Thermoplastic resin, thermoplastic resin composition, and molded article

Abstract

To provide a thermoplastic resin that is suitable for use in a high temperature environment, offering high heat resistance, durability, and resistance to heat-induced yellowing, and also exhibits a high refractive index and low birefringence, qualities beneficial for optical molding materials.SOLUTION: A thermoplastic resin contains a structural unit (A), represented by a bisphenol with a fluorene structure, and a structural unit (B), represented by a specific bisphenol, in a mol ratio of (A) / (B)=50 / 50-99 / 1. The thermoplastic resin is molded to give a molded article, which serves as an optical member.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin having high heat resistance, durability, and resistance to heat yellowing, enabling use in high-temperature environments, as well as a thermoplastic resin having a high refractive index and low birefringence useful as an optical molding material, and a thermoplastic resin composition containing this thermoplastic resin. The present invention also relates to a molded article made from this thermoplastic resin or thermoplastic resin composition. [Background technology]

[0002] Polycarbonate resins are used as molding materials for optical applications due to their excellent transparency, dimensional stability, and mechanical properties. Patent Document 1 discloses a polycarbonate resin with excellent optical properties, which mainly contains repeating units having a 9,9-bisphenylfluorene skeleton. In the examples of Patent Document 1, a polycarbonate resin is prepared using 2,2'-[9H-fluorene-9-ylidenebis(4,1-phenyleneoxy)]-bisethanol [9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (abbreviation: BPEF)] as a polymerization component. The glass transition temperature of the polycarbonate resin described in Patent Document 1 is relatively high, at around 145°C. However, it may not be suitable for applications where manufacturing or use in high-temperature environments is expected (for example, automotive lenses).

[0003] Patent Document 2 proposes a polycarbonate copolymer for optical lenses that has the characteristics of high transparency, high refractive index, low birefringence, and high moldability. Patent Document 2 describes a resin with a relatively high Tg of about 149°C to 159°C, but it does not describe the presence or absence of deformation / cracking or thermal yellowing, which are important characteristics for practical use in high-temperature environments, so there is room for improvement. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-101787

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a thermoplastic resin having high heat resistance, durability, and heat-resistant yellowing resistance that can withstand use in a high-temperature environment, a high refractive index and low birefringence useful as an optical molding material, a thermoplastic resin composition containing this thermoplastic resin, and a molded body made of them.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic resin containing two specific structural units in a specific mol ratio has high heat resistance, durability and heat-resistant yellowing resistance that can withstand use in a high-temperature environment, and a high refractive index and low birefringence useful as an optical molding material, and have reached the present invention. That is, the gist of the present invention resides in the following [1] to

[18] .

[0007] [1] A thermoplastic resin containing a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2) in a ratio of (A) / (B) = 50 / 50 to 99 / 1 in terms of mol ratio.

[0008]

Chem.

[0009] (In formula (1), ring Z1 and Z2 each independently represent an aromatic hydrocarbon ring. R1 to R 10 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms which may contain an aromatic group. However, R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9, and R9 and R 10Among the pairs, 1 to 4 pairs may be joined together to form a ring. i and ii independently represent the number obtained by subtracting 3 from the number of ring members of rings Z1 and Z2, respectively. Multiple R1 and R2 may be the same or different. X represents an alkylene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 12 carbon atoms, or an arylene group with 6 to 20 carbon atoms. n represents an integer between 0 and 10.

[0010] [2] The thermoplastic resin according to [1], wherein the amount of phenolic hydroxyl groups derived from the aromatic dihydroxy compound represented by the following formula (3) is 100 to 1500 ppm.

[0011] [ka]

[0012] [3] The thermoplastic resin according to [1] or [2], wherein the hydrolyzed product obtained by hydrolyzing the thermoplastic resin contains compounds represented by the following formulas (3) to (5), and the sum of the content of the compound represented by the following formula (4) and the compound represented by the following formula (5) in the hydrolyzed product is 1.00% by mass or more relative to the content of the compound represented by the following formula (3).

[0013] [ka]

[0014] [4] The thermoplastic resin according to any one of [1] to [3], wherein X in formula (1) is an ethylene group.

[0015] [5] A thermoplastic resin according to any of [1] to [4], wherein n in formula (1) is 1.

[0016] [6] The thermoplastic resin according to any one of [1] to [5], wherein the structural unit (A) is represented by the following formula (6) or (7).

[0017] [ka]

[0018] (In formulas (6) and (7), R 11 ~R 14 each independently represents a hydrogen atom, a methyl group, or a phenyl group. R3 to R 10 has the same meaning as in the above formula (1). However, one of the pairs of R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9, and R9 and R 10 may be bonded to each other to form a ring.)

[0019] [7] The thermoplastic resin according to any one of [1] to [6], wherein in the formula (1), all of R3 to R 10 are hydrogen atoms.

[0020] [8] The thermoplastic resin according to [6] or [7], wherein the structural unit (A) is represented by the following formula (8).

[0021] [Chemical formula]

[0022] [9] The thermoplastic resin according to any one of [1] to [8], wherein the viscosity average molecular weight (Mv) is 5000 or more and 50000 or less.

[0023]

[10] The thermoplastic resin according to any one of [1] to [9], wherein the refractive index (n D ) at a wavelength of 589 nm is 1.590 or more.

[0024]

[11] The thermoplastic resin according to any one of [1] to

[10] , wherein the Abbe number (ν D ) is 35.0 or less.

[0025]

[12] The thermoplastic resin according to any one of [1] to

[11] , wherein the glass transition temperature (Tg) is 110°C or more and 200°C or less.

[0026]

[13] The thermoplastic resin according to any one of [1] to

[12] , wherein in a 3 mm thick test specimen made of the thermoplastic resin, the increase in YI per hour (ΔYI / hour) [1 / Hr] calculated by the following formula is 0.0500 or less. Increase in YI per hour (ΔYI / hour) = (Yellowness of the test specimen after heating - Yellowness of the test specimen before heating) / Heating time In the above formula, the yellowness of the test specimen after heating is the yellowness measured in accordance with JIS K7373 after conducting a heat resistance test in which the test specimen is left standing in an environment of normal pressure and 135°C for 280 hours, and the yellowness of the test specimen before heating is the yellowness measured in accordance with JIS K7373 before conducting the heat resistance test, with a heating time of 280 hours.

[0027] A thermoplastic resin composition comprising a thermoplastic resin described in any of [1] to

[13] , at least one additive selected from the group consisting of heat stabilizers, antioxidants, ultraviolet absorbers, brightness enhancers, dyes, pigments, mold release agents, flow modifiers, and impact resistance enhancers, and / or other resins other than the thermoplastic resin.

[0028]

[15] The thermoplastic resin composition according to

[14] , wherein in a 3 mm thick test specimen made of the thermoplastic resin composition, the increase in YI per hour (ΔYI / hour) [1 / Hr] calculated by the following formula is 0.0500 or less. Increase in YI per hour (ΔYI / hour) = (Yellowness of the test specimen after heating - Yellowness of the test specimen before heating) / Heating time In the above formula, the yellowness of the test specimen after heating is the yellowness measured in accordance with JIS K7373 after conducting a heat resistance test in which the test specimen is left standing in an environment of normal pressure and 135°C for 280 hours, and the yellowness of the test specimen before heating is the yellowness measured in accordance with JIS K7373 before conducting the heat resistance test, with a heating time of 280 hours.

[0029]

[16] A molded article obtained by molding a thermoplastic resin described in any of [1] to

[13] , or a thermoplastic resin composition described in

[14] or

[15] .

[0030]

[17] The molded body according to

[16] , wherein the molded body is an optical component.

[0031]

[18] The molded body according to

[17] , wherein the optical component is at least one optical lens selected from the group consisting of automotive lenses, spectacle lenses, pickup lenses, camera lenses, microarray lenses, projector lenses and Fresnel lenses. [Effects of the Invention]

[0032] The thermoplastic resin of the present invention has a structural unit (A) which is a carbonate structure derived from a diol component having a fluorene ring in a cardo structure, and a structural unit (B) which is a carbonate structure derived from 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (hereinafter sometimes referred to as "BP-TMC"), in a specific composition ratio. This provides high heat resistance, durability, and resistance to heat yellowing, enabling use in high-temperature environments, as well as high refractive index and low birefringence, making it useful as an optical molding material. Furthermore, by adjusting the amount of phenolic hydroxyl groups derived from BP-TMC in the thermoplastic resin and the amount of specific trace components in the hydrolysate obtained by hydrolyzing the resin, the thermoplastic resin of the present invention exhibits better initial color tone when molded and reduced yellowing during heating tests. [Modes for carrying out the invention]

[0033] The present invention will be described in detail below with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples shown below. In this specification, unless otherwise specified, "~" means that the values ​​before and after it are included as the lower and upper limits. Furthermore, "structural unit" refers to a substructure sandwiched between adjacent linking groups in a polymer, and a substructure sandwiched between a polymerization-reactive group at the terminal end of a polymer and a linking group adjacent to that polymerization-reactive group. Furthermore, linking groups refer to carbonate bond portions (carbonate groups) and ester bond portions (ester groups).

