Thermoplastic resin composition and optical lens including same

Abstract

The present invention addresses the problem of providing a thermoplastic resin composition that has favorable properties, facilitates thermoplastic resin recycling, and can reduce the environmental load.　The problem is solved by the following thermoplastic resin composition. Specifically provided is a thermoplastic resin composition including, as a mixture, a first thermoplastic resin that includes a structural unit (A) derived from a monomer represented by general formula (1), and a second thermoplastic resin that includes a structural unit (B) derived from a monomer represented by any one of general formulas (2a)-(2c), wherein at least one of the first thermoplastic resin and the second thermoplastic resin is a copolymer having both the structural unit (A) and the structural unit (B), and the structural unit (A) content is 5-95 mol% and the structural unit (B) content is 5-95 mol% on the basis of the total number of structural units of the first thermoplastic resin and the second thermoplastic resin.

Description

Thermoplastic resin composition and optical lens containing same

[0001] The present invention relates to a composition containing a thermoplastic resin such as polycarbonate, and in particular to a composition containing a mixture of a plurality of predetermined thermoplastic resins.

[0002] Thermoplastic resins used as optical materials have been known (for example, Patent Documents 1 and 2). Optical thermoplastic resins are generally required to have good properties such as refractive index and Abbe number.

[0003] Furthermore, thermoplastic resins are usually molded into products such as lenses and optical films through a molding process such as injection molding.

[0004] International Publication No. WO 2014 / 073496 International Publication No. WO 2015 / 166951

[0005] Conventional thermoplastic resins, such as those primarily used for optical applications, do not necessarily have fully satisfactory properties, and no thermoplastic resin has been developed that has a good balance of properties in terms of refractive index, Abbe number, birefringence, moldability, thermal stability, etc.

[0006] Furthermore, it is not easy to produce only molded products through molding processes such as injection molding of thermoplastic resins. Usually, waste materials other than molded products are generated due to the thermoplastic resin injected into gaps in the mold, such as sprues, runners, and gates. These waste materials are often discarded as waste because they are difficult to recycle. Therefore, conventional thermoplastic resin molded products can have problems with yields not reaching sufficient levels. Furthermore, there is a need to reduce the environmental impact of the thermoplastic resin molding process and expand recycling.

[0007] As a result of intensive research to solve the above problems, the present inventors have found that a thermoplastic resin composition obtained by mixing multiple thermoplastic resins of predetermined types can achieve good properties, mainly for optical applications, and also facilitates the recycling of the thermoplastic resin, thereby reducing the environmental burden.

[0008] The present invention includes the following: [1] A thermoplastic resin composition comprising a mixture of a first thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1), and a second thermoplastic resin containing a structural unit (B) derived from a monomer represented by any one of the following general formulae (2a) to (2c), wherein at least one of the first thermoplastic resin and the second thermoplastic resin is a copolymer containing both the structural unit (A) and the structural unit (B), and the content of the structural unit (A) is 5 to 95 mol % and the content of the structural unit (B) is 5 to 95 mol %, based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin. (In general formula (1), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ R is selected from the group consisting of ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent; X represents a single bond or an alkylene group having 3 or less carbon atoms which may have a substituent; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; m and n each independently represent an integer of 0 to 6; and a and b each independently represent an integer of 0 to 10. (In general formulas (2a) to (2c), R ｃ and R ｄare each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent; Y each independently represents a fluorene group which may have a substituent; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; p and q each independently represent an integer of 0 to 4; and a and b each independently represent an integer of 0 to 10. [2] The thermoplastic resin composition according to [1] above, wherein the first thermoplastic resin and the second thermoplastic resin are both copolymers having the structural unit (A) and the structural unit (B). [3] The thermoplastic resin composition according to [1] above, wherein the second thermoplastic resin has only the structural unit (B). [4] The thermoplastic resin composition according to the above [1], wherein the content of the structural unit (A) is 30 to 65 mol% and the content of the structural unit (B) is 35 to 70 mol%, based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin.

[0009] [5] At least one of the first and second thermoplastic resins further has a structural unit (C) derived from a monomer represented by the following formula (3): The thermoplastic resin composition according to [1]. (In formula (3), R １ ~R ４ are each independently a hydrogen atom, an alkyl group, or an aryl group, Z is a single bond or a group represented by the following general formula (4): (In formula (4), R ５ and R ６are each a hydrogen atom, an alkyl group, or an aryl group, and c is an integer of 1 to 3. [6] The thermoplastic resin composition according to the above [1], wherein the thermoplastic resin composition contains two or more types of thermoplastic resins containing the structural unit (A). [7] The thermoplastic resin composition according to the above [1], wherein the thermoplastic resin composition contains two or more types of thermoplastic resins containing the structural unit (B). [8] The thermoplastic resin composition according to the above [1], wherein the thermoplastic resin contains a mold release agent and / or an antioxidant. [9] The thermoplastic resin composition according to any one of the above [1] to [8], wherein the average value of in-plane birefringence of the thermoplastic resin composition for a lens is 50 nm or less.

[10] The thermoplastic resin composition according to any one of the above [1] to [8], wherein the maximum value of in-plane birefringence of the thermoplastic resin composition for a lens is 60 nm or less.

[11] An optical lens comprising the thermoplastic resin composition according to any one of the above [1] to

[10] .

[0010] According to the present invention, a thermoplastic resin composition containing a mixture of multiple predetermined types of thermoplastic resins and having excellent properties useful in particular for optical applications can be realized. The thermoplastic resin composition of the present invention has a high refractive index, a low Abbe number, a low in-plane birefringence, and the like, as well as excellent moldability and thermal stability. Furthermore, according to the present invention, the thermoplastic resin can be easily reused in forming the thermoplastic resin composition, thereby expanding recycling and reducing the environmental burden.

[0011] 1. Components of Thermoplastic Resin Composition 1-1. Thermoplastic Resin Composition The thermoplastic resin composition of the present invention comprises a mixture of at least a first thermoplastic resin containing a structural unit (A) derived from a monomer represented by the general formula (1) above, and a second thermoplastic resin containing a structural unit (B) derived from a monomer represented by any one of the general formulas (2a) to (2c) above. The structural unit (A) derived from the monomer represented by the general formula (1) has a binaphthalene ring, and therefore is hereinafter also referred to as a binaphthalene structural unit. Furthermore, the structural unit (B) derived from the monomer represented by the general formula (2) has a fluorene ring, and therefore is hereinafter also referred to as a fluorene structural unit. Details of the first and second thermoplastic resins will be described later.

