Polyester carbonate resin, and optical lens and optical film which use same

Abstract

The present invention is capable of providing a polyester carbonate resin which includes a constituent unit (A) represented by general formula (1), a constituent unit (B) represented by general formula (2), and a constituent unit (i) derived from a carboxylic acid diester or a dicarboxylic acid represented by general formula (I). In formula (1), X represents a single bond or a fluorene group, Ra and Rb each independently represent a halogen atom or the like when X is a single bond, Ra and Rb each independently represent a hydrogen atom or the like when X is a fluorene group, A and B each independently represent a C1-4 alkylene group, m and n each independently represent an integer of 1-6, and a and b each independently represent an integer of 0-10. In formula (2), Rz and Rx each independently represent a hydrogen atom or a C1-3 alkyl group, i represents an integer of 2-16, and p represents an integer of 1-600. In formula I, R1 and R2 each independently represent a hydrogen atom. a and b each independently represent an integer of 0-5. n and m each independently represent an integer of 1-5. Ri and Rii each independently represent a hydrogen atom or a C1–5 alkyl group.

Description

Polyester carbonate resin, and optical lens and optical film using the same

[0001] The present invention relates to novel polyester carbonate resins and optical lenses and optical films formed therefrom.

[0002] Optical glass or optical transparent resins are used as materials for optical elements used in the optical systems of various cameras, such as cameras with integrated film and video cameras. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, and the like, and there are many types of optical glass with various refractive indices (nD) and Abbe numbers (νD). However, optical glass has problems such as high material costs, poor moldability, and low productivity. In particular, processing it into aspherical lenses used for aberration correction requires extremely advanced technology and high costs, which poses a major obstacle to practical use.

[0003] On the other hand, optical lenses made of optical transparent resins, especially thermoplastic transparent resins, have the advantage that they can be mass-produced by injection molding and that aspherical lenses can be easily manufactured, and are currently used for camera lenses. Examples of such resins include polycarbonate made from bisphenol A, polystyrene, poly-4-methylpentene, polymethyl methacrylate, and amorphous polyolefins.

[0004] However, when optical transparent resins are used as optical lenses, in addition to refractive index and Abbe number, transparency, heat resistance, and low birefringence are required, so the areas where they can be used are limited by the balance of the resin's properties. For example, polystyrene has low heat resistance and high birefringence, poly-4-methylpentene has low heat resistance, polymethyl methacrylate has a low glass transition temperature, low heat resistance, and a small refractive index, so its areas of use are limited, and polycarbonate made from bisphenol A has high birefringence, so its areas of use are limited and undesirable.

[0005] On the other hand, generally, if the refractive index of an optical material is high, a lens element having the same refractive index can be realized with a surface having a smaller curvature, thereby reducing the amount of aberration that occurs at this surface, and enabling a reduction in the number of lenses, a reduction in the sensitivity of the lenses to decentering, and a reduction in the lens thickness, thereby making the lens system smaller and lighter. Therefore, a high refractive index is useful.

[0006] In the optical design of optical units, it is known to correct chromatic aberration by combining a plurality of lenses with different Abbe numbers. For example, chromatic aberration is corrected by combining a lens made of an alicyclic polyolefin resin with an Abbe number of 45 to 60 with a lens made of a polycarbonate resin (nD=1.59, νD=29) containing bisphenol A, which has a low Abbe number.

[0007] Among the optical transparent resins that have been put into practical use for optical lenses, those with high Abbe numbers include polymethyl methacrylate (PMMA), cycloolefin polymers, etc. In particular, cycloolefin polymers have been widely used for optical lenses because of their excellent heat resistance and mechanical properties.

[0008] Examples of resins with low Abbe numbers include polyester and polycarbonate. For example, the resin described in Patent Document 1 is characterized by a high refractive index and a low Abbe number.

[0009] There is a difference in the coefficient of expansion when cycloolefin polymer, which has a high Abbe number, and polycarbonate resin, which is a polymer with a low Abbe number, so when lenses from both materials are combined to form a lens unit, the lens size will differ when it absorbs water in the environment in which it is used, such as in a smartphone. This difference in expansion coefficient impairs the performance of the lens.

[0010] Patent Documents 2 to 4 describe polycarbonate copolymers containing a perhydroxydimethanonaphthalene skeleton, but because the dihydroxymethyl groups are all located at the 2- and 3-positions, they have low strength and are not suitable for optical lens applications. Furthermore, the polycarbonates described in Patent Documents 2 to 4 have a low glass transition temperature (Tg), resulting in problems with heat resistance. For example, the HOMO polycarbonate described in Example 1 of Patent Document 4 has a number average molecular weight of 38,000, but a low glass transition temperature (Tg) of 125°C.

[0011] International Publication No. 2014 / 73496 JP 5-70584 JP 2-69520 JP 5-341124

[0012] An object of the present invention is to solve at least one of the above-mentioned problems in the prior art. A preferred embodiment of the present invention is to provide a polyester carbonate resin excellent in at least one of refractive index, Abbe number, glass transition temperature, polydispersity, and melt volume-flow rate. A further object of the present invention is to provide an optical lens and an optical film produced from this resin.