[0034] Furthermore, in the present invention, polycarbonate resin refers to a resin in which the structural units constituting the resin include portions (carbonate groups) linked by carbonate bonds. The polycarbonate resin according to the present invention may optionally contain portions (ester groups) linked by ester bonds, as long as this does not hinder the effects of the present invention. That is, the polycarbonate resin according to the present invention also includes polyester carbonate resin.

[0035] [Thermoplastic resin] The thermoplastic resin of the present invention is a thermoplastic resin comprising a structural unit (A) represented by formula (1) (hereinafter simply referred to as "carbonate structural unit (A)") and a structural unit (B) represented by formula (2) (hereinafter simply referred to as "carbonate structural unit (B)"), and is commonly referred to as "polycarbonate resin," but is not limited to polycarbonate resin in any way. In the thermoplastic resin of the present invention, carbonate structural units (A) and carbonate structural units (B) may exist in the same polymer chain by copolymerization, or they may exist by blending a resin containing carbonate structural units (A) with a resin containing carbonate structural units (B). A blend of a resin containing carbonate structural units (A) and a resin containing carbonate structural units (B) is also called a "thermoplastic resin composition," but in the present invention it is referred to as a "thermoplastic resin."

[0036] <Carbonate structural unit (A)> The carbonate structural unit (A) is a structural unit represented by the following formula (1).

[0037] [ka]

[0038] (In formula (1), rings Z1 and Z2 each independently represent an aromatic hydrocarbon ring.) R1~R 10Each of these independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, which may contain a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an aromatic group. However, R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9 and R 10 Among the pairs, 1 to 4 pairs may be joined together to form a ring. i and ii independently represent the number obtained by subtracting 3 from the number of ring members of rings Z1 and Z2, respectively. Multiple R1 and R2 may be the same or different. X represents an alkylene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 12 carbon atoms, or an arylene group with 6 to 20 carbon atoms. n represents an integer between 0 and 10.

[0039] In formula (1) above, rings Z1 and Z2 each independently represent an aromatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings. From the viewpoint of improving the fluidity of thermoplastic resins, rings Z1 and Z2 are preferably benzene rings and naphthalene rings, respectively, and a benzene ring is more preferred.

[0040] In equation (1) above, R1 to R 10 Each of these independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, which may contain a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an aromatic group.

[0041] Examples of the C1-C20 hydrocarbon group mentioned above include saturated or unsaturated aliphatic or alicyclic hydrocarbon groups or aromatic hydrocarbon groups having C1-C20. If the C1-C20 hydrocarbon group has substituents, the substituents are not particularly limited as long as they do not hinder the effects of the present invention, but they are preferably selected from C1-C10 alkyl groups, C6-C10 aryl groups, and halogen atoms.

[0042] R1~R 10Of these, hydrogen atoms, methyl groups, cyclohexyl groups, phenyl groups, and naphthyl groups are preferred, hydrogen atoms, methyl groups, cyclohexyl groups, and phenyl groups are more preferred, hydrogen atoms, methyl groups, and phenyl groups are even more preferred, hydrogen atoms and methyl groups are particularly preferred, and hydrogen atoms are most preferred.

[0043] R1~R 10 If selected from the above, the thermoplastic resin of the present invention has a good balance of refractive index, heat resistance, strength, and raw material availability. In particular, R1~R 10 If the atom is a hydrogen atom, it is preferable from the viewpoint of high strength and easy availability of raw materials for the thermoplastic resin of the present invention.

[0044] In formula (1) above, when R1 and R2 are substituents other than hydrogen atoms, the number of substituents other than hydrogen atoms substituted on rings Z1 and Z2 is preferably 2 or less, more preferably 1 or less, and even more preferably R1 and R2 are all hydrogen atoms, from the viewpoint of achieving an excellent balance of refractive index, heat resistance, strength, and raw material availability for the thermoplastic resin of the present invention.

[0045] In equation (1) above, R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9 and R9 and R 10 Of these sets, 1 to 4 sets may bond to each other to form a ring. From the viewpoint of improving the refractive index of the thermoplastic resin of the present invention, when these bond to form a ring, it is preferable that they bond with hydrocarbon groups having a total of 4 carbon atoms, because this expands the conjugated system of the fluorene ring in formula (1).

[0046] In equation (1) above, R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9 and R9 and R 10 Preferably, one of these pairs of rings is bonded to each other to form a ring, or they do not form a ring. If the number of condensed rings is 0 or 1 pair, the thermoplastic resin of the present invention has a good balance of refractive index, heat resistance, strength, and raw material availability. In particular, if the number of condensed rings is 0 pairs, it is preferable from the viewpoint of high strength and high raw material availability for the thermoplastic resin of the present invention.

[0047] In formula (1) above, X represents an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms. From the viewpoint of balancing the heat resistance, thermal stability, strength, and raw material availability of the thermoplastic resin of the present invention, X is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, even more preferably an alkylene group having 2 to 4 carbon atoms, particularly preferably an alkylene group having 2 to 3 carbon atoms, and most preferably an alkylene group having 2 carbon atoms, i.e., an ethylene group.

[0048] In formula (1) above, n represents an integer from 0 to 10. From the viewpoint of balancing the heat resistance, thermal stability, strength, and raw material availability of the thermoplastic resin of the present invention, n is preferably from 0 to 8, more preferably from 0 to 5, even more preferably from 0 to 2, particularly preferably from 0 to 1, and most preferably 1. In formula (1), the two n values ​​may be the same or different, but it is preferable that they be the same from the viewpoint of raw material availability. Also, if there are multiple X values ​​in formula (1), the multiple X values ​​may be the same or different, but it is preferable that they be the same from the viewpoint of raw material availability.

[0049] From the viewpoint of balancing heat resistance, thermal stability, strength, and raw material availability of the thermoplastic resin of the present invention, the carbonate structural unit (A) is preferably a structural unit represented by the following formula (6) or (7), and most preferably a structural unit represented by the following formula (8).

[0050] [ka]

[0051] In the above equations (6) and (7), R 11 ~R 14 Each of these independently represents a hydrogen atom, a methyl group, or a phenyl group, preferably a hydrogen atom. R3~R 10 This is equivalent to the one in equation (1) above. However, R3 and R4, R4 and R5, R5 and R6, R7 and R8, R8 and R9 and R9 and R 10One of the pairs may be joined together to form a ring, but it is preferable that they are not joined together to form a ring.

[0052] [ka]

[0053] The carbonate structural unit (A) in the thermoplastic resin of the present invention is formed in the thermoplastic resin of the present invention by polymerization using a dihydroxy compound as a raw material and a carbonate-forming compound described later.

[0054] Examples of dihydroxy compounds used as raw materials include dihydroxy compounds represented by the following formula (9).

[0055] [ka]

[0056] (In formula (9), Z1, Z2, R1~R 10 The definitions and preferred examples of X, n, i, and ii are the same as in formula (1) above.

[0057] The thermoplastic resin of the present invention may contain only one type of carbonate structural unit (A), or it may contain two or more types.

[0058] <Carbonate structural unit (B)> The carbonate structural unit (B) is a structural unit represented by the following formula (2).

[0059] [ka]

[0060] The carbonate structural unit (B) in the thermoplastic resin of the present invention is formed in the thermoplastic resin of the present invention by polymerization using an aromatic dihydroxy compound as a raw material and a carbonate-forming compound described later.

[0061] Examples of aromatic dihydroxy compounds used as raw materials include aromatic dihydroxy compounds represented by the following formula (3).