[0012] In the thermoplastic resin composition, the content of the binaphthalene structural unit of the structural unit (A) is 5 to 95 mol %, and the content of the fluorene structural unit of the structural unit (B) is 5 to 95 mol %, based on the total number of structural units, i.e., the total number of moles, of the first thermoplastic resin and the second thermoplastic resin.

[0013] The content of the structural unit (A) based on the total number of moles of the first thermoplastic resin and the second thermoplastic resin is preferably 5 to 85 mol% or 10 to 80 mol%, more preferably 15 to 70 mol% or 20 to 65 mol%, even more preferably 30 to 70 mol%, 30 to 65 mol%, 35 to 70 mol%, or 35 to 65 mol%, and particularly preferably 40 to 60 mol%, 40 to 55 mol%, 45 to 55 mol%, or 45 to 50 mol%. Furthermore, the content of the structural unit (A), based on the total number of moles of the structural units of the thermoplastic resin composition, is preferably 5 to 85 mol% or 10 to 80 mol%, more preferably 15 to 70 mol% or 20 to 65 mol%, even more preferably 30 to 70 mol%, 30 to 65 mol%, 35 to 70 mol%, or 35 to 65 mol%, and particularly preferably 40 to 60 mol%, 40 to 55 mol%, 45 to 55 mol%, or 45 to 50 mol%.

[0014] The content of the structural unit (B) based on the total number of moles of the first thermoplastic resin and the second thermoplastic resin is preferably 10 to 90 mol% or 15 to 85 mol%, more preferably 20 to 75 mol% or 20 to 70 mol%, even more preferably 35 to 75 mol%, 35 to 70 mol%, 40 to 75 mol%, or 40 to 70 mol%, and particularly preferably 45 to 65 mol%, 45 to 60 mol%, 50 to 60 mol%, or 50 to 55 mol%. Furthermore, the content of the structural unit (B) based on the total number of moles of the structural units of the thermoplastic resin composition is preferably 10 to 90 mol% or 15 to 85 mol%, more preferably 20 to 75 mol% or 20 to 70 mol%, even more preferably 35 to 75 mol%, 35 to 70 mol%, 40 to 75 mol%, or 40 to 70 mol%, and particularly preferably 45 to 65 mol%, 45 to 60 mol%, 50 to 60 mol%, or 50 to 55 mol%.

[0015] In the thermoplastic resin composition, the content of the first thermoplastic resin containing the structural unit (A) is preferably 5 to 95% by weight, 5 to 85% by weight, or 10 to 80% by weight, more preferably 15 to 70% by weight or 20 to 65% by weight, even more preferably 30 to 70% by weight, 30 to 65% by weight, 35 to 70% by weight, or 35 to 65% by weight, and particularly preferably 40 to 60% by weight, 40 to 55% by weight, 45 to 55% by weight, or 45 to 50% by weight, based on the total weight of all thermoplastic resins. Furthermore, in the thermoplastic resin composition, the content of the second thermoplastic resin containing the structural unit (B) is preferably 5 to 95% by weight, 10 to 90% by weight, or 15 to 85% by weight, more preferably 20 to 75% by weight or 20 to 70% by weight, even more preferably 35 to 75% by weight, 35 to 70% by weight, 40 to 75% by weight, or 40 to 70% by weight, and particularly preferably 45 to 65% by weight, 45 to 60% by weight, 50 to 60% by weight, or 50 to 55% by weight, based on the total weight of all thermoplastic resins.

[0016] In the thermoplastic resin composition, the total content of the first thermoplastic resin containing the structural unit (A) and the second thermoplastic resin containing the structural unit (B) is preferably 40% by weight or more, more preferably 50% by weight or more or 60% by weight or more, even more preferably 70% by weight or more or 80% by weight or more, and particularly preferably 90% by weight or more or 95% by weight or more, based on the total weight of all thermoplastic resins. It is particularly preferred that all of the thermoplastic resins contained in the thermoplastic resin composition are substantially the first thermoplastic resin or the second thermoplastic resin.

[0017] In the thermoplastic resin composition, the total content of the first thermoplastic resin containing the structural unit (A) and the second thermoplastic resin containing the structural unit (B) is preferably 40% by weight or more, more preferably 50% by weight or more, even more preferably 70% by weight or more, and particularly preferably 90% by weight or more, based on the total weight of the thermoplastic resin composition. Thus, the thermoplastic resin composition may contain components other than the first and second thermoplastic resins. For example, the thermoplastic resin composition may contain thermoplastic resins, additives, etc., the details of which will be described later, other than the first and second thermoplastic resins.

[0018] The type of thermoplastic resin contained in the thermoplastic resin composition is not particularly limited, but is preferably a polycarbonate resin, a polyester resin, or a polyestercarbonate resin, and more preferably a polycarbonate resin. The thermoplastic resin contained in the thermoplastic resin composition may have a random copolymer, a block copolymer, or an alternating copolymer structure, or may be a homopolymer.

[0019] 1-2. First Thermoplastic Resin The first thermoplastic resin contains at least a structural unit (A) derived from a monomer represented by general formula (1): In general formula (1), R ａ and R ｂeach independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ and R ｈ is an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent.

[0020] R in general formula (1) ａ and R ｂ is preferably selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent, and more preferably selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent. ａ and R ｂ is more preferably selected from a hydrogen atom and an aryl group having 6 to 20 carbon atoms which may have a substituent.

[0021] In general formula (1), X is a single bond or an alkylene group having 3 or less carbon atoms which may have a substituent, preferably a single bond or an alkylene group having 2 or less carbon atoms which may have a substituent, more preferably a single bond or an alkylene group having 1 carbon atom which may have a substituent, and particularly preferably a single bond. In general formula (1), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent, and more preferably an alkylene group having 1 or 2 carbon atoms which may have a substituent. In general formula (1), m and n each independently represent an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1. In general formula (1), a and b each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and particularly preferably 0 or 1.