[0013] The present inventors conducted extensive research to solve the above-mentioned problems, and as a result, discovered that a polyester carbonate resin made from a specific combination of diol compounds can solve the above-mentioned problems, and arrived at the present invention. That is, the present invention is as follows: <1> A polyester carbonate resin characterized by containing a structural unit (A) represented by the following general formula (1), a structural unit (B) represented by the following general formula (2), and a structural unit (i) derived from a dicarboxylic acid or a carboxylic acid diester represented by the following general formula (I): In formula (1), X represents a single bond or a fluorene group; ａ and R ｂWhen X is a single bond, each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ａ and R ｂ When X is a fluorene group, each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10. In formula (2), R z and R ｘ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; i represents an integer of 2 to 16; and p represents an integer of 1 to 600. In formula (I), R １ and R ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may contain a heterocyclic atom selected from O, N, and S, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. a and b each independently represent an integer of 0 to 5. n and m each independently represent an integer of 1 to 5. R ｉ and R ｉｉeach independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. <2> The polyester carbonate resin according to <1> above, wherein the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is 99.9 / 0.1 to 0.1 / 99.9. <3> The polyester carbonate resin according to <1> or <2> above, wherein in general formula (2), i is an integer of 2 to 10, and p is 1 to 3. <4> The polyester carbonate resin according to any one of <1> to <3> above, further comprising a structural unit (C) represented by the following general formula (3): In formula (3), R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; Y represents -O-, -S-, -SO-, -SO ２ represents -, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by the following general formula (4) or (5), wherein the cycloalkylene group may be substituted with an alkyl group having 1 to 12 carbon atoms and 1 to 3 carbon atoms; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; and a and b each independently represent an integer of 1 to 10. In formula (4), R ｃ and R ｄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms; R ｃ and R ｄ The alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in R may each have a substituent; ｃ and R ｄmay be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring each may have a substituent, and n represents an integer of 0 to 20. In formula (5), R ｅ and R ｆ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, and the alkyl group, alkoxy group, aryl group, aralkyl group, and alkenyl group each optionally have a substituent; R ｅ and R ｆ may be bonded to each other to form a carbon ring having 3 to 20 carbon atoms or a hetero ring having 1 to 20 carbon atoms, and the carbon ring and the hetero ring may each have a substituent. <5> The polyester carbonate resin according to <4> above, wherein Y in general formula (3) is a fluorene group. <6> The polyester carbonate resin according to any one of <1> to <5> above, further comprising a structural unit (D) represented by the following general formula (6): In formula (6), X represents an alkylene group having 1 to 4 carbon atoms. <7> The polyester carbonate resin according to any one of <1> to <6> above, wherein the monomer constituting the structural unit (A) represented by general formula (1) includes at least one monomer represented by the following structural formula: <8> The polyester carbonate resin according to any one of <1> to <7> above, wherein the monomer constituting the structural unit (B) represented by the general formula (2) is at least one compound selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol (C12-diol). <9> The polyester carbonate resin according to any one of <1> to <8> above, wherein the dicarboxylic acid or carboxylic acid diester represented by the general formula (I) includes at least one of the dicarboxylic acid or carboxylic acid diester represented by the following structural formula: In the formula, R ｉ and R ｉｉ each independently represent an alkyl group having 1 to 5 carbon atoms. <10> The polyester carbonate resin according to <4> or <5> above, in which the monomer constituting the structural unit (C) represented by general formula (3) includes at least one monomer represented by the following structural formula: <11> The polyester carbonate resin according to <6> above, wherein the monomer constituting the structural unit (D) represented by the general formula (6) is a monomer represented by the following structural formula: <12> The polyester carbonate resin according to any one of <1> to <11> above, wherein the refractive index (nD) of the polyester carbonate resin is 1.693 to 1.710. <13> The polyester carbonate resin according to any one of <1> to <12> above, wherein the Tg of the polyester carbonate resin is 145 to 161°C. <14> The polyester carbonate resin according to any one of <1> to <13> above, wherein the polydispersity (Mw / Mn) of the polyester carbonate resin is 2.0 to 8.0. <15> The polyester carbonate resin has a melt volume-flow rate (cm ３ <16> An optical lens comprising the polyester carbonate resin according to any one of <1> to <15> above. <17> An optical film comprising the polyester carbonate resin according to any one of <1> to <15> above.

[0014] According to a preferred embodiment of the present invention, a polyester carbonate resin excellent in at least one of refractive index, Abbe number, glass transition temperature, polydispersity, and melt volume-flow rate can be obtained. Furthermore, an optical lens and an optical film made from this resin can be obtained.

[0015] (A) Polyester Carbonate Resin The polyester carbonate resin of the present invention contains a structural unit (A) represented by the following general formula (1), a structural unit (B) represented by the following general formula (2), and a structural unit (i) derived from a dicarboxylic acid or a carboxylic acid diester represented by the following general formula (I): In one embodiment of the present invention, the polyester carbonate resin may contain one of the units represented by general formula (1) and one of the units represented by general formula (2) alone, or two or more of them in combination.