[0062] [ka]

[0063] <Content ratio of carbonate structural unit (A) and carbonate structural unit (B)> The thermoplastic resin of the present invention contains carbonate structural units (A) and carbonate structural units (B) in the molar ratio described below. Preferably, the sum of the content ratios of carbonate structural units (A) and carbonate structural units (B) in the thermoplastic resin of the present invention is 30 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, particularly preferably 90 mol% or more, and most preferably 93 to 100 mol%. The effects of the invention can be fully realized if the sum of the content ratios of the carbonate structural unit (A) and the carbonate structural unit (B) contained in the thermoplastic resin of the present invention is equal to or greater than the above lower limit.

[0064] The ratio of carbonate structural units (A) to carbonate structural units (B) in the thermoplastic resin of the present invention is in the range of (A) / (B) = 50 / 50 to 99 / 1 in molar ratio, but this ratio is preferably (A) / (B) = 55 / 45 to 99 / 1 in molar ratio, more preferably (A) / (B) = 60 / 40 to 95 / 5, even more preferably (A) / (B) = 65 / 35 to 92 / 8, particularly preferably (A) / (B) = 65 / 35 to 90 / 10, and most preferably (A) / (B) = 65 / 35 to 85 / 15.

[0065] If the ratio of carbonate structural units (A) to carbonate structural units (B) in the thermoplastic resin of the present invention is within the above range, it can have high heat resistance, durability, and resistance to heat yellowing, as well as a high refractive index and low birefringence that are useful as optical molding materials. If the proportion of carbonate structural units (A) in the thermoplastic resin of the present invention is less than the lower limit and the proportion of carbonate structural units (B) exceeds the upper limit, high refractive index and low birefringence cannot be achieved. If the proportion of carbonate structural units (A) exceeds the upper limit and the proportion of carbonate structural units (B) is less than the lower limit, high heat resistance and durability cannot be achieved.

[0066] The content ratios of carbonate structural unit (A), carbonate structural unit (B), and other structural units described below, which may be included as needed, in the thermoplastic resin of the present invention are determined by the proportion of dihydroxy compounds used as raw materials for producing the thermoplastic resin of the present invention, which are used to form these structural units in the thermoplastic resin of the present invention.

[0067] <Content of compounds (3) to (4) in the hydrolysate> The hydrolyzed product obtained by hydrolyzing the thermoplastic resin of the present invention contains compounds represented by the following formulas (3) to (5), and it is preferable that the sum of the content of the compound represented by the following formula (4) (hereinafter sometimes referred to as "compound (4)") and the compound represented by the following formula (5) (hereinafter sometimes referred to as "compound (5)") in the hydrolyzed product is 1.00% by mass or more relative to the content of the compound represented by the following formula (3) (hereinafter sometimes referred to as "compound (3)"). When this ratio (hereinafter sometimes referred to as "{(4)+(5)} / (3) ratio") is 1.00% by mass or more, the initial color tone of the thermoplastic resin of the present invention is good.

[0068] [ka]

[0069] From the viewpoint of initial color tone, the {(4)+(5)} / (3) ratio in the hydrolysate is more preferably 1.02% by mass or more, even more preferably 1.05% by mass or more, and particularly preferably 1.10% by mass or more. On the other hand, from the viewpoint of improving strength, the {(4)+(5)} / (3) ratio in the hydrolysate is preferably 5% by mass or less, and particularly preferably 3% by mass or less.

[0070] To set the {(4)+(5)} / (3) ratio of the hydrolyzed product of the thermoplastic resin within the above preferred range, this can be achieved, for example, by appropriately adjusting the purity of compound (3), 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (BP-TMC), which is a raw material for the thermoplastic resin of the present invention. Specifically, compounds (4) and (5) are impurities present in compound (3) during its production. This can be achieved by using compound (3) with an appropriate amount of compounds (4) and (5) in the raw material for the thermoplastic resin of the present invention, by appropriately purifying compound (3) to adjust the content of compounds (4) and (5), or by appropriately blending compound (3) with different content levels of these compounds. It can also be achieved by appropriately adjusting the pressure, temperature, and setting conditions at the end of the polymerization reaction during the production of the thermoplastic resin.

[0071] <Other structural units> The thermoplastic resin of the present invention may contain structural units other than carbonate structural unit (A) and carbonate structural unit (B) (hereinafter sometimes referred to as "other structural units"). Examples of monomers that form other structural units in the thermoplastic resin of the present invention include dihydroxy compounds and diester compounds containing aromatic components. Among these, dihydroxy compounds containing aromatic components are preferred from the viewpoint of improving reaction efficiency.

[0072] (Dihydroxy compounds containing aromatic components) Examples of dihydroxy compounds containing aromatic components include the following dihydroxy compounds. 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)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 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(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-Bis(4-hydroxyphenyl)cyclohexane, Bis(4-hydroxyphenyl)sulfone, 2,4'-Dihydroxydiphenylsulfone, Bis(4-hydroxyphenyl) sulfide, Bis(4-hydroxy-3-methylphenyl) sulfide, Bis(4-hydroxyphenyl) disulfide, 4,4'-Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobindan, 7,7'-dimethyl-6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobindan, Aromatic bisphenol compounds 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, Bis(4-(2-hydroxyethoxy)phenyl) sulfone, Dihydroxy compounds having an ether group bonded to an aromatic group such as:

[0073] However, since dihydroxy compounds having an ether group bonded to an aromatic group and carbonate structural units derived from carbonate-forming compounds or carbonate esters described later reduce the thermal stability of the resin, it is preferable to use a smaller amount of dihydroxy compounds having an ether group bonded to an aromatic group.

[0074] As for dihydroxy compounds containing aromatic components that form other structural units, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is preferred in terms of the balance between heat resistance and raw material cost.

[0075] (Diester compounds) Examples of diester compounds that can be used include the dicarboxylic acids listed below. 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, and 2,6-naphthalenedicarboxylic acid; Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and decalin-2,6-dicarboxylic acid; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid: These dicarboxylic acid components can be used as raw materials for polyester carbonate as dicarboxylic acids themselves, but depending on the manufacturing method, dicarboxylic acid esters such as methyl esters and phenyl esters, or dicarboxylic acid derivatives such as dicarboxylic acid halides can also be used as raw materials. Since the polymerization reactivity of diester compounds is relatively low, from the viewpoint of improving reaction efficiency, it is preferable to use fewer other diester compounds, excluding carbonate esters and diester compounds having oligofluorene structural units.

[0076] Dihydroxy compounds and diester compounds for forming other structural units may be used alone or in combination of two or more, depending on the required performance of the resulting resin. The content of other structural units in the resin is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 10% by mass or less, when the total mass of all structural units and linking groups constituting the thermoplastic resin is taken as 100% by mass. Other structural units mainly play a role in adjusting the heat resistance of the resin and imparting flexibility and toughness, but if their content is too high, the heat resistance and optical properties may deteriorate.

[0077] <Amount of phenolic hydroxyl groups derived from compound (3)> The thermoplastic resin of the present invention preferably has a phenolic hydroxyl group content of 100 to 1500 ppm by mass derived from the aromatic dihydroxy compound (3) represented by the following formula (3).

[0078] [ka]

[0079] Because the amount of phenolic hydroxyl groups derived from compound (3) is limited to a range of 100 to 1500 ppm by mass, the thermoplastic resin of the present invention has better initial color when molded and less yellowing during heating tests. The amount of phenolic hydroxyl groups derived from compound (3) of the thermoplastic resin of the present invention is more preferably 100 to 1200 ppm by mass, even more preferably 300 to 1000 ppm by mass, particularly preferably 600 to 900 ppm by mass, and most preferably 500 to 850 ppm by mass.

[0080] The amount of phenolic hydroxyl groups derived from compound (3) represents the total amount M of terminal hydroxyl groups represented by the following formula (10), where the unit of terminal hydroxyl group amount is expressed in ppm as the mass of terminal hydroxyl groups relative to the mass of thermoplastic resin. The measurement method is colorimetric determination by the titanium tetrachloride / acetic acid method (as described in Macromol. Chem. 88 215 (1965)).

[0081] [ka]

[0082] The amount of terminal hydroxyl groups in thermoplastic resins can be adjusted to a desirable value by controlling the molar ratio of raw materials, the amount of catalyst, and the temperature and vacuum level during the reaction.

[0083] Furthermore, the thermoplastic resin of the present invention may be a mixture of two or more thermoplastic resins with different amounts of phenolic hydroxyl groups derived from compound (3). In this case, thermoplastic resins with amounts of phenolic hydroxyl groups derived from compound (3) that are outside the above preferred range may be used, and these may be mixed and controlled to obtain the above preferred amount of phenolic hydroxyl groups derived from compound (3).