[0022] R in general formula (1) ａ and R ｂ Among the options, the number of carbon atoms in the alkyl group having 1 to 20 carbon atoms, which may have a substituent, and the alkoxy group having 1 to 20 carbon atoms, which may have a substituent, is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3, or 1. ａ and R ｂ Among the options, the carbon number of the cycloalkyl group having 5 to 20 carbon atoms, which may have a substituent, and the carbon number of the cycloalkoxy group having 5 to 20 carbon atoms, which may have a substituent, is preferably 5 to 10, more preferably 6 to 8, and even more preferably 6 or 7. ａ and R ｂ Among the options above, the number of carbon atoms in the aryl group having 6 to 20 carbon atoms which may have a substituent, the heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, and the aryloxy group having 6 to 20 carbon atoms which may have a substituent are each preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 to 8, or 6.

[0023] Examples of the substituent that can be contained in the structural unit (A) of formula (1) include a halogen atom, a hydroxy group, a carboxy group, a cyano group, an amide group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyloxy group having 5 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, a cycloalkyloxycarbonyl group having 5 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, an alkylcarbonyloxy group having 2 to 10 carbon atoms, a cycloalkylcarbonyloxy group having 5 to 10 carbon atoms, an arylcarbonyloxy group having 7 to 15 carbon atoms, a hydroxyalkylcarbonyl group having 2 to 10 carbon atoms, and a glycidyloxycarbonyl group. The number of carbon atoms in formula (1) includes the number of carbon atoms of the substituent.

[0024] Specific preferred examples of the monomer that forms the structural unit (A) include 2,2'-bis(hydroxy(poly)alkoxy)-diaryl-1,1'-binaphthalenes, 2,2'-bis(hydroxy(poly)alkoxy)-dinaphthyl-1,1'-binaphthalenes, and the like. Of these monomer compounds, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthalene, and 2,2'-bis(2-hydroxypropoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthalene are preferred. The above-mentioned monomer compounds may be used alone or in combination of two or more to form the structural unit (A).

[0025] The first thermoplastic resin is preferably a copolymer having both the above-mentioned structural unit (A) and the structural unit (B), which will be described in detail later. In such a copolymer, the content of the structural unit (A) is preferably 5 to 85 mol% or 10 to 80 mol%, more preferably 15 to 70 mol% or 20 to 65 mol%, even more preferably 30 to 70 mol%, 30 to 65 mol%, 35 to 70 mol%, or 35 to 65 mol%, and particularly preferably 40 to 60 mol%, 40 to 55 mol%, 35 to 55 mol%, or 45 to 50 mol%, based on the total number of moles of the binaphthalene structural unit (A) and the fluorene structural unit (B).

[0026] In the first thermoplastic resin, the content of the structural unit (A) in all structural units is preferably 40 mol% or more, more preferably 50 mol or 60 mol% or more, even more preferably 70 mol or 80 mol% or more, and particularly preferably 90 mol or 95 mol% or more. Furthermore, in the first thermoplastic resin, structural units other than the structural unit (A) and the structural unit (B) may be contained, but the content of the structural unit (A) and the structural unit (B) in all structural units is preferably 40 mol% or more, more preferably 50 mol or 60 mol% or more, even more preferably 70 mol or 80 mol% or more, and particularly preferably 90 mol or 95 mol% or more.

[0027] The thermoplastic resin composition preferably contains a mixture of multiple thermoplastic resins containing the above-mentioned structural unit (A), such as the first thermoplastic resin. A thermoplastic resin composition containing a mixture of the first thermoplastic resin and the second thermoplastic resin, and more preferably a mixture of multiple types of thermoplastic resins containing the structural unit (A), is expected to have favorable properties, as described below.

[0028] 1-3. Second Thermoplastic Resin The second thermoplastic resin contains at least a structural unit (B) derived from a monomer represented by any one of general formulas (2a) to (2c). In the general formulas (2a) to (2c), 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 which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent. ｃ and R ｄ are preferably each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent, and more preferably are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent. ｃ and R ｄ is more preferably selected from a hydrogen atom and an aryl group having 6 to 20 carbon atoms which may have a substituent.

[0029] In general formulas (2a) to (2c), Y each independently represents a fluorene group which may have a substituent. In general formulas (2a) to (2c), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent, and more preferably an alkylene group having 1 or 2 carbon atoms which may have a substituent. In general formulas (2a) to (2c), p and q each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1. Furthermore, in general formulas (2a) to (2c), a and b each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and particularly preferably 0 or 1.

[0030] R in general formulas (2a) to (2c) ｃ and R ｄAmong the options, the number of carbon atoms in the alkyl group having 1 to 20 carbon atoms, which may have a substituent, and the alkoxy group having 1 to 20 carbon atoms, which may have a substituent, is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3, or 1. ｃ and R ｄ Among the options, the number of carbon atoms in the cycloalkyl group having 5 to 20 carbon atoms, which may have a substituent, and the number of carbon atoms in the cycloalkoxy group having 5 to 20 carbon atoms, which may have a substituent, are preferably 5 to 10, more preferably 6 to 8, and even more preferably 6 or 7. ｃ and R ｄ Among the options above, the number of carbon atoms in the aryl group having 6 to 20 carbon atoms, which may have a substituent, is preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 to 8, or 6.

[0031] Examples of the substituents that can be contained in the structural unit (B) of the above formulas (2a) to (2c) include halogen atoms, hydroxy groups, carboxy groups, cyano groups, C1 to C10 amide groups, C1 to C10 alkyl groups, C5 to C10 cycloalkyl groups, C1 to C10 alkoxy groups, C5 to C10 cycloalkyloxy groups, C2 to C10 alkyloxycarbonyl groups, C5 to C10 cycloalkyloxycarbonyl groups, C7 to C15 aryloxycarbonyl groups, C2 to C10 alkylcarbonyloxy groups, C5 to C10 cycloalkylcarbonyloxy groups, C7 to C15 arylcarbonyloxy groups, C2 to C10 hydroxyalkylcarbonyl groups, and glycidyloxycarbonyl groups. The carbon numbers in the general formulas (2a) to (2c) include the number of carbon atoms in the substituents.

[0032] Specific preferred examples of the monomer that forms the above-mentioned structural unit (B) include BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene), BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), and the like. The above-mentioned monomer compounds may be used alone, or two or more types may be used in combination to form the structural unit (B).