[0016] <Structural Unit (A)> In formula (1), X represents a single bond or a fluorene group; ａ and R ｂ When X is a single bond, each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ａ and R ｂ When X is a fluorene group, each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10.

[0017] In a preferred embodiment of the present invention, in formula (1), R ａand R ｂ each independently represents an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and —C≡C—R ｈ and R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S. The aryl group more preferably has 6 to 18 carbon atoms, more preferably has 6 to 16 carbon atoms, more preferably has 6 to 14 carbon atoms, more preferably has 6 to 12 carbon atoms, and even more preferably has 6 to 10 carbon atoms. The heteroaryl group more preferably has 6 to 18 carbon atoms, more preferably has 8 to 16 carbon atoms, and even more preferably has 10 to 14 carbon atoms. The aryloxy group more preferably has 6 to 18 carbon atoms, more preferably has 6 to 16 carbon atoms, and even more preferably has 6 to 14 carbon atoms.

[0018] In a preferred embodiment of the present invention, in formula (1), R ａ and R ｂ When X is a single bond, each of the groups may independently be selected from a phenyl group, a naphthyl group, or the group consisting of the following: When X is a fluorene group, each of the groups may independently be selected from a hydrogen atom, a phenyl group, a naphthyl group, or the group consisting of the following:

[0019] In the present invention, a preferred embodiment is that the monomer that constitutes the structural unit (A) represented by the general formula (1) includes at least one monomer represented by the following structural formula:

[0020] <Structural Unit (B)> In formula (2), R z and R ｘ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; i represents an integer of 2 to 16; and p represents an integer of 1 to 600.

[0021] In a preferred embodiment of the present invention, in formula (2), i is an integer of 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 6, 2 to 4, 4 to 16, 4 to 14, 4 to 12, 4 to 10, 4 to 8, 4 to 6, 6 to 16, 6 to 14, 6 to 12, 6 to 10, or 6 to 8, and p is an integer of 1 to 500, 1 to 400, 1 to 300, 1 to 200, 1 to 100, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 15, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, or 2 to 3. Preferred examples of the aliphatic dihydroxy compound for the structural unit (B) represented by formula (2) include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and poly-n-propylene glycol. Preferred examples of the poly-n-propylene glycol include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypentamethylene glycol, and polyhexamethylene glycol. Additionally, an example of a commercially available polytrimethylene glycol is the trade name "VELVETOL" manufactured by Allesa, Inc. In an embodiment of the present invention, the monomer constituting the structural unit (B) represented by the general formula (2) is more preferably at least one compound selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol (C12-diol).

[0022] <Structural Unit (C)> The polyester carbonate resin of the present invention may further contain a structural unit (C) represented by the following general formula (3). In formula (3), R ａ and R ｂeach independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; Y represents -O-, -S-, -SO-, -SO2-, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by the following general formula (4) or (5), wherein the cycloalkylene group is optionally substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; and a and b each independently represent an integer of 1 to 10. In formula (4), R ｃ and R ｄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 8 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 10 carbon atoms), and an alkenyl group having 2 to 15 carbon atoms (preferably 2 to 10 carbon atoms), and are preferably selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a phenyl group. More preferably, R ｃ and R ｄ Both of these represent a methyl group. ｃ and R ｄ The alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in R may each have a substituent. ｃ and R ｄ may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 5 to 15 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 5 to 10 carbon atoms), and the carbocyclic ring and the heterocyclic ring may each have a substituent. Preferred examples of the substituent include a cyclohexyl group, an adamantyl group, a cyclododecane group, and a norbornane group. In general formula (4), n represents an integer of 0 to 20, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2. In formula (5), in general formula (5), R ｅ and R ｆ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 3 carbon atoms), an alkoxy group having 1 to 7 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 11 carbon atoms), and an alkenyl group having 2 to 15 carbon atoms, and are preferably selected from the group consisting of a hydrogen atom and a phenyl group. More preferably, R ｅ and R ｆ Both of R and R represent a hydrogen atom. The alkyl group, alkoxy group, aryl group, aralkyl group, and alkenyl group may each have a substituent, and a preferred example of the substituent is a phenyl group. ｅ and R ｆ may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and the carbocyclic ring and the heterocyclic ring each may have a substituent.

[0023] In a preferred embodiment of the present invention, in formula (3), Y represents a divalent group represented by general formula (4) or a divalent group represented by general formula (5). In addition, in formula (3), Y is more preferably a fluorene group.

[0024] In the present invention, a preferred embodiment is one in which the monomer that constitutes the structural unit (C) represented by general formula (3) includes at least one of the monomers represented by the following structural formulas:

[0025] <Structural Unit (D)> The polyester carbonate resin of the present invention may further contain a structural unit (D) represented by the following general formula (6). In formula (6), X is an alkylene group having 1 to 4 carbon atoms.

[0026] In the present invention, a preferred embodiment is that the monomer that constitutes the structural unit (D) represented by general formula (6) is a monomer represented by the following structural formula.