[0084] <Properties of thermoplastic resins> (Glass transition temperature (Tg)) The thermoplastic resin of the present invention has a high glass transition temperature (Tg) and excellent heat resistance. The Tg of the thermoplastic resin of the present invention is preferably 110°C or higher, more preferably 120°C or higher, even more preferably 140°C or higher, and particularly preferably 150°C or higher. If the Tg of the thermoplastic resin of the present invention is too low, the heat resistance of the resin will be poor, such as causing deformation of the test piece during heat resistance testing.

[0085] On the other hand, from the viewpoint of ensuring good durability, the Tg of the thermoplastic resin of the present invention is preferably 200°C or lower, more preferably 190°C or lower, and even more preferably 180°C or lower. If the Tg of the thermoplastic resin of the present invention is too high, the durability of the resin will be poor, such as when cracks occur in the test specimen during heat resistance testing.

[0086] The thermoplastic resin of the present invention contains carbonate structural units (A) and carbonate structural units (B) within the above-described preferred range, allowing for easy adjustment of Tg to a range that achieves both high heat resistance and good durability. Therefore, the thermoplastic resin of the present invention is suitable for applications that are expected to be exposed to high-temperature environments, such as automotive optical lenses.

[0087] The glass transition temperature (Tg) of the thermoplastic resin is measured by the method described in the Examples section below.

[0088] (Viscosity average molecular weight (Mv)) The molecular weight of the thermoplastic resin of the present invention is the viscosity-average molecular weight (Mv) calculated from the solution viscosity, preferably 5,000 to 50,000. If the viscosity-average molecular weight is above the lower limit, the mechanical properties of the molded article made from the thermoplastic resin of the present invention will be good. Furthermore, if the viscosity-average molecular weight is below the upper limit, the fluidity and moldability of the thermoplastic resin of the present invention tend to be good. From this viewpoint, the viscosity-average molecular weight (Mv) of the thermoplastic resin of the present invention is more preferably 6,000 to 30,000, and even more preferably 7,000 to 20,000.

[0089] The viscosity-average molecular weight (Mv) of the thermoplastic resin of the present invention is determined by using methylene chloride as the solvent and calculating the intrinsic viscosity (intrinsic viscosity) [η] (unit: dL / g) at a temperature of 20°C using an Ubbelohde viscometer, and then using Schnell's viscosity formula, i.e., η = 1.23 × 10⁻¹⁰ -4 Mv 0.83 It refers to the value calculated from [the above]. Intrinsic viscosity (intrinsic viscosity) [η] is the specific viscosity [η] at each solution concentration [C] (g / dL). sp This value was calculated by measuring [the value] and using the following formula.

[0090]

number

[0091] <Refractive index (n D )> The refractive index (n) of the thermoplastic resin of the present invention at a wavelength of 589 nm and a temperature of 20°C. D The refractive index is, for example, 1.590 or higher, preferably 1.601 to 1.700, more preferably 1.605 to 1.680, and even more preferably 1.610 to 1.660. If the refractive index is 1.601 or higher, the added value when the thermoplastic resin of the present invention is used as an optical material such as a lens is higher. In order to make a thermoplastic resin with a refractive index exceeding 1.700, it is necessary to form structural units with a high refractive index in the thermoplastic resin of the present invention, and in this case, there is a risk that the Tg will become excessively high, the thermal stability of the resin will decrease, and mold contamination will increase.

[0092] (Abbe number (ν D )) The Abbe number (ν) of the thermoplastic resin of the present invention at a temperature of 20°C D The Abbe number is, for example, 35.0 or less, preferably 15.0 to 35.0, more preferably 16.0 to 32.0, even more preferably 20.0 to 30.0, particularly preferably 21.0 to 27.0, and most preferably 22.0 to 25.9. If the Abbe number is small, it is useful as a material for low Abbe number concave lenses for aberration correction used in combination with high Abbe number convex lenses such as COP (cycloolefin polymer). If the Abbe number is smaller than the lower limit, it is necessary to form structural units with a high refractive index in the thermoplastic resin of the present invention, in which case there is a risk that the Tg will become excessively high, the thermal stability of the resin will decrease, or mold contamination will increase.

[0093] Here, the refractive index (n D ) rounds to the fourth decimal place, Abbe number (ν D The value shown is rounded to two decimal places. The refractive index and Abbe number of the thermoplastic resin are measured by the method described in the Examples section below.

[0094] (Increase in YI per hour (ΔYI / hour)) In the thermoplastic resin of the present invention, it is preferable that the increase in YI per hour (ΔYI / hour) [1 / Hr] calculated by the following formula in a 3 mm thick test specimen made of the thermoplastic resin of the present invention is 0.0500 or less. If the increase in YI per hour (ΔYI / hour) is 0.0500 or less, it exhibits excellent long-term heat resistance. From the viewpoint of long-term heat resistance, the smaller the increase in YI per hour (ΔYI / hour), the more preferable it is, more preferably 0.0400 or less, and particularly preferably 0.0300 or less. Increase in YI per hour (ΔYI / hour) = (Yellowness of the test specimen after heating - Yellowness of the test specimen before heating) / Heating time In the above formula, the yellowness of the test specimen after heating is the yellowness measured in accordance with JIS K7373 after conducting a heat resistance test in which the test specimen is left standing in an environment of normal pressure and 135°C for 280 hours, and the yellowness of the test specimen before heating is the yellowness measured in accordance with JIS K7373 before conducting the heat resistance test, with a heating time of 280 hours. The increase in YI per hour (ΔYI / hour) is measured by the method described in the Examples section below.

[0095] [Method for manufacturing thermoplastic resins] The thermoplastic resin of the present invention can be produced by conventional polymerization methods, and the polymerization method is not particularly limited. Examples of polymerization methods include interfacial polymerization, molten transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Particularly preferred methods among these will be described in detail below.

[0096] <Interfacial polymerization method> In the interfacial polymerization method, a thermoplastic resin is obtained by reacting a dihydroxy compound and a carbonate-forming compound in the presence of an organic solvent and an alkaline aqueous solution that are inert to the reaction, usually maintaining a pH of 9 or higher, and then carrying out interfacial polymerization in the presence of a polymerization catalyst. A molecular weight modifier (end-terminating agent) may be added to the reaction system as needed, and an antioxidant may be added to prevent oxidation of the dihydroxy compound.

[0097] The organic solvent that is inert to the reaction is not particularly limited, but examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; and so on. One organic solvent may be used, or two or more may be used in any combination and ratio.

[0098] The alkali compounds contained in the alkaline aqueous solution are not particularly limited, but examples include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate, as well as alkaline earth metal compounds. Among these, sodium hydroxide and potassium hydroxide are preferred. Note that one alkali compound may be used, or two or more may be used in any combination and ratio.

[0099] There are no restrictions on the concentration of the alkali compound in the alkaline aqueous solution, but typically, to control the pH of the alkaline aqueous solution to 10-12, the alkali compound concentration is used at 5-10% by mass. Furthermore, for example, when bubbling in phosgene, in order to control the pH of the aqueous phase to 10-12, preferably 10-11, it is preferable to set the molar ratio of the starting material dihydroxy compound to the alkali compound to 1:1.9 or higher, more preferably 1:2.0 or higher, and more preferably 1:3.2 or lower, more preferably 1:2.5 or lower.

[0100] By using a dihydroxy compound as a raw material that contains both the aromatic dihydroxy compound necessary for forming the aforementioned carbonate structural unit (A) and the aromatic dihydroxy compound necessary for forming the carbonate structural unit (B), the thermoplastic resin of the present invention having carbonate structural units (A) and carbonate structural units (B) can be produced.

[0101] Carbonyl halides are preferably used as carbonate-forming compounds, and among these, phosgene is preferred. The method using phosgene is specifically called the phosgene method.

[0102] The polymerization catalyst is not particularly limited, but examples include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; guanine; salts of guanidine; and so on. Note that one polymerization catalyst may be used, or two or more may be used in any combination and ratio.

[0103] While not particularly limited, examples of molecular weight modifiers include aromatic alcohols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; and phthalimides, among which aromatic alcohols are preferred.

