resin described in any one of claims 1 to 3, wherein n in the general formula (1) is 1.

5. The thermoplastic resin according to claim 1, wherein in said general formula (1), R 10 is a methylene group, R 9 is an ethylene group, and n is 1.

6. The thermoplastic resin according to any one of claims 1 to 5, comprising 1% by weight or more and 70% by weight or less of the structural unit represented by the formula (1).

7. The absolute value of the photoelastic coefficient is 20×10 －１２ P －１ The thermoplastic resin according to any one of claims 1 to 6, wherein:

8. The thermoplastic resin according to any one of claims 1 to 7, having a glass transition temperature of 110°C or higher and 160°C or lower.

9. The thermoplastic resin according to any one of claims 1 to 8, wherein the thermoplastic resin is at least one selected from the group consisting of polycarbonate, polyester, and polyester carbonate.

10. The thermoplastic resin according to any one of claims 1 to 9, further comprising at least one of a structural unit represented by the following formula (10) and a structural unit represented by the following formula (11): [Case 2] [C3]

11. The structural unit represented by the formula (1) is at least one selected from the group consisting of the following formulas (V-1), (V-2), and (V-3): The thermoplastic resin according to any one of claims 1 to 10. [C4] [C5] [C6]

12. A transparent film comprising the resin according to any one of claims 1 to 11.

13. A retardation film obtained by stretching the transparent film according to claim 12 in at least one direction.

14. 14. The retardation film according to claim 13, wherein a ratio (R450 / R550) of a retardation at a wavelength of 450 nm (R450) to a retardation at a wavelength of 550 nm (R550) satisfies the following formula (I): 0.50≦R450 / R550≦1.02 (I)

15. A circularly polarizing plate comprising the retardation film according to claim 13 or 14.

16. A diol compound represented by the following general formula (7): [C7] (7) In the formula, A １ ~A ８ Each independently represents ═CH— or ═N—. １ ~A ８ At least one of R contains =N-. １ ~R ８ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl or ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. １ ~R ８ At least two adjacent groups among R may be bonded to each other to form a ring. ９ and R １０ are each independently a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, and n is an integer of 0 to 1.

17. The thermoplastic resin according to claim 16, wherein R 10 in the general formula (7) is a methylene group.

18. The thermoplastic resin according to claim 16, wherein R 9 in the general formula (7) is an ethylene group.

19. The thermoplastic resin described in any one of claims 16 to 18, wherein n in the general formula (7) is 1.

20. The thermoplastic resin according to claim 16, wherein in said general formula (1), R 10 is a methylene group, R 9 is an ethylene group, and n is 1.

21. The diol compound according to any one of claims 16 to 20, wherein the formula (7) is at least one of the following formula (W-1) and the following formula (W-2): [C8] [C9]

22. A diester compound represented by the following general formula (8): [C10] (8) In the formula, A １ ~A ８ Each independently represents ═CH— or ═N—. １ ~A ８ At least one of R contains =N-. １ ~R ８ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 6 to 11 carbon atoms, an optionally substituted amino group, an optionally substituted vinyl or ethynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. １ ~R ８ At least two adjacent groups among R may be bonded to each other to form a ring. ９ and R １０ are each independently a direct bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. １１ and R １２R is a hydrogen atom, an optionally substituted aryl group having 6 to 11 carbon atoms, an optionally substituted heteroaryl group having 3 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms. １１ and R １２ may be the same or different, and n represents an integer value of 0 to 1.

23. The thermoplastic resin according to claim 22, wherein R 10 in said general formula (1) is a methylene group.

24. The thermoplastic resin according to claim 22 or 23, wherein R 9 in the general formula (1) is an ethylene group.

25. The thermoplastic resin according to claim 22, wherein n in the general formula (1) is 1.

26. The thermoplastic resin according to claim 22, wherein in said general formula (1), R 10 is a methylene group, R 9 is an ethylene group, and n is 1.

27. The diester compound according to any one of claims 22 to 26, wherein the formula (8) is at least one of the following formula (X-1) and the following formula (X-2): [C11] [C12]

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