[0027] The polyestercarbonate resin of the present invention may include, for example, a combination of compounds set forth in Table 1 below.

[0028] Here, the combinations of compounds listed in Table 1 will be explained. In Table 1, Nos. 1 to 4 indicate cases where the structural unit (A) contains a compound in which X in formula (1) is a single bond (hereinafter referred to as formula (1-1)). Furthermore, Nos. 5 to 8 indicate cases where the structural unit (A) contains a compound in which X in formula (1) is a fluorene group (hereinafter referred to as formula (1-2)). Nos. 9 to 12 indicate cases where the structural unit (A) contains both a compound represented by formula (1-1) and a compound represented by formula (1-2). Furthermore, in Table 1, Nos. 2, 4, 6, 8, 10, and 12 indicate cases where the structural unit (C) contains a compound in which Y in formula (3) is a fluorene group (hereinafter referred to as formula (3-1)). Each combination will be explained individually below.

[0029] (No. 1) In one embodiment of the present invention, the polyester carbonate resin may contain a structural unit (A) represented by the following general formula (1-1) and a structural unit (B) represented by the above general formula (2). In formula (1-1), X represents a single bond, and R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10.

[0030] Moreover, the general formula (1-1) may be represented by the following general formula (1-1A). In formula (1-1A), R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10.

[0031] (No. 2) In one embodiment of the present invention, the polyester carbonate resin may contain a structural unit (A) represented by the general formula (1-1), a structural unit (B) represented by the general formula (2), and a structural unit (C) represented by the following general formula (3-1): In formula (3-1), R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; Y represents a fluorene group; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; and a and b each independently represent an integer of 1 to 10.

[0032] (No. 3) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1), the structural unit (B) represented by the general formula (2), and the structural unit (D) represented by the general formula (6).

[0033] (No. 4) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1), the structural unit (B) represented by the general formula (2), the structural unit (C) represented by the general formula (3-1), and the structural unit (D) represented by the formula (6).

[0034] (No. 5) In one embodiment of the present invention, the polyester carbonate resin may contain a structural unit (A) represented by the following general formula (1-2) and a structural unit (B) represented by the general formula (2). In formula (1-2), X represents a fluorene group; ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10.

[0035] Moreover, the general formula (1-2) may be represented by the following general formula (1-2A). In formula (1-2A), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-Rｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; and a and b each independently represent an integer of 0 to 10.

[0036] (No. 6) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-2), the structural unit (B) represented by the general formula (2), and the structural unit (C) represented by the general formula (3-1).

[0037] (No. 7) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-2), the structural unit (B) represented by the general formula (2), and the structural unit (D) represented by the general formula (6).

[0038] (No. 8) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-2), the structural unit (B) represented by the general formula (2), the structural unit (C) represented by the general formula (3-1), and the structural unit (D) represented by the formula (6).

[0039] (No. 9) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), and the structural unit (B) represented by the general formula (2).

[0040] (No. 10) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), the structural unit (B) represented by the general formula (2), and the structural unit (C) represented by the general formula (3-1).

[0041] (No. 11) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), the structural unit (B) represented by the general formula (2), and the structural unit (D) represented by the general formula (6).

[0042] (No. 12) In one embodiment of the present invention, the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), the structural unit (B) represented by the general formula (2), the structural unit (C) represented by the general formula (3-1), and the structural unit (D) represented by the formula (6).

[0043] The molar ratio (A / B) of the structural unit (A) to the structural unit (B) is preferably 99.9 / 0.1 to 0.1 / 99.9, more preferably 99 / 1 to 1 / 99, even more preferably 99 / 1 to 50 / 50, particularly preferably 99 / 1 to 60 / 40, and most preferably 90 / 10 to 70 / 30. By increasing the molar ratio of the structural unit (B) above the lower limit, the flowability of the polyester carbonate resin can be improved. Furthermore, by decreasing the molar ratio of the structural unit (B) below the upper limit, the optical properties of a molded article using the polyester carbonate resin of the present invention can be maintained within a preferred range for an optical material.

[0044] <Structural Unit (i)> In formula (I), R １ and R ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may contain a heterocyclic atom selected from O, N, and S, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. a and b each independently represent an integer of 0 to 5. n and m each independently represent an integer of 1 to 5. R ｉ and R ｉｉ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0045] In the present invention, the dicarboxylic acid or carboxylic acid diester represented by general formula (I) preferably includes at least one of the dicarboxylic acid or carboxylic acid diester represented by the following structural formula: In the formula, R ｉ and R ｉｉ each independently preferably represents an alkyl group having 1 to 5 carbon atoms, more preferably represents a methyl group or an ethyl group, and particularly preferably represents a methyl group.

[0046] In the present invention, the molar ratio of the total amount of diol components constituting structural units (A) to (D) to the total amount of dicarboxylic acid or carboxylic acid diester constituting structural unit (i) (diol component:carboxylic acid component) is preferably from 90:10 to 10:90, more preferably from 90:10 to 50:50, more preferably from 75:25 to 50:50, even more preferably from 70:30 to 50:50, still more preferably from 65:35 to 50:50, and particularly preferably from 60:40 to 50:50. Ratios of from 75:25 to 40:60 and from 65:35 to 45:55 are also preferred.