[0104] Examples of such aromatic alcohols include phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, mn-nonylphenol, pn-nonylphenol Examples include ol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, monoalkylphenols having a linear or branched alkyl group with an average of 12 to 35 carbon atoms in the ortho, meta, or para position, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, 4-(1-adamantyl)phenol, etc. Among these, pt-butylphenol, p-phenylphenol, and p-cumylphenol are preferably used.

[0105] Furthermore, one molecular weight adjusting agent may be used, or two or more may be used in any combination and ratio.

[0106] The amount of molecular weight modifier used is not particularly limited, but for example, it is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the dihydroxy compound raw material. By using the amount of molecular weight modifier within this range, the thermal stability and hydrolysis resistance of the thermoplastic resin can be improved.

[0107] While not particularly limited, examples of antioxidants include hindered phenol-based antioxidants. Specific examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphoate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6- Examples include triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[0108] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Examples of commercially available phenolic antioxidants include BASF's "Irganox 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60."

[0109] Other antioxidants include, for example, phosphite-based antioxidants. Specific examples include tris(2,4-di-tert-butylphenyl) phosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylphenyl phosphite, tris(nonylphenyl) phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyl diphosphite, 2-ethylhexyldiphenyl phosphite, isodecyldiphenyl phosphite, triisodecyl phosphite, and triphenyl phosphite.

[0110] Among these, tris(2,4-di-tert-butylphenyl)phosphite and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are preferred. Examples of commercially available phosphite-based antioxidants include BASF's "Irgaphos 168," ADEKA's "ADEKA Stab 2112," and "ADEKA Stab PEP-36."

[0111] Furthermore, one type of antioxidant may be used, or two or more types may be used in any combination and ratio.

[0112] The amount of antioxidant used is not particularly limited, but for example, it is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, per 100 parts by mass of the raw material dihydroxy compound. If the amount of antioxidant used is below the lower limit of the above range, the antioxidant effect may be insufficient, and if the amount of antioxidant used exceeds the upper limit of the above range, gas may be more easily released during injection molding.

[0113] During the reaction, the order in which the reaction substrate (reaction raw material), reaction solvent (organic solvent), catalyst, additives, etc. are mixed is arbitrary as long as the desired thermoplastic resin is obtained, and any appropriate order can be set. For example, when phosgene is used as the carbonate-forming compound, the molecular weight modifier can be mixed at any time between the reaction between the starting material dihydroxy compound and phosgene (phosgenation) and the start of the polymerization reaction. The reaction temperature is not particularly limited, but is usually between 0 and 40°C, and the reaction time is not particularly limited, but is usually between a few minutes (e.g., 10 minutes) and several hours (e.g., 6 hours).

[0114] <Fusion transesterification method> In the molten transesterification method, for example, a transesterification reaction is carried out between a carbonate ester and a starting dihydroxy compound. The starting dihydroxy compound is the same as that used in the interfacial polymerization method. Furthermore, the monomers necessary to form the other structural units are also the same as those used in the interfacial polymerization method.

[0115] Examples of carbonate esters include compounds represented by the following formula (I), such as aryl carbonates, dialkyl carbonates, biscarbonate forms of dihydroxy compounds, monocarbonate forms of dihydroxy compounds, and carbonate forms of dihydroxy compounds such as cyclic carbonates.

[0116] [ka]

[0117] (In formula (I), R 21 , R 22 Each of these independently represents a C1-C30 alkyl group, aryl group, or arylalkyl group, which may have substituents.

[0118] Below, R 21 and R 22 However, when it is an alkyl group or arylalkyl group, it is sometimes called a dialkyl carbonate, and when it is an aryl group, it is sometimes called a diaryl carbonate. In particular, from the viewpoint of reactivity with aromatic dihydroxy compounds, R 21 and R 22 Both are preferably aryl groups, and the carbonate ester is more preferably a diaryl carbonate represented by the following formula (II).

[0119] [ka]

[0120] (In formula (II), R 23 , R 24 Each of these is independently a halogen atom, a nitro group, a cyano group, a C1-C20 alkyl group, a C1-C20 alkoxycarbonyl group, a C4-C20 cycloalkyl group, or a C6-C20 aryl group, and p and q each independently represent an integer from 0 to 5.

[0121] Examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), diaryl carbonates (which may have substituents) such as bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate, bis(4-fluorophenyl) carbonate, bis(2-chlorophenyl) carbonate, bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, bis(2-nitrophenyl) carbonate, bis(methylsalicylphenyl) carbonate, and ditril carbonate, but among these, diphenyl carbonate is preferred.

[0122] These carbonate esters can be used individually or in combination of two or more.

[0123] Furthermore, the carbonate ester may be substituted with a diester compound such as a dicarboxylic acid or a dicarboxylic acid ester, in which case a polyester carbonate is obtained. Since the polymerization reactivity of diester compounds is relatively low, it is preferable to use fewer other diester compounds from the viewpoint of increasing reaction efficiency. The substitution ratio of the carbonate ester with a diester compound is preferably 50 mol% or less, and more preferably 30 mol% or less. Typical diester compounds are as described above.

[0124] The ratio of the raw material dihydroxy compound to the carbonate ester is arbitrary as long as the desired thermoplastic resin is obtained, but it is preferable to use these carbonate esters in excess of the raw material dihydroxy compound when polymerizing them. That is, the amount of carbonate ester used is preferably 1.01 to 1.30 times (mol ratio) of the raw material dihydroxy compound, and more preferably 1.02 to 1.20 times (mol ratio). If this mol ratio is too small, the amount of terminal hydroxyl groups in the resulting thermoplastic resin will be large, and the thermal stability of the resin will tend to deteriorate. On the other hand, if this mol ratio is too large, the reaction rate of transesterification will decrease, making it difficult to produce a thermoplastic resin with the desired molecular weight, or the amount of residual carbonate ester in the resin will be large, which may cause odor during molding or in the molded product.

[0125] When producing thermoplastic resins by the molten transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, alkali metal compounds and / or alkaline earth metal compounds are preferred. In addition, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination as auxiliary agents. One type of transesterification catalyst may be used, or two or more types may be used in any combination and ratio.

[0126] In the molten transesterification method, the reaction temperature is not particularly limited, but is usually between 100 and 320°C. The reaction pressure is also not particularly limited, but is usually under reduced pressure of 2 mmHg or less. Specifically, the molten polycondensation reaction can be carried out under the above conditions while removing by-products.

[0127] In this case, the thermoplastic resin of the present invention is significantly affected by thermal history and oxidation in the presence of an alkaline catalyst, leading to deterioration of its hue. Therefore, it is preferable to keep the reaction temperature below 320°C and to select reduced pressure conditions with a lower limit of approximately 0.05 mmHg to prevent oxygen leakage from the equipment due to excessive reduced pressure.

[0128] The reaction can be carried out using either a batch or continuous reaction method. In the case of a batch reaction, the order in which the reaction substrate, reaction solvent, catalyst, additives, etc. are mixed is arbitrary as long as the desired thermoplastic resin is obtained, and any appropriate order can be set.

[0129] In the molten transesterification process, a catalyst deactivator may be used as needed. Any compound that neutralizes the transesterification catalyst can be used as the catalyst deactivator. Examples include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc. One catalyst deactivator may be used, or two or more may be used in any combination and ratio.

[0130] The amount of catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, relative to the transesterification catalyst, and is usually 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less. The amount of catalyst deactivator used is usually 1 ppm or more, and 100 ppm or less, relative to the thermoplastic resin, and is preferably 50 ppm or less.

[0131] [Thermoplastic resin composition] The thermoplastic resin composition of the present invention is a mixture of the thermoplastic resin of the present invention and known additives and / or resins other than the thermoplastic resin of the present invention (hereinafter sometimes referred to as "other resins").

[0132] As long as the additive does not impair the excellent physical properties of the thermoplastic resin of the present invention, any known additive can be used without particular limitation. Examples of such additives include the various additives exemplified below as additives that may be contained in the molded articles of the present invention, but among them, at least one selected from the group consisting of heat stabilizers, antioxidants, ultraviolet absorbers, brightness enhancers, dyes, pigments, mold release agents, flow modifiers, and impact resistance enhancers is particularly noteworthy. Of these additives, for example, antioxidants are preferably used in a ratio of 100 to 10,000 ppm, particularly 500 to 5,000 ppm, relative to the thermoplastic resin of the present invention, and the total amount of these additives is preferably 10,000 ppm or less relative to the thermoplastic resin of the present invention.