[0033] The second thermoplastic resin is preferably a copolymer having the structural unit (A) together with the structural unit (B). In such a copolymer, the content of the structural unit (B) is preferably 5 to 90 mol%, 10 to 90 mol%, or 15 to 85 mol%, more preferably 20 to 75 mol% or 20 to 70 mol%, even more preferably 35 to 75 mol%, 35 to 70 mol%, 40 to 75 mol%, or 40 to 70 mol%, and particularly preferably 45 to 65 mol%, 45 to 60 mol%, 50 to 60 mol%, or 50 to 55 mol%, based on the total number of moles of the fluorene structural unit (B) and the binaphthalene structural unit (A).

[0034] In the second thermoplastic resin, the content of the structural unit (B) in all structural units is preferably 40 mol% or more, more preferably 50 mol% or 60 mol% or more, even more preferably 70 mol% or 80 mol% or more, and particularly preferably 90 mol% or 95 mol% or more.

[0035] In the thermoplastic resin composition, it is preferable that at least one of the second thermoplastic resin and the first thermoplastic resin is a copolymer containing both the structural unit (A) and the structural unit (B). Furthermore, in the thermoplastic resin composition, both the second thermoplastic resin and the first thermoplastic resin may be a copolymer containing both the structural unit (A) and the structural unit (B).

[0036] The thermoplastic resin composition preferably contains a mixture of multiple thermoplastic resins containing the above-mentioned structural unit (B), such as the second thermoplastic resin. A thermoplastic resin composition containing a mixture of the second thermoplastic resin and the first thermoplastic resin, and more preferably a mixture of multiple types of thermoplastic resins containing the structural unit (B), is expected to have favorable properties, as described below.

[0037] 1-4. Other Thermoplastic Resins The thermoplastic resin composition may contain a thermoplastic resin (other thermoplastic resin) other than the first thermoplastic resin and the second thermoplastic resin described above. For example, a specific example of the other thermoplastic resin is a structural unit (C) derived from a monomer represented by the following formula (3): In formula (3), R １ ~R ４ are each independently a hydrogen atom, an alkyl group, or an aryl group. １ ~R ４ is preferably selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms, more preferably selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and even more preferably selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 8 carbon atoms. １ ~R ４ In formula (3), Z is a single bond or a group represented by the following general formula (4), preferably a group represented by the following general formula (4): In formula (4), R ５ and R ６ are each a hydrogen atom, an alkyl group, or an aryl group. ５ and R ６ are each preferably selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms, more preferably selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and even more preferably selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 8 carbon atoms.５ and R ６ may be a substituted alkyl group or a substituted aryl group. ５ and R ６ The lowercase letter c, which is bonded to and is not C meaning a carbon atom, represents an integer of 1 to 3. c is preferably 1 or 2, and more preferably 1. Examples of the substituents that can be contained in the structural unit (C) of the above formulas (3) and (4) include a halogen atom, a hydroxy group, a carboxy group, a cyano group, an amide group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyloxy group having 5 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, a cycloalkyloxycarbonyl group having 5 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, an alkylcarbonyloxy group having 2 to 10 carbon atoms, a cycloalkylcarbonyloxy group having 5 to 10 carbon atoms, an arylcarbonyloxy group having 7 to 15 carbon atoms, a hydroxyalkylcarbonyl group having 2 to 10 carbon atoms, and a glycidyloxycarbonyl group. The number of carbon atoms in the general formulae (3) and (4) includes the number of carbon atoms in the substituents.

[0038] 1-5. Secondary Components The thermoplastic resin composition may contain components other than the thermoplastic resin. For example, at least one additive selected from a mold release agent, an antioxidant, and the like. The thermoplastic resin composition preferably contains either a mold release agent or an antioxidant, or both. In the thermoplastic resin composition, the content of secondary components such as additives other than the thermoplastic resin is preferably 20% by weight or less, more preferably 15% by weight or less or 10% by weight or less, even more preferably 7% by weight or less or 5% by weight or less, and particularly preferably 3% by weight or less or 2% by weight or less, based on the total weight.

[0039] Specific examples of additives contained in the thermoplastic resin composition include the following. Mold Release Agents Examples of mold release agents include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin-based). Specific examples include at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number-average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils. Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, and more preferred are saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetraacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid. The same aliphatic carboxylic acids as those described above can be used as the aliphatic carboxylic acids in the esters of aliphatic carboxylic acids and alcohols. On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols having 30 or less carbon atoms are more preferred. Here, aliphatic compounds also include alicyclic compounds. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, etc. The above-mentioned ester compounds may contain aliphatic carboxylic acids and / or alcohols as impurities, or may be a mixture of multiple compounds.Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture primarily composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. Aliphatic hydrocarbons having a number-average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbon compounds may also be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxidized polyethylene wax are preferred, with paraffin wax and polyethylene wax being more preferred. The number average molecular weight is preferably 200 to 5000. These aliphatic hydrocarbons may be a single substance or a mixture of substances with various constituent components and molecular weights, as long as the main component is within the above range. Examples of polysiloxane-based silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.

[0040] The addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the thermoplastic resin. Only one type of release agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0041] Antioxidant Examples of the antioxidant include phenol-based antioxidants, hindered phenol-based antioxidants, bisphenol-based antioxidants, and polyphenol-based antioxidants.

[0042] Specifically, 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4'-butylidenebis-(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert t-butyl-4-hydroxy-5-methylphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N' -hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxa hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)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-triazin-2-ylamino)phenol, and the like.Examples of phenol-based antioxidants include "Irganox 1010" (registered trademark, the same applies hereinafter) and "Irganox 1076" manufactured by BASF, and "Adekastab AO-50" and "Adekastab AO-60" manufactured by Adeka Corporation.

[0043] The antioxidant is preferably added in an amount of 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin. Only one type of antioxidant may be contained, or two or more types may be contained. When two or more types are contained, it is preferable that the total amount is within the above range.

[0044] 2. Method for Producing Thermoplastic Resin Composition The method for producing a thermoplastic resin composition is described below. Thermoplastic resins such as the first and second thermoplastic resins can be produced by known methods. For example, a thermoplastic resin can be produced by carrying out a polymerization reaction in a reaction system containing a monomer compound and a catalyst at a polymerization temperature of 200 to 250°C and a pressure of 760 to 200 mmHg. For example, a thermoplastic resin such as a polycarbonate resin can be produced by melt polycondensation using monomer compounds represented by the above general formulas (1) to (3) and carbonate precursors such as carbonate diesters as raw materials in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst containing both, or in the absence of a catalyst.