[0047] It is preferable to add an antioxidant, a mold release agent, an ultraviolet absorber, a flowability improver, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, an antibacterial agent, or the like to the polyester carbonate resin of the present invention.

[0048] The polyester carbonate resin of the present invention may contain impurities such as phenol generated during production or residual unreacted carbonate diester. The phenol content in the polyester carbonate resin is preferably 0.1 to 3,000 ppm, more preferably 0.1 to 2,000 ppm, and particularly preferably 1 to 1,000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm. The carbonate diester content in the polyester carbonate resin is preferably 0.1 to 1,000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm. By adjusting the amounts of phenol and carbonate diester contained in the polyester carbonate resin, resins with desired physical properties can be obtained. The phenol and carbonate diester contents can be appropriately adjusted by changing the polycondensation conditions and equipment. They can also be adjusted by the conditions of the extrusion process after polycondensation.

[0049] If the content of phenol or carbonic acid diester exceeds the above range, problems such as a decrease in strength of the resulting resin molded body or the generation of an odor may occur. On the other hand, if the content of phenol or carbonic acid diester is below the above range, there is a risk of a decrease in plasticity when the resin is melted. Furthermore, raw material monomers may remain in the resin. The amount of each raw material monomer remaining in the resin is preferably 3000 ppm or less, more preferably 1 to 1000 ppm.

[0050] (B) Method for Producing Polyester Carbonate Resin The polyester carbonate resin of the present invention can be produced by a melt polycondensation method using the diol compound constituting the structural unit (A), the diol compound constituting the structural unit (B), the dicarboxylic acid or carboxylic acid diester constituting the structural unit (i), and the carbonate diester as raw materials. Furthermore, other diol compounds may be used in combination. In this reaction, the polyester carbonate resin can be produced in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst consisting of both, as a polycondensation catalyst.

[0051] Examples of carbonate diesters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is particularly preferred from the standpoint of reactivity and purity. The amount of carbonate diester added can be determined by assuming that equimolar amounts of the diol component and the dicarboxylic acid component react, with the remainder reacting with the carbonate diester. The carbonate diester is preferably used in a ratio of 0.60 to 1.50 moles per mole of the difference between the diol component and the dicarboxylic acid component, more preferably 0.80 to 1.40 moles, even more preferably 1.00 to 1.30 moles, even more preferably 1.00 to 1.25 moles, and particularly preferably 1.00 to 1.20 moles. Adjusting this molar ratio allows for control of the molecular weight of the polyester carbonate resin.

[0052] Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

[0053] Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. From the viewpoints of catalytic effect, price, distribution volume, and effect on the color of the resin, sodium carbonate and sodium hydrogen carbonate are preferred.

[0054] Examples of alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds.

[0055] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and salts thereof, and amines.

[0056] As the transesterification catalyst, zinc, tin, zirconium, and lead salts are preferably used, and these may be used alone or in combination, or may be used in combination with the above-mentioned alkali metal compounds or alkaline earth metal compounds.

[0057] Specific examples of the transesterification catalyst include tris(2,4-pentanedionato)aluminum(III), diethyl (4-methylbenzyl)phosphonate, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, lead(IV) acetate, zirconium acetate, and titanium tetrabutoxide. Of these, zinc acetate, zirconium acetate, tris(2,4-pentanedionato)aluminum(III), and diethyl (4-methylbenzyl)phosphonate are preferred, and tris(2,4-pentanedionato)aluminum(III) and diethyl (4-methylbenzyl)phosphonate are more preferred.

[0058] These catalysts are used so that the metal components in the catalyst are preferably 0.001 ppm to 1000 ppm, more preferably 0.01 ppm to 100 ppm, and particularly preferably 0.1 ppm to 100 ppm relative to the theoretically produced amount of resin. In the examples described below, the catalyst was added so that the Al element was 6.5 ppm and the P element was 13.5 ppm.

[0059] The melt polycondensation method involves using the above-mentioned raw materials and catalyst to carry out melt polycondensation under heating at normal pressure or reduced pressure while removing by-products through an ester exchange reaction.

[0060] Specifically, the reaction is carried out at a temperature of 120 to 260°C, preferably 180 to 260°C, for 0.1 to 5 hours, preferably 0.5 to 3 hours. The reaction temperature is then increased while increasing the degree of vacuum in the reaction system, and the diol compound and the carbonate diester are reacted. Finally, the polycondensation reaction is carried out at a temperature of 200 to 350°C for 0.05 to 2 hours under a reduced pressure of 1 mmHg or less. This reaction may be carried out continuously or batchwise. The reaction apparatus used in carrying out the reaction may be a vertical type equipped with an anchor-type impeller, Maxblend impeller, helical ribbon impeller, or the like; a horizontal type equipped with a paddle impeller, lattice impeller, spectacle impeller, or the like; or an extruder type equipped with a screw. It is also preferable to use a suitable combination of these types of reaction apparatus taking into consideration the viscosity of the polymer.