[0133] Furthermore, the thermoplastic resin composition of the present invention may contain other resins in addition to the thermoplastic resin of the present invention, as necessary, as long as the desired physical properties are not significantly impaired. Other resins are not particularly limited, but examples include polycarbonate resins other than the thermoplastic resin of the present invention, and resins other than polycarbonate resins. The polycarbonate resin is not particularly limited, but examples include polycarbonate resins derived from bisphenol A. Among such polycarbonate resins, those derived from bisphenol A are preferred because they have relatively high heat resistance and refractive index, and are inexpensive. Examples of resins other than polycarbonate resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; styrene-based resins such as polystyrene resin, high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; and polymethacrylate resin.

[0134] Furthermore, the other resins may be present in any single form, or in any combination and ratio of two or more forms.

[0135] In order to more effectively obtain the effects of the present invention by including the thermoplastic resin of the present invention in the thermoplastic resin composition of the present invention, the content of the thermoplastic resin of the present invention in the thermoplastic resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 70% by mass or more.

[0136] Similar to the thermoplastic resin of the present invention, it is preferable that the increase in YI per hour (ΔYI / hour) [1 / Hr] calculated by the following formula in a 3 mm thick test piece made of the thermoplastic resin composition of the present invention is 0.0500 or less. If the increase in YI per hour (ΔYI / hour) is 0.0500 or less, it exhibits excellent long-term heat resistance when heated. From the viewpoint of long-term heat resistance, a smaller increase in YI per hour (ΔYI / hour) is preferable, more preferably 0.0400 or less, and particularly preferably 0.0300 or less. Increase in YI per hour (ΔYI / hour) = (Yellowness of the test specimen after heating - Yellowness of the test specimen before heating) / Heating time In the above formula, the yellowness of the test specimen after heating is the yellowness measured in accordance with JIS K7373 after conducting a heat resistance test in which the test specimen is left standing in an environment of normal pressure and 135°C for 280 hours, and the yellowness of the test specimen before heating is the yellowness measured in accordance with JIS K7373 before conducting the heat resistance test, with a heating time of 280 hours.

[0137] [Molded body] The molded article of the present invention can be manufactured by molding the thermoplastic resin of the present invention, or a thermoplastic resin composition of the present invention containing the thermoplastic resin of the present invention.

[0138] The shape of the molded article of the present invention is not particularly limited and can include, for example, a one-dimensional structure (e.g., linear, thread-like, etc.), a two-dimensional structure (e.g., film-like, sheet-like, plate-like, etc.), or a three-dimensional structure (e.g., concave or convex lens-like, rod-like, hollow (tubular), etc.).

[0139] The molded articles of the present invention may contain various additives [for example, fillers or reinforcing agents, colorants (e.g., dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (e.g., antioxidants, UV absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, defoaming agents, surface modifiers, stress-reducing agents (e.g., silicone oil, silicone rubber, various plastic powders, various engineering plastic powders, etc.), carbon materials, etc.]. These additives may be used individually or in combination of two or more.

[0140] The molded articles of the present invention can be manufactured using methods such as injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, and casting molding.

[0141] When manufacturing a molded article of the present invention by such a molding method, it is preferable that the maximum molding temperature be 250°C or higher. If the maximum molding temperature is 250°C or higher, the fluidity during molding is increased, and a molded article with further reduced birefringence can be obtained. That is, the thermoplastic resin of the present invention has excellent heat resistance and can be used for molding over a wide temperature range, especially injection molding, so birefringence can be further reduced by molding at such high temperatures. From the viewpoint of reducing birefringence, it is more preferable that the maximum molding temperature be 255°C or higher, and even more preferable that be 260°C or higher. However, if the molding temperature is excessively high, the resin may undergo thermal decomposition during molding, so it is preferable that the maximum molding temperature be 320°C or lower.

[0142] Because the molded articles of the present invention have excellent heat resistance and optical properties (high refractive index, low birefringence, etc.), they can be used as optical components such as optical films, optical lenses, and optical sheets.

[0143] In particular, the thermoplastic resin of the present invention is suitable for injection molding, similar to conventional polycarbonate lenses, and is therefore useful for forming optical lenses. Examples of optical lenses are not particularly limited, but include automotive lenses, eyeglass lenses, pickup lenses, camera lenses, microarray lenses, projector lenses, and Fresnel lenses. In particular, because the thermoplastic resin of the present invention has high heat resistance, it can be suitably used even in applications where use in high-temperature environments is anticipated, such as automotive optical lenses. [Examples]

[0144] The present invention will be described more specifically below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below.

[0145] The physical properties of the thermoplastic resins produced in the following examples and comparative examples were evaluated by the method described below.

[0146] (1) Viscosity average molecular weight (Mv) The sample was dissolved in methylene chloride (concentration 6.0 g / L), and the specific viscosity [η] was measured using an Ubbelohde viscometer (manufactured by Moritomo Rika Kogyo Co., Ltd.). sp The following was measured. Then, the intrinsic viscosity (intrinsic viscosity) [η] (unit dL / g) at 20°C was determined using the aforementioned formula, and the viscosity-average molecular weight (Mv) was calculated from Schnell's viscosity formula (see below). η = 1.23 × 10 -4 Mv 0.83

[0147] (2) Glass transition temperature (Tg) Using a differential calorimeter DSC6220 manufactured by SII Nanotechnology, approximately 10 mg of the sample was heated at a heating rate of 20°C / min, and the heat content was measured. In accordance with JIS K7121, the extrapolated glass transition onset temperature was determined as the temperature at the intersection of a straight line extending from the low-temperature baseline to the high-temperature side and a tangent line drawn at the point where the slope of the curve representing the stepwise transition of the glass transition is maximum. This extrapolated glass transition temperature was defined as the glass transition temperature (Tg).

[0148] (3) Refractive index (nD ), Abbe number (ν D ) Approximately 4 g of the sample, vacuum-dried at 100°C for 2 hours, was subjected to a hot press using a spacer measuring 8 cm wide, 8 cm long, and 0.5 mm thick. The press was heated at 200-250°C for 1-3 minutes, preheated for 1-3 minutes, and then pressurized at 20 MPa for 1 minute. The spacer was then removed and allowed to cool at room temperature to produce a film with a thickness of 100-300 μm. From this film, rectangular test pieces measuring 40 mm long and 8 mm wide were cut out to be used as measurement samples. The refractive index and n of each wavelength were measured using a multi-wavelength Abbe refractometer (DRM4 / 1550, manufactured by Atago Co., Ltd.) with interference filters at wavelengths of 656 nm (C line), 589 nm (D line), and 486 nm (F line). C , n D , n F The following measurements were taken. The measurements were performed at 20°C using monobromonaphthalene as the interfacial liquid. Abbe number ν D This was calculated using the following formula. ν D =(1-n D ) / (n C -n F )

[0149] (4) Birefringence A dumbbell-shaped resin plate with a total length of 75 mm, a parallel section length of 30 mm, a parallel section width of 5 mm, a thickness of 2 mm, and a gripping section width of 10 mm was placed between two polarizers that were in a crossed nicol state at the angle in which the polarized color was most strongly displayed. Under conditions where white light was irradiated from behind on an observation table, the polarized color appearing on the test piece was visually observed, and the degree of birefringence was evaluated according to the following criteria. ◎: No polarized color is visible, or polarized color is only visible in the 5mm wide parallel section and only one color is visible. ○: Polarized color is visible only in the 5mm wide parallel section, and there are two colors. △: Polarized color is visible only in the 5mm wide parallel section, and there are three or more colors. ×: Polarized coloration is visible throughout the entire test specimen. The dumbbell-shaped resin plate, with a total length of 75 mm, a parallel section length of 30 mm, a parallel section width of 5 mm, a thickness of 2 mm, and a gripping section width of 10 mm, was obtained using a small injection molding machine. Specifically, pellets of thermoplastic resin or a thermoplastic resin composition dried at 105°C for 5 hours or more were supplied to a small injection molding machine (C, Mobile, manufactured by Shinko Cellbic Co., Ltd.), and injection molding was performed under conditions of a final cylinder temperature of 260°C and a mold temperature of 110-120°C.