[0045] A thermoplastic resin composition can be produced by melt-kneading multiple types of thermoplastic resins obtained by polymerization reactions and the secondary components described above, or by dissolving and blending them in a solvent, followed by volatilizing the solvent. Suitable solvents include halogenated organic solvents and THF.

[0046] 3. Properties of Thermoplastic Resin Composition and Thermoplastic Resin Preferred properties of the thermoplastic resin composition and thermoplastic resin are as follows:

[0047] 3-1. Total Light Transmittance (TT (%)) The total light transmittance (%) of the thermoplastic resin composition, measured by the method described below and conforming to JIS K 7361-1:1997, is preferably 60% or more, more preferably 70% or more, more preferably 80% or more, and particularly preferably 85% or more. 3-2. YI Value The YI value of the thermoplastic resin composition, measured by the method described below and conforming to JIS K 7373:2006, is preferably 20 or less, more preferably 16 or less, more preferably 14 or less, and particularly preferably 13.5 or less.

[0048] 3-3. Haze The haze value of the thermoplastic resin composition, measured by the method described below in accordance with JIS K-7136:2000, is preferably 2.0 or less, more preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.6 or less. 3-4. Refractive Index The refractive index (nD) value of the thermoplastic resin composition, measured by the method described below in accordance with JIS B 7071-2:2018, is preferably 1.630 or more, more preferably 1.640 or more, more preferably 1.650 or more, and particularly preferably 1.660 or more or 1.670 or more. 3-5. Abbe Number (νd) The Abbe number (νd) value of the thermoplastic resin composition, measured by the method described below, is preferably 24 or less, more preferably 22 or less, more preferably 21 or less, and particularly preferably 20 or less or 19 or less.

[0049] 3-6. Melt volume rate (MVR) The MVR value (unit: cm) of a thermoplastic resin composition according to JIS K7210 ３ / 10 min) is preferably 30 or more, more preferably 40 or more, more preferably 45 or more or 50 or more, and particularly preferably 55 or more or 65 or more. A resin or resin composition with a high MVR value can be said to have high fluidity. As will be described later, it has been confirmed that, in a thermoplastic resin mixture and a thermoplastic resin copolymer that have roughly the same type and content of structural units, the MVR value tends to be higher in the thermoplastic resin mixture. Thus, the thermoplastic resin composition of the present invention containing a mixture of thermoplastic resins can be said to have good fluidity and moldability.

[0050] 3-7. In-Plane Birefringence (Average and Maximum) The average in-plane birefringence of the lens of the thermoplastic resin composition, measured by the method described below, is preferably 50 nm or less or 40 nm or less, more preferably 30 nm or less, more preferably 15 nm or less, and particularly preferably 13 nm or less or 11 nm or less. Furthermore, the maximum in-plane birefringence of the lens of the thermoplastic resin composition, measured by the method described below, is preferably 90 nm or less or 80 nm or less, more preferably 70 nm or less or 60 nm or less, more preferably 50 nm or less or 35 nm or less, and particularly preferably 30 nm or less or 20 nm or less. As is clear from the results of the Examples and Comparative Examples described below, it was confirmed that in a thermoplastic resin mixture and a thermoplastic resin copolymer, which have roughly the same type and content of structural units, the in-plane birefringence value (mm) tends to be lower in the thermoplastic resin mixture. Thus, the thermoplastic resin composition of the present invention, which contains a mixture of thermoplastic resins, can be said to have excellent birefringence.

[0051] The weight average molecular weight of the thermoplastic resin contained in the thermoplastic resin composition is preferably 10,000 to 300,000, more preferably 10,000 to 200,000, and even more preferably 10,000 to 100,000, for example, more preferably 20,000 to 80,000, still more preferably 30,000 to 70,000, and particularly preferably 40,000 to 65,000. The weight average molecular weight of the thermoplastic resin is measured, for example, as a polystyrene-equivalent weight average molecular weight (Mw) as follows.

[0052] Using GPC (gel permeation chromatography), a calibration curve is prepared using chloroform as a developing solvent and standard polystyrene (Shodex STANDARD, SM-105) of known molecular weight (molecular weight distribution = 1). The elution time and molecular weight value of each peak from the measured standard polystyrene are plotted, and a calibration curve is prepared by approximating using a cubic equation. Then, based on the obtained calibration curve, the weight average molecular weight (Mw) can be calculated as a polystyrene equivalent value using the following formula. [Calculation formula] Mw = Σ(W ｉ ×M ｉ ) / Σ(W ｉ ) (In the above formula, i is the i-th division point when dividing the molecular weight M, W ｉ is the i-th weight, M ｉ represents the i-th molecular weight. The molecular weight M represents the molecular weight in polystyrene equivalent at the same elution time on the calibration curve.)

[0053] 3-9. Glass Transition Temperature (Tg) The glass transition temperature (Tg) of the thermoplastic resin composition according to JIS K7121-1987 is preferably 100 to 200°C, more preferably 110 to 180°C, even more preferably 120 to 160°C, and particularly preferably 130 to 150°C.

[0054] 4. Molded Articles Comprising Thermoplastic Resin Composition The thermoplastic resin composition of the present invention can be used for extrusion molding, blow molding, injection molding, etc. Molded articles (molded articles) obtained from the thermoplastic resin composition include extrusion molded articles, hollow molded articles, precision parts, thin injection molded articles, etc. Specific examples of molded articles using the thermoplastic resin of the present invention as optical materials include optical components such as optical lenses, optical films, liquid crystal displays, light guide plates, various films such as optical disk substrates, and housings for electronic devices such as smartphones.

[0055] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0056] The methods for measuring the various properties of the thermoplastic resins or thermoplastic resin compositions obtained in the examples and comparative examples described below are as follows. (1) Lens In-Plane Birefringence (Average Value) - Molding of Test Pieces The obtained resins or resin compositions were injection molded to obtain concave lens test pieces with a diameter of 4.5 mm and a center thickness of 0.2 mm. Molding machine: SUMITOMO SHI DEMAG SE50EV. Molding conditions: Cylinder temperature 260°C, mold temperature: glass transition temperature (Tg) -15°C, injection speed 30 mm / s, VP pressure 65 MPa (position 2.3 mm), dwell pressure 65 MPa for 1 second + 55 MPa for 1.5 seconds. - Measurement of Lens In-Plane Birefringence The retardation of the concave lens test pieces obtained by the above method was measured. Measuring device: Photonic Lattice WPA-100. Data processing method: The average retardation value was calculated using Photonic Lattice's software "PA / WPA View," and this was used as the lens in-plane birefringence (average value).