[0061] In the method for producing a polyester carbonate resin of the present invention, the catalyst may be removed or deactivated after the polymerization reaction to maintain thermal stability and hydrolytic stability. Generally, a method of deactivating the catalyst by adding a known acidic substance is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid, phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, and dioctyl phosphate. Suitable deactivators include phosphate esters such as octyl phosphate and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane, boric acids such as boric acid and phenylboric acid, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonyl chloride, alkyl sulfates such as dimethyl sulfate, and organic halides such as benzyl chloride. From the viewpoints of deactivation effect, resin hue, and stability, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate are preferred. These deactivators are used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times, the molar amount of the catalyst. Less than 0.01 times the molar amount of the catalyst results in insufficient deactivation effect, which is undesirable. On the other hand, if the amount is more than 50 times by mole the amount of the catalyst, the heat resistance decreases and the molded article tends to be discolored, which is undesirable.

[0062] After catalyst deactivation, a step of removing low-boiling compounds in the polymer by volatilization at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C may be provided. For this purpose, a horizontal apparatus equipped with stirring blades with excellent surface renewal ability, such as paddle blades, lattice blades, or spectacle blades, or a thin-film evaporator is preferably used.

[0063] It is desirable that the polyester carbonate resin of the present invention have as little foreign matter content as possible, and therefore filtration of the molten raw material and the catalyst solution is preferably carried out. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, filtration of the produced resin through a polymer filter is preferably carried out. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the process of collecting resin pellets must naturally be carried out in a low-dust environment, preferably class 1000 or less, more preferably class 100 or less.

[0064] (C) Physical Properties of Polyester Carbonate Resin The polyester carbonate resin of the present invention is excellent in at least one of refractive index, Abbe number, glass transition temperature, polydispersity, and melt volume-flow rate. The polystyrene-equivalent weight-average molecular weight (Mw) of the polyester carbonate resin of the present invention is preferably 5,000 to 300,000. The polystyrene-equivalent weight-average molecular weight (Mw) is more preferably 20,000 to 120,000, and particularly preferably 20,000 to 60,000. An Mw of less than 5,000 is undesirable because the optical lens becomes brittle. An Mw of more than 300,000 is undesirable because the melt viscosity becomes high, making it difficult to extract the resin after production, and further because the fluidity becomes poor, making it difficult to injection mold in a molten state.

[0065] The polyester carbonate resin of the present invention preferably has a glass transition point (Tg) of 145°C to 1610°C, more preferably 147°C to 158°C.

[0066] The refractive index of the molded article produced from the polyester carbonate resin of the present invention is preferably 1.693 to 1.710, and more preferably 1.695 to 1.705.

[0067] The molded article produced from the polyester carbonate resin of the present invention preferably has an Abbe number of 24 or less, more preferably 23 or less, and particularly preferably 22 or less. There is no particular lower limit on the Abbe number, but when used as an optical lens, taking into account the specifications for use, the Abbe number is preferably 13 or more, and more preferably 15 or more.

[0068] The polyester carbonate resin of the present invention preferably has a polydispersity (Mw / Mn) of 2.0 to 8.0, more preferably 3.0 to 7.6.

[0069] The polyester carbonate resin of the present invention has a melt volume flow rate (MVR) of 9.0 cm ３ / 10 min or more is preferable, 15 cm ３ / 10 min or more is more preferable, and 22 cm ３ The upper limit of the MVR is not particularly limited, but from the viewpoint of moldability, it is more preferable that the MVR is 100 cm / min or more. ３ / 10 min or less is preferable, ３ / 10 min or less is more preferable, and 60 cm ３ It is more preferable that the time is 10 min or less.

[0070] (D) Optical Lenses Optical lenses produced using the polyester carbonate resin of the present invention have a high refractive index and excellent heat resistance, making them extremely useful in fields where expensive high-refractive index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors. If necessary, they are preferably used in the form of aspherical lenses. Aspherical lenses can essentially eliminate spherical aberration with a single lens, eliminating the need to combine multiple spherical lenses to eliminate spherical aberration, thereby enabling weight reduction and reduced production costs. Therefore, aspherical lenses are particularly useful as camera lenses. Furthermore, optical lenses can be molded by any method, such as injection molding, compression molding, or injection-compression molding. The present invention makes it possible to more easily obtain high-refractive index, low-birefringence aspherical lenses, which are technically difficult to process using glass lenses.

[0071] To prevent foreign matter from getting into the optical lens as much as possible, the molding environment must naturally be a low-dust environment, preferably class 6 or less, more preferably class 5 or less.

[0072] (E) Optical Films Optical films produced using the polyester carbonate resin of the present invention are excellent in transparency and heat resistance, and are therefore suitable for use as films for liquid crystal substrates, optical memory cards, and the like.

[0073] In order to prevent foreign matter from being mixed into the optical film as much as possible, the molding environment must naturally be a low-dust environment, preferably class 6 or less, more preferably class 5 or less.