[0150] (5) Initial color pellet YI The initial color tone of thermoplastic resins or thermoplastic resin compositions was evaluated by measuring the YI value (Yellow Index value) in the reflected light of the pellets, in accordance with ASTM D1925. Specifically, a Konica Minolta CM-5 spectrophotometer was used, with measurement conditions of a 30 mm measurement diameter and SCE (Semiconductor Optimum Concentration). A CM-A212 calibration glass for petri dish measurement was fitted into the measurement section, and a CM-A124 zero calibration box was placed over it to perform zero calibration. Subsequently, white calibration was performed using the built-in white calibration plate. Measurements were performed using a white calibration plate CM-A210, confirming that L* was 99.40±0.05, a* was 0.03±0.01, b* was -0.43±0.01, and YI was -0.58±0.01. Pellet measurements were performed by filling a cylindrical glass container with an inner diameter of 30 mm and a height of 50 mm with pellets to a depth of approximately 40 mm. The process of removing the pellets from the glass container and measuring again was repeated twice, and the average of the three measured values ​​was used.

[0151] (6) Initial color test piece YI The initial color tone (YI) of thermoplastic resins or thermoplastic resin compositions was measured in accordance with JIS K7373 for test specimens of thermoplastic resins or thermoplastic resin compositions measuring 3 mm in thickness, 60 mm in length, and 60 mm in width, using the YI value (Yellow Index value) for transmitted light in the thickness direction. The instrument used was a Konica Minolta CM3700d spectrophotometer. The test specimens, measuring 3 mm thick, 60 mm long, and 60 mm wide, were obtained using a standard injection molding machine. Specifically, pellets of thermoplastic resin or thermoplastic resin composition dried at 105°C for 5 hours or more were supplied to an injection molding machine (J75EII model, manufactured by Japan Steel Works), and plate-type injection-molded pieces were obtained under conditions of a final cylinder temperature of 260°C and a mold temperature of 110-120°C.

[0152] (7) Long-term heat resistance The long-term heat resistance of thermoplastic resins or thermoplastic resin compositions was evaluated by a heat resistance test using test specimens of the thermoplastic resin or thermoplastic resin composition measuring 3 mm in thickness, 60 mm in length, and 60 mm in width. Specifically, the top of each test specimen was clamped with a double clip having a fastening portion measuring 15 mm in width, 25 mm in length, and 6 mm in height, and the specimens were suspended in a hot air dryer by passing a wire through the hole in the knob of each double clip. The hot air dryer was operated at a set temperature of 135°C, and the specimens were left standing in an environment of 135°C at atmospheric pressure for 280 hours. The evaluation items were the following two evaluation items A and B. <Evaluation Item A: YI increase per hour (ΔYI / hour)> The increase in YI per hour (ΔYI / hour) [1 / Hr] was calculated using the following formula. Increase in YI per hour (ΔYI / hour) = (Yellowness of the test specimen after heating - Yellowness of the test specimen before heating) / Heating time In the above formula, the yellowness of the test specimen before heating was the value obtained from the initial color test specimen YI in (6) above. The yellowness of the test specimen after heating was measured using the same method as for the initial color test specimen YI in (6) above, for the test specimen after the heat resistance test was performed. The heating time was 280 hours. <Evaluation Item B: Presence or absence of changes in appearance> The presence or absence of changes in appearance was evaluated visually according to the following criteria. Crack occurred: A crack has occurred. Deformation present: No cracks were found, but deformation was observed. None: No cracks or deformation were observed.

[0153] [Examples of synthesis and characterization of thermoplastic resins or thermoplastic resin compositions] The abbreviations for the compounds used in the following examples and comparative examples are as follows. • BPEF: 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) • BP-TMC: 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (manufactured by Honshu Chemical Co., Ltd. or Songwon Co., Ltd.) • DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation) • Phosphorous acid: Catalyst deactivator, phosphonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • PTSB: Catalyst deactivator, butyl p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) • AS2112: Antioxidant, ADEKA Stab 2112 (manufactured by ADEKA Corporation) • Irg1076: Antioxidant, Irganox 1076 (manufactured by BASF)

[0154] [Example 1] When the total amount of dihydroxy compounds used as raw materials is 100 mol parts, 70 mol parts of BPEF, 30 mol parts of BP-TMC (manufactured by Honshu Chemical Co., Ltd.), 105.0 mol parts of DPC, and a 0.2 mass% aqueous solution of calcium acetate as a catalyst are used, with calcium acetate content 0.5 × 10 -4 The substance was added to a 40L capacity first reactor equipped with a stirrer, heat transfer jacket, vacuum pump, and reflux condenser to form a molar portion.

[0155] Next, the pressure inside the first reactor was reduced to 1.33 kPa (10 Torr), and then the pressure was restored to atmospheric pressure with nitrogen. This process was repeated five times to purge the inside of the first reactor with nitrogen. After nitrogen purging, the internal temperature of the first reactor was gradually increased by passing a heat transfer medium at 230°C through the heat transfer medium jacket to dissolve the mixture. Subsequently, the temperature inside the first reactor was controlled by rotating a stirrer at 330 rpm to maintain the internal temperature of the first reactor at 220°C. Then, while distilling off the phenol produced as a by-product by the oligomerization reaction of the dihydroxy compound and DPC occurring inside the first reactor, the pressure inside the first reactor was reduced from an absolute pressure of 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) over 40 minutes.

[0156] Next, the pressure in the first reactor was maintained at 13.3 kPa, and the transesterification reaction was carried out for 5 minutes while the phenol was further distilled off. The system was then repressurized with nitrogen to an absolute pressure of 101.3 kPa, and then increased to a gauge pressure of 0.2 MPa. The oligomer from the first reactor was then pumped to the second reactor via a transfer pipe that had been preheated to over 200°C. The second reactor had a volume of 30 L and was equipped with a stirrer, a heat transfer medium jacket, a vacuum pump, and a reflux condenser. The internal pressure was controlled to atmospheric pressure and the internal temperature to 230°C.

[0157] Next, the oligomer pumped into the second reactor was stirred at 20 rpm, and the internal temperature was controlled by a heat transfer jacket. The pressure inside the second reactor was reduced from 101.3 kPa to 13.3 kPa over 40 minutes. Then, the temperature was increased, and the internal pressure was reduced from 13.3 kPa to 399 Pa (3 Torr) over another 40 minutes to remove the distilled phenol from the system. The pressure was further reduced to carry out the polycondensation reaction. The polycondensation reaction was terminated when the stirrer in the second reactor reached a predetermined stirring power (equivalent to a viscosity-average molecular weight of 6,500 to 9,500), and the mixture was then converted into resin pellets. The polymerization reaction time in the second reactor was approximately 127 minutes. The maximum temperature in the second reactor was 230°C. The final pressure in the second reactor was 200 Pa. The obtained resin pellets were mixed with the additive components phosphorous acid, PTSB, AS2112, and Irg1076 in the proportions (mass ppm) shown in Table 1 below. The mixture was then supplied to a Japan Steel Works (TEX30HSS) machine equipped with one vent, and kneaded under the conditions of a screw rotation speed of 160 rpm, a discharge rate of 15 kg / h, and a barrel temperature of 230°C. The molten resin extruded into strands was rapidly cooled in a water bath and pelletized using a pelletizer to obtain pellets of thermoplastic resin composition. Each evaluation was performed on this thermoplastic resin composition using the procedure described above. The results are shown in Table 1.

[0158] [Example 2, Comparative Example 1] A thermoplastic resin composition pellet was obtained in the same manner as in Example 1, except that the raw materials and additives for melt polymerization were as shown in Table 1. Each evaluation was performed on this thermoplastic resin composition using the procedure described above. The results are shown in Table 1.

[0159] [Examples 3-6, Comparative Example 2] The raw materials and additives for melt polymerization were as shown in Table 1, and the resin pellets obtained from the second reactor were evaluated as a thermoplastic resin without adding any additive components, in the same manner as in Example 1. The results are shown in Table 1.