[0057] (2) Lens in-plane birefringence (maximum value) The retardation value of the test piece was measured in the same manner as in the method described in (1) above, and the maximum value of the obtained measurements was taken as the lens in-plane birefringence (maximum value). (3) Total light transmittance (TT), YI, and haze The obtained resin was molded into a thickness of 3 mm, and the total light transmittance (TT), YI, and haze were measured using a spectroscopic haze meter. The total light transmittance (TT) was a value obtained in accordance with JIS K 7361-1:1997, the YI value was a value obtained in accordance with JIS K 7373:2006, and the haze was a value obtained in accordance with JIS K-7136:2000. Measuring instrument: "SH 7000" manufactured by Nippon Denshoku Industries Co., Ltd.

[0058] (4) Refractive index (nD) Based on JIS B 7071-2:2018, the obtained resin or resin composition was molded to obtain a V-block of a predetermined shape and used as a test piece. The refractive index was measured at 23 ° C. using a refractometer (KPR-3000 manufactured by Shimadzu Corporation). (5) Abbe number (νd) 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 a wavelength of 589 nm nC: refractive index at a wavelength of 656 nm nF: refractive index at a wavelength of 486 nm Refractometer: KPR-3000 manufactured by Shimadzu Corporation

[0059] (6) Glass transition temperature (Tg) Measured using a differential scanning calorimeter with a temperature rise program of 10°C / min based on JIS K7121-1987. Differential scanning calorimeter: X-DSC7000 manufactured by Hitachi High-Tech Science Corporation. (7) Melt volume rate (MVR) The obtained resin or resin composition was dried in vacuum at 120°C for 4 hours and measured in accordance with JIS K7210. Measuring device: Melt Indexer T-111 manufactured by Toyo Seiki Seisaku-sho, Ltd. Measurement 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. ３The MVR is an index showing the fluidity of a resin, and a larger value indicates higher fluidity in the resin or resin composition.

[0060] Polymerization Example 1 7.67 kg (20.48 mol) of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene (BNE), 14.80 kg (25.05 mol) of 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), 10.28 kg (48.00 mol) of DPC, and 2.41×10 sodium bicarbonate －２ g (2.86 x 10 －４ (mol) was placed in a 50-liter reactor equipped with a stirrer and a distillation device. After nitrogen replacement in the reaction system, the reaction system was heated to 205°C over 20 minutes under a nitrogen atmosphere of 760 Torr. The raw materials were then melted while the pressure was reduced to 700 Torr over 10 minutes. The mixture was held as is for 10 minutes, stirred, and then held for another 100 minutes, after which the pressure in the reaction system was reduced to 205 Torr over 20 minutes. After holding as is for 60 minutes, the pressure in the reaction system was adjusted to 180 Torr over 10 minutes and maintained under conditions of 215°C and 180 Torr for 20 minutes. The pressure in the reaction system was further adjusted to 150 Torr over 10 minutes and maintained under conditions of 230°C and 150 Torr for 30 minutes, after which the pressure was reduced to 120 Torr and the temperature was increased. Thereafter, the pressure in the reaction system was reduced to 100 Torr over 10 minutes and maintained for 10 minutes. The pressure in the reaction system was further reduced to 1 Torr or less over 50 minutes and maintained at 235°C and 1 Torr or less for 40 minutes. After the reaction was completed, nitrogen was blown into the reactor to pressurize it, and the produced polycarbonate resin was removed while being pelletized.

[0061] 100 parts by weight of the extracted polycarbonate resin pellets were compounded with 0.2 parts by weight of glycerin monostearate (Rikemal S-100A, manufactured by Riken Vitamin Co., Ltd.), 0.1 part by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA Corporation), and 0.03 part by weight of 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADK STAB PEP-36, manufactured by ADEKA Corporation) as additives using a vented twin-screw extruder (TEM-26SX, manufactured by Shibaura Machine Co., Ltd., rotating in the same direction) to obtain a polycarbonate resin mixed with the additives. The extrusion conditions were a discharge rate of 15 kg / h, a screw rotation speed of 300 rpm, and a vent vacuum of 3 kPa. The extrusion temperatures from the first feed port to the die were 200, 220, 240, 260, 260, 260, 260, 260, 255, and 255°C, respectively.

[0062] (Recovery of Waste Resin 1) The polycarbonate resin obtained in Polymerization Example 1 was used to mold an optical lens, and a recycled product (recycled product 1) including a spool and runner of the obtained molded product was recovered.

[0063] Polymerization Example 2 As raw materials, 5.56 kg (10.32 mol) of BNEF, 7.45 kg (19.90 mol) of BNE, 4.76 kg (8.06 mol) of BPPEF, 8.449 kg (39.44 mol) of DPC, and 0.034 g (4.0×10 －４(mol) was placed in a 50 L reactor equipped with a stirrer and a distillation device, and the reaction system was purged with nitrogen. Then, the mixture was heated to 180°C under a nitrogen atmosphere of 760 mmHg. Complete dissolution of the raw materials was confirmed 30 minutes after the start of heating, and stirring was then continued for 120 minutes under the same conditions. The vacuum pressure in the reaction system was then adjusted to 200 mmHg, and the temperature was raised to 200°C at a rate of 60°C / hr. At this time, the start of distillation of by-produced phenol was confirmed. The reaction system was then maintained at 200°C for 40 minutes to continue the reaction. The temperature was then raised to 230°C at a rate of 75°C / hr, and 10 minutes after the temperature increase, the vacuum pressure was reduced to 1 mmHg or less over 2 hours while maintaining the temperature. The reaction system was then heated to 245°C at a rate of 60°C / hr, and stirring was continued for an additional 50 minutes. After the reaction was completed, nitrogen was introduced into the reactor to return the pressure to normal, and the produced polycarbonate resin was discharged while being pelletized. The polycarbonate resin thus discharged was mixed with additives in the same manner as in Polymerization Example 1 to obtain a polycarbonate resin.

[0064] (Recovery of Waste Resin 2) A recycled product (recycled product 2) including a spool and a runner was recovered from the polycarbonate resin obtained in Polymerization Example 2 in the same manner as in the above-mentioned (Recovery of Waste Resin 1).