[0074] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The measurements in the examples were measured using the following methods or devices. 1) Refractive index (nD) Based on JIS B 7071-2:2018, a polyester carbonate resin composition was molded to obtain a V-block, which was used as a test piece. The refractive index was measured at 23°C using a refractometer (Shimadzu KPR-3000).

[0075] 2) Abbe number (ν) Using the same test piece (V-block) as used in the refractive index measurement, the refractive index was measured at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C using a refractometer, and the Abbe number was calculated using the following formula: Refractometer: KPR-3000 manufactured by Shimadzu Corporation ν=(nD-1) / (nF-nC) nD: refractive index at wavelength 589 nm nC: refractive index at wavelength 656 nm nF: refractive index at wavelength 486 nm

[0076] 3) Glass transition temperature (Tg): Measured using a differential scanning calorimeter with a temperature rise program of 10°C / min in accordance with JIS K7121-1987. Differential scanning calorimeter: X-DSC7000 manufactured by Hitachi High-Tech Science Corporation

[0077] 4) Dispersity (Mw / Mn) Calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn) converted to standard polystyrene by gel permeation chromatography (GPC). The apparatus, column, and measurement conditions used are as follows: GPC apparatus: HLC-8420GPC, manufactured by Tosoh Corporation Columns: TSKgel Super HM-M x 3, manufactured by Tosoh Corporation TSKgel guard column Super H-H x 1, manufactured by Tosoh Corporation TSKgel Super H-RC x 1, manufactured by Tosoh Corporation Detector: RI detector Standard polystyrene: Standard polystyrene kit PStQuick C, manufactured by Tosoh Corporation Sample solution: 0.2% by mass tetrahydrofuran solution Eluent: tetrahydrofuran Eluent flow rate: 0.6 mL / min Column temperature: 40°C

[0078] 5) Melt Volume Flow Rate (MVR) Measured in accordance with JIS K7210. Measuring device: Melt Indexer T-111 manufactured by Toyo Seiki Seisakusho, Ltd. Measuring conditions: Measured at a temperature of 260°C and a load of 2160 g. Procedure: MVR (unit: cm) was calculated from the amount of resin extruded per 10 minutes from a standard die installed at the bottom of the cylinder. ３ / 10 min) was calculated.

[0079] (Example 1) As raw materials, 7500.0 g (12.0 mol) of 6,6'-di-(2-naphthyl)-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl (2DNBINOL-2EO) represented by the following structural formula, 4958.2 g (9.2 mol) of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) represented by the following structural formula, 838.1 g (4.1 mol) of 1,12-dodecanediol (C12-diol) represented by the following structural formula, 8334.2 g (20.7 mol) of 2,2'-([1,1'-binaphthalene]-2,2'-diylbis(oxy))acetoacetic acid (BINOL-DC) represented by the structural formula, 1167.4 g (5.4 mol) of diphenyl carbonate (DPC), 1.68 g of tris(2,4-pentanedionato)aluminum(III) as a catalyst, and 2.1 mL of diethyl (4-methylbenzyl)phosphonate were placed in a 50-liter reactor equipped with a stirrer and a distillation device, and the inside of the reactor was replaced with nitrogen. The mixture was heated to 200°C over 20 minutes under a nitrogen atmosphere of 760 Torr and stirred. After adjusting the vacuum to 300 Torr over 20 minutes, the temperature was raised to 240°C over 40 minutes and maintained at 240°C and 300 Torr for 10 minutes to carry out a transesterification reaction. The pressure was returned to normal with nitrogen gas, the trap was replaced, and the pressure was again adjusted to 240°C and 300 Torr and maintained for 10 minutes. Thereafter, the temperature was raised to 250°C over 70 minutes, while the vacuum was adjusted to 50 Torr over 50 minutes. The vacuum was then further adjusted to 1 Torr or less over 20 minutes, and a polymerization reaction was carried out under stirring at 250°C and 1 Torr or less for 30 minutes. After completion of the reaction, nitrogen was introduced into the reactor to pressurize the reaction system, and the resulting polyester carbonate resin was pelletized and extracted to obtain a polyester carbonate resin. Further, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADEGASTABE PEP-36; manufactured by ADEKA Corporation); 300 ppm relative to polyester carbonate resin, pentaerythol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADEKA STAB AO-60; manufactured by ADEKA Corporation); 1000 ppm relative to polyester carbonate resin, glycerin monostearate (stearic acid monoglyceride, Rikemal S-100A; manufactured by Riken Vitamin Co., Ltd.); 1500 ppm relative to polyester carbonate resin, Dodecylbenzenesulfonate tetrabutylphosphonium salt (MGA-614; manufactured by Takemoto Yushi Co., Ltd.) was added in an amount of 15 ppm relative to the polyester carbonate resin, and the following mixture, a 90:10 mixture of 3,4-dimethyl and 2,4-dimethyl forms (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount of 200 ppm relative to the polyester carbonate resin, and the mixture was kneaded in a twin-screw extruder. Details of the extrusion are as follows: Twin-screw extruder: TEM-18SS manufactured by Shibaura Machine Co., Ltd. Resin temperature: 260° C. Screw rotation speed: 200 rpm The physical properties of the obtained polyester carbonate resin are shown in Table 2 below.