[0160] [Table 1]

[0161] [Discussion of evaluation results] The thermoplastic resin composition of Comparative Example 1, which lacks carbonate structural unit (B), underwent deformation in the long-term heat resistance test, indicating poor heat resistance. Comparative Example 2, a thermoplastic resin in which the proportion of carbonate structural units (B) is outside the scope of the present invention, shows cracking in long-term heat resistance tests, indicating poor durability. Furthermore, n D The optical properties are inferior because the coefficient of refraction is somewhat low and the birefringence of the molded material is large. On the other hand, the thermoplastic resins and thermoplastic resin compositions of Examples 1 to 6 have high Tg, show no change in appearance in long-term heat resistance tests, and exhibit excellent heat resistance, durability, and resistance to heat yellowing. Furthermore, n D It possesses excellent optical properties, such as high spectroscopy and low birefringence of the molded body. Furthermore, the thermoplastic resins or thermoplastic resin compositions of Examples 1 to 5, which had a small amount of phenolic hydroxyl groups derived from the aromatic dihydroxy compound represented by formula (3), were characterized by a small increase in YI per hour (ΔYI / hour) during the heat resistance test. Furthermore, compared to the thermoplastic resin in Example 5, which used BP-TMC manufactured by Songwon Co., Ltd. alone as the raw material, the thermoplastic resins or thermoplastic resin compositions in Examples 1 to 4, which used BP-TMC manufactured by Honshu Chemical Co., Ltd. alone or in combination, exhibited a smaller initial color test specimen YI.

[0162] From the above, it can be seen that the thermoplastic resin and thermoplastic resin composition of the present invention have higher heat resistance, durability and heat yellowing resistance, and also possess excellent optical properties such as high refractive index and low birefringence, compared to the thermoplastic resin and thermoplastic resin composition of the comparative example. [Industrial applicability]

[0163] Compared to the resins and thermoplastic resin compositions of the present invention, the thermoplastic resins and thermoplastic resin compositions of the present invention have higher heat resistance, durability, and resistance to heat yellowing, as well as excellent optical properties such as high refractive index and low birefringence. Therefore, the thermoplastic resin and thermoplastic resin composition of the present invention can be easily processed into optical components by methods such as injection molding. Compared to conventional optical components using polycarbonate resins such as polycarbonate resin derived from bisphenol A, these optical components are superior in that they have high heat resistance, high refractive index, and low birefringence.

[0164] Examples of such optical components include optical lenses, optical films, and optical sheets. Examples of optical lenses include automotive lenses, eyeglass lenses, pickup lenses, camera lenses, microarray lenses, projector lenses, and Fresnel lenses. In particular, the thermoplastic resin and thermoplastic resin composition of the present invention have high heat resistance, durability, and resistance to heat-induced yellowing, making them suitable for use as materials for optical components intended for use in high-temperature environments, such as automotive lenses.

Claims

1. A thermoplastic resin containing structural units (A) represented by the following formula (1) and structural units (B) represented by the following formula (2) in a molar ratio of (A) / (B) = 65 / 35 to 92 / 8, A thermoplastic resin in which the sum of the content ratios of structural unit (A) and structural unit (B) in the total structural units of the thermoplastic resin is 93 to 100 mol%. 【Chemistry 1】 (In formula (1), ring Z １ Z ２ Each of these independently represents an aromatic hydrocarbon ring. R １ ~R １０ each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an aromatic group. However, R ３ and R ４ , R ４ and R ５ , R ５ and R ６ , R ７ and R ８ , R ８ and R ９ and R ９ and R １０ in the set of may be bonded to each other to form a ring. i and ii each independently represent a number obtained by subtracting 3 from the number of ring members of ring Z １ , Z ２ . A plurality of R 1 , R ２ may be the same or different. X represents an alkylene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 12 carbon atoms, or an arylene group with 6 to 20 carbon atoms. n represents an integer from 0 to 10.

2. The thermoplastic resin according to claim 1, wherein the sum of the content ratios of structural unit (A) and structural unit (B) in the total structural units of the thermoplastic resin is 100 mol%.

3. The thermoplastic resin according to claim 1, wherein the amount of phenolic hydroxyl groups derived from the aromatic dihydroxy compound represented by the following formula (3) is 100 to 1500 ppm. 【Chemistry 2】

4. The thermoplastic resin according to claim 1, wherein the hydrolyzed product obtained by hydrolyzing the thermoplastic resin contains compounds represented by the following formulas (3) to (5), and the sum of the content of the compound represented by the following formula (4) and the compound represented by the following formula (5) in the hydrolyzed product is 1.00% by mass or more relative to the content of the compound represented by the following formula (3). 【Transformation 3】

5. The thermoplastic resin according to claim 1, wherein X in formula (1) is an ethylene group.

6. The thermoplastic resin according to claim 1, wherein n in formula (1) is 1.

7. The thermoplastic resin according to claim 1, wherein the structural unit (A) is represented by the following formula (6) or (7). 【Chemistry 4】 (In formulas (6) and (7), R １１ ~R １４ Each of these independently represents a hydrogen atom, a methyl group, or a phenyl group. ３ ~R １０ This is equivalent to the expression in equation (1) above. However, R ３ and R ４ , R ４ and R ５ , R ５ and R ６ , R ７ and R ８ , R ８ and R ９ and R ９ and R １０ (One of the pairs may be joined together to form a ring.)

8. In the above formula (1), R ３ ~R １０ The thermoplastic resin according to claim 1, wherein all atoms are hydrogen atoms.

9. The thermoplastic resin according to claim 1, wherein the structural unit (A) is represented by the following formula (8). 【Transformation 5】

10. The thermoplastic resin according to claim 1, wherein the viscosity-average molecular weight (Mv) is 5,000 or more and 50,000 or less.

11. Refractive index at a wavelength of 589 nm (n Ｄ The thermoplastic resin according to claim 1, wherein the ratio is 1.590 or higher.

12. The thermoplastic resin according to claim 1, wherein the refractive index (nD) at a wavelength of 589 nm is 1.601 or more.

13. Abbe number (ν Ｄ The thermoplastic resin according to claim 1, wherein the ratio is 35.0 or less.

14. The thermoplastic resin according to claim 1, wherein the glass transition temperature (Tg) is 110°C or higher and 200°C or lower.

15. The thermoplastic resin according to claim 1, wherein in a 3 mm thick test specimen made of the thermoplastic resin, the increase in YI per hour (ΔYI / hour) [1 / Hr] calculated by the following formula is 0.0500 or less. Increase in YI per hour (ΔYI / hour) = (Yellowness of the test specimen after heating - Yellowness of the test specimen before heating) / Heating time In the above formula, the yellowness of the test specimen after heating is the yellowness measured in accordance with JIS K7373 after conducting a heat resistance test in which the test specimen is left standing in an environment of normal pressure and 135°C for 280 hours, and the yellowness of the test specimen before heating is the yellowness measured in accordance with JIS K7373 before conducting the heat resistance test, with a heating time of 280 hours.

16. A thermoplastic resin composition comprising a thermoplastic resin according to any one of claims 1 to 15, at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, an ultraviolet absorber, a brightness enhancer, a dye, a pigment, a mold release agent, a flow modifier, and an impact resistance enhancer, and / or another resin other than the thermoplastic resin.

17. The thermoplastic resin composition according to claim 16, wherein in a 3 mm thick test specimen made of the thermoplastic resin composition, the increase in YI per hour (ΔYI / hour) [1 / Hr] calculated by the following formula is 0.0500 or less. Increase in YI per hour (ΔYI / hour) = (Yellowness of the test specimen after heating - Yellowness of the test specimen before heating) / Heating time In the above formula, the yellowness of the test specimen after heating is the yellowness measured in accordance with JIS K7373 after conducting a heat resistance test in which the test specimen is left standing in an environment of normal pressure and 135°C for 280 hours, and the yellowness of the test specimen before heating is the yellowness measured in accordance with JIS K7373 before conducting the heat resistance test, with a heating time of 280 hours.

18. A molded article obtained by molding a thermoplastic resin according to any one of claims 1 to 15.

19. A molded article obtained by molding the thermoplastic resin composition described in Claim 16.

20. A molded article obtained by molding the thermoplastic resin composition described in Claim 17.

21. The molded body according to claim 18, wherein the molded body is an optical component.

22. The molded body according to claim 19, wherein the molded body is an optical member.

23. The molded body according to claim 20, wherein the molded body is an optical member.

24. The molded article according to claim 21, wherein the optical component is at least one optical lens selected from the group consisting of automotive lenses, spectacle lenses, pickup lenses, camera lenses, microarray lenses, projector lenses, and Fresnel lenses.

25. The molded body according to claim 22, wherein the optical member is at least one optical lens selected from the group consisting of automotive lenses, spectacle lenses, pickup lenses, camera lenses, microarray lenses, projector lenses and Fresnel lenses.

26. The molded body according to claim 23, wherein the optical member is at least one optical lens selected from the group consisting of automotive lenses, spectacle lenses, pickup lenses, camera lenses, microarray lenses, projector lenses and Fresnel lenses.

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