[0065] Example 1 A resin composition was obtained by melt-mixing 100 parts by weight of a thermoplastic resin consisting of 85% by mass of the above-mentioned recycled product 1 and 15% by mass of the above-mentioned recycled product 2, 0.2 parts by weight of glycerin monostearate (manufactured by Riken Vitamin Co., Ltd.; Rikemal S-100A) as an additive, and 0.1 parts by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation; Adekastab AO-60) in an extruder. The extruder used for melt mixing was a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machine Co., Ltd.; rotation in the same direction), and the extrusion conditions were a discharge rate of 15 kg / h, a screw rotation speed of 300 rpm, a vent vacuum of 3 kPa, and extrusion temperatures from the first feed port to the die portion were 200, 220, 240, 260, 260, 260, 260, 255, and 255° C. The physical properties of the obtained composition are shown in Table 1 below.

[0066] Examples 2 and 3, Comparative Examples 1 and 2 Resin compositions were obtained in the same manner as in Example 1, except that the components were melt-mixed in the proportions shown in Table 1. The physical properties of the obtained compositions are shown in Table 1 below.

[0067] Polymerization Example 3 20.43 kg (46.00 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 10.28 kg (48.00 mol) of DPC, and 2.41×10 sodium bicarbonate －２ g (2.86 x 10 －４ (mol) was placed in a 50-liter reactor equipped with a stirrer and a distillation device. After nitrogen replacement in the reaction system, the reaction system was heated to 205°C over 20 minutes under a nitrogen atmosphere of 760 Torr. The raw materials were then melted while the pressure was reduced to 700 Torr over 10 minutes. The mixture was held in this state for 10 minutes, stirred, and then held for another 100 minutes, after which the pressure was reduced to 205 Torr over 20 minutes. The pressure in the reaction system was then adjusted to 180 Torr over 10 minutes and held under conditions of 215°C and 180 Torr for 20 minutes. The pressure in the reaction system was then adjusted to 150 Torr over another 10 minutes and held under conditions of 230°C and 150 Torr for 30 minutes, after which the pressure was reduced to 120 Torr and 235°C and the temperature was increased. The pressure in the reaction system was then reduced to 100 Torr over 10 minutes and held for 10 minutes. The pressure in the reaction system was further reduced to 1 Torr or less over 50 minutes, and the reaction system was maintained at 235° C. and 1 Torr or less for 40 minutes. After the reaction was completed, nitrogen was blown into the reactor to pressurize it, and the produced polycarbonate resin was removed while being pelletized.

[0068] 100 parts by weight of the extracted polycarbonate resin pellets were compounded with 0.2 parts by weight of glycerin monostearate (Rikemal S-100A, manufactured by Riken Vitamin Co., Ltd.) and 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADEKA Corporation; Adekastab AO-60) as additives using a vented twin-screw extruder (TEM-26SX, manufactured by Shibaura Machine Co., Ltd.; co-rotating) to obtain a polycarbonate resin mixed with the additives. The extrusion conditions were a discharge rate of 15 kg / h, a screw rotation speed of 300 rpm, and a vent vacuum of 3 kPa. The extrusion temperatures from the first feed port to the die were 200, 220, 240, 260, 260, 260, 260, 260, 255, and 255°C, respectively.

[0069] (Recovery of Waste Resin 3) The polycarbonate resin obtained in Polymerization Example 3 was used to mold an optical lens, and the spool and runner of the obtained molded product (recycled product 3) were collected.

[0070] Polymerization Example 4 7.84 kg (20.96 mol) of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene (BNE), 10.03 kg (18.63 mol) of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), 3.68 kg (6.99 mol) of DPBHBNA, 10.28 kg (48.00 mol) of DPC, and 2.41×10 sodium bicarbonate －２ g (2.86 x 10 －４(mol) was placed in a 50-liter reactor equipped with a stirrer and a distillation device. After nitrogen replacement in the reaction system, the reaction system was heated to 205°C over 20 minutes under a nitrogen atmosphere of 760 Torr. The raw materials were then melted while the pressure was reduced to 700 Torr over 10 minutes. The mixture was held as is for 10 minutes, stirred, and then held for another 100 minutes, after which the pressure in the reaction system was reduced to 205 Torr over 20 minutes. After holding as is for 60 minutes, the pressure in the reaction system was adjusted to 180 Torr over 10 minutes and maintained under conditions of 215°C and 180 Torr for 20 minutes. The pressure in the reaction system was further adjusted to 150 Torr over 10 minutes and maintained under conditions of 230°C and 150 Torr for 30 minutes, after which the pressure was reduced to 120 Torr and the temperature was increased. Thereafter, the pressure in the reaction system was reduced to 100 Torr over 10 minutes and maintained for 10 minutes. The pressure in the reaction system was further reduced to 1 Torr or less over 50 minutes and maintained at 235°C and 1 Torr or less for 40 minutes. After the reaction was completed, nitrogen was blown into the reactor to pressurize it, and the produced polycarbonate resin was removed while being pelletized.

[0071] 100 parts by weight of the extracted polycarbonate resin pellets were compounded with 0.2 parts by weight of glycerin monostearate (Rikemal S-100A, manufactured by Riken Vitamin Co., Ltd.), 0.1 part by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA Corporation), and 0.03 part by weight of 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADK STAB PEP-36, manufactured by ADEKA Corporation) as additives using a vented twin-screw extruder (TEM-26SX, manufactured by Shibaura Machine Co., Ltd., rotating in the same direction) to obtain a polycarbonate resin mixed with the additives. The extrusion conditions were a discharge rate of 15 kg / h, a screw rotation speed of 300 rpm, and a vent vacuum of 3 kPa. The extrusion temperatures from the first feed port to the die were 200, 220, 240, 260, 260, 260, 260, 260, 255, and 255°C, respectively.