[0080] Examples 2 and 3, Comparative Examples 1 to 3 Polyester carbonate resins were obtained in the same manner as in Example 1, except that the types and charging ratios of raw materials were changed so as to obtain the compositions shown in Table 2 below. The physical properties of the polyester carbonate resin obtained are shown in Table 2 below.

Claims

1. A polyester carbonate resin characterized by containing a structural unit (A) represented by the following general formula (1), a structural unit (B) represented by the following general formula (2), and a structural unit (i) derived from a dicarboxylic acid or a carboxylic acid diester represented by the following general formula (I): 【Chemical 1】 In formula (1), X represents a single bond or a fluorene group; R ａ and R ｂ When X is a single bond, each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ａ and R ｂ When X is a fluorene group, each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C≡C-R ｈ is selected from R ｈ represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms and containing one or more hetero ring atoms selected from O, N, and S; A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 1 to 6; a and b each independently represent an integer of 0 to 10. 【Chemistry 2】 In formula (2), R z and R ｘ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; i represents an integer of 2 to 16; and p represents an integer of 1 to 600. 【Chemistry 3】 In formula (I), R １ and R ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms which may contain a heterocyclic atom selected from O, N, and S, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. a and b each independently represent an integer of 0 to 5; n and m each independently represent an integer of 1 to 5; R ｉ and R ｉｉ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

2. 2. The polyester carbonate resin according to claim 1, wherein the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is 99.9 / 0.1 to 0.1 / 99.

9.

3. 2. The polyester carbonate resin according to claim 1, wherein i in the general formula (2) is an integer of 2 to 10, and p is an integer of 1 to 3.

4. The polyester carbonate resin according to claim 1, further comprising a structural unit (C) represented by the following general formula (3): 【Chemistry 4】 In formula (3), R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; Y is -O-, -S-, -SO-, -SO ２ represents -, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by the following general formula (4) or the following general formula (5), wherein the cycloalkylene group is optionally substituted with an alkyl group having 1 to 12 carbon atoms and 1 to 3 carbon atoms, A and B each independently represent an alkylene group having 1 to 4 carbon atoms; m and n each independently represent an integer of 0 to 4; a and b each independently represent an integer of 1 to 10. 【Chemistry 5】 R ｃ and R ｄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms; R ｃ and R ｄ The alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in R may each have a substituent; ｃ and R ｄ may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring each may have a substituent, and n represents an integer of 0 to 20. 【Chemistry 6】 In formula (5), R ｅ and R ｆ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, and the alkyl group, alkoxy group, aryl group, aralkyl group, and alkenyl group each optionally have a substituent; R ｅ and R ｆ may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring each may have a substituent.

5. 5. The polyester carbonate resin according to claim 4, wherein Y in the general formula (3) is a fluorene group.

6. The polyester carbonate resin according to claim 1, further comprising a structural unit (D) represented by the following general formula (6): 【Chemistry 7】 In formula (6), X represents an alkylene group having 1 to 4 carbon atoms.

7. 2. The polyester carbonate resin according to claim 1, wherein the monomer constituting the structural unit (A) represented by the general formula (1) includes at least one monomer represented by the following structural formula: 【Chemistry 8】

8. The polyester carbonate resin according to claim 1, wherein the monomer constituting the structural unit (B) represented by the general formula (2) is at least one compound selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol (C12-diol).

9. 2. The polyester carbonate resin according to claim 1, wherein the dicarboxylic acid or carboxylic acid diester represented by the general formula (I) includes at least one of a dicarboxylic acid or a carboxylic acid diester represented by the following structural formula: 【Chemistry 9】 In the formula, R ｉ and R ｉｉ each independently represents an alkyl group having 1 to 5 carbon atoms.

10. The polyester carbonate resin according to claim 4, wherein the monomer constituting the structural unit (C) represented by the general formula (3) includes at least one monomer represented by the following structural formula: 【Chemistry 10】

11. The polyester carbonate resin according to claim 6, wherein the monomer constituting the structural unit (D) represented by the general formula (6) is a monomer represented by the following structural formula: 【Chemistry 11】

12. The polyester carbonate resin according to claim 1, wherein the refractive index (nD) of the polyester carbonate resin is 1.693 to 1.

710.

13. 2. The polyester carbonate resin according to claim 1, wherein the polyester carbonate resin has a Tg of 145 to 161°C.

14. 2. The polyester carbonate resin according to claim 1, wherein the polydispersity (Mw / Mn) of the polyester carbonate resin is 2.0 to 8.

0.

15. The melt volume flow rate (cm ３ 2. The polyester carbonate resin according to claim 1, wherein the viscosity (Tc) of the polyester carbonate resin is 9.0 to 100.

16. An optical lens comprising the polyester carbonate resin according to any one of claims 1 to 15.

17. An optical film comprising the polyester carbonate resin according to any one of claims 1 to 15.

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