[0072] Example 4 100 parts by weight of a thermoplastic resin consisting of 90% by mass of the above-mentioned recycled product 3 and 10% by mass of the above-mentioned recycled product 2, 0.2 parts by weight of glycerin monostearate (manufactured by Riken Vitamin Co., Ltd.; Rikemal S-100A) as an additive, and 0.1 parts by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation; Adekastab AO-60) were melt-mixed in an extruder to obtain a resin composition. The extruder used for melt mixing was a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machine Co., Ltd.; unidirectional rotation), and the extrusion conditions were a discharge rate of 15 kg / h, a screw rotation speed of 300 rpm, a vent vacuum of 3 kPa, and extrusion temperatures from the first feed port to the die portion were 200, 220, 240, 260, 260, 260, 260, 260, 255, and 255°C, respectively. The physical properties of the obtained compositions are shown in Table 1. (Examples 5 and 6) Resin compositions were obtained in the same manner as in Example 4, except that the components were melt mixed in the proportions shown in Table 2. The physical properties of the obtained compositions are shown in Table 2.

[0073]

[0074] Example 7 100 parts by weight of a thermoplastic resin consisting of 70% by weight of the recycled product 2 described above and 30% by weight of the recycled product 4 described above, and 0.2 parts by weight of glycerin monostearate (manufactured by Riken Vitamin Co., Ltd.; Rikemal S-100A) and 0.1 parts by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation; Adekastab AO-60) were melt-mixed in an extruder to obtain a resin composition. The extruder used for melt mixing was a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machine Co., Ltd.; rotation in the same direction), and the extrusion conditions were a discharge rate of 15 kg / h, a screw rotation speed of 300 rpm, a vent vacuum of 3 kPa, and extrusion temperatures from the first feed port to the die portion were 200, 220, 240, 260, 260, 260, 260, 255, and 255° C. The physical properties of the obtained composition are shown in Table 3.

[0075] Examples 8 and 9 Resin compositions were obtained in the same manner as in Example 7, except that the components were melt-mixed in the proportions shown in Table 2. The physical properties of the resulting compositions are shown in Table 3.

[0076]

[0077] The molecular structures and abbreviations of the monomer compounds used in the above polymerization examples are as follows:

[0078] As is clear from the results of the above-described Examples and Comparative Examples, the thermoplastic resins of the blends tend to have lower in-plane birefringence values ​​(mm) compared to thermoplastic resins of copolymers having roughly the same type and content of structural units (particularly, Examples 1-3 and Comparative Examples 1 and 2; Examples 4-6 and Comparative Examples 3 and 2; Examples 7-9 and Comparative Example 4, etc.). Thus, it can be said that the thermoplastic resin compositions of the present invention containing blends of thermoplastic resins have excellent birefringence. Furthermore, it can be said that the thermoplastic resins of the blends tend to have larger MVR values ​​and higher fluidity compared to thermoplastic resins of copolymers having roughly the same type and content of structural units (particularly, Examples 7-9 and Comparative Example 4, etc.). Thus, it can be said that the thermoplastic resin compositions of the present invention containing blends of thermoplastic resins have good fluidity and moldability.

[0079] Furthermore, when comparing the polymerization examples, which can be considered reference examples, i.e., the thermoplastic resin or resin composition immediately after production that has not been recycled, with the thermoplastic resin compositions of the examples, which have similar compositions and have been recycled, a decrease in the in-plane birefringence value or an increase in the MVR value, i.e., improved fluidity, is observed. Furthermore, since the thermoplastic resin composition of the present invention contains the essential thermoplastic resins as a mixture, it can easily and effectively reuse and utilize, for example, the thermoplastic resin scraps generated by injection into gaps such as sprues, runners, and gates of a mold. Therefore, the thermoplastic resin composition of the present invention can be produced by a simple manufacturing method, including recycling, and can easily achieve excellent properties, particularly in optical applications.

Claims

1. A thermoplastic resin composition comprising a mixture of a first thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1) and a second thermoplastic resin containing a structural unit (B) derived from a monomer represented by any one of the following general formulas (2a) to (2c): at least one of the first thermoplastic resin and the second thermoplastic resin is a copolymer having both the structural unit (A) and the structural unit (B); a thermoplastic resin composition, wherein the content of the structural unit (A) is 5 to 95 mol % and the content of the structural unit (B) is 5 to 95 mol %, based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin. 【Chemistry 1】 (In general formula (1), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ selected from the group consisting of R ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, X represents a single bond or an alkylene group having 3 or less carbon atoms which may have a substituent; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; m and n each independently represent an integer of 0 to 6; a and b each independently represent an integer of 0 to 10. 【Chemistry 2】 (In general formulas (2a) to (2c), R ｃ and R ｄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 5 to 20 carbon atoms, an optionally substituted cycloalkoxyl group having 5 to 20 carbon atoms, and an optionally substituted aryl group having 6 to 20 carbon atoms; Each Y independently represents a fluorene group which may have a substituent; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; p and q each independently represent an integer of 0 to 4; a and b each independently represent an integer of 0 to 10.

2. The thermoplastic resin composition according to claim 1, wherein the first thermoplastic resin and the second thermoplastic resin are both copolymers having the structural unit (A) and the structural unit (B).

3. The thermoplastic resin composition according to claim 1 , wherein the second thermoplastic resin contains only the structural unit (B).

4. 2. The thermoplastic resin composition according to claim 1, wherein the content of the structural unit (A) is 30 to 65 mol% and the content of the structural unit (B) is 35 to 70 mol%, based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin.

5. The thermoplastic resin composition according to claim 1, wherein at least one of the first and second thermoplastic resins further has a structural unit (C) derived from a monomer represented by the following formula (3): 【Transformation 3】 (In formula (3), R １ ~R ４ are each independently a hydrogen atom, an alkyl group, or an aryl group, Z is a single bond or a group represented by the following general formula (4): 【Chemistry 4】 (In formula (4), R ５ and R ６ are each a hydrogen atom, an alkyl group, or an aryl group, and c is an integer of 1 to 3.

6. The thermoplastic resin composition according to claim 1 , wherein the thermoplastic resin composition comprises two or more types of thermoplastic resins containing the structural unit (A).

7. The thermoplastic resin composition according to claim 1 , wherein the thermoplastic resin composition comprises two or more types of thermoplastic resins containing the structural unit (B).

8. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin contains a mold release agent and / or an antioxidant.

9. 9. The thermoplastic resin composition according to claim 1, wherein the average value of in-plane birefringence of the lens of the thermoplastic resin composition is 50 nm or less.

10. 9. The thermoplastic resin composition according to claim 1, wherein the maximum value of in-plane birefringence of the thermoplastic resin composition is 60 nm or less.

11. An optical lens comprising the thermoplastic resin composition according to any one of claims 1 to 8.

Images