Thermoplastic resin composition and optical lens comprising same

Abstract

The present invention provides a thermoplastic resin composition and the like which not only have good performance, but also can easily recycle a thermoplastic resin and reduce environmental burden. The technical problem can be solved by the following thermoplastic resin composition. Namely, the thermoplastic resin composition contains, as a mixture, a first thermoplastic resin having a structural unit (A) derived from a monomer represented by general formula (1) and a second thermoplastic resin having a structural unit (B) derived from a monomer represented by any of general formulae (2a)-(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), and the content of the structural unit (A) is 5-95 mol% and the content of the structural unit (B) is 5-95 mol% based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin. .

Description

Technical Field

[0001] This invention relates to compositions comprising thermoplastic resins such as polycarbonate, and particularly to compositions comprising a variety of specified thermoplastic resins in the form of a mixture. Background Technology

[0002] Thermoplastic resins currently known for use as optical materials (e.g., Patent Documents 1 and 2). In optical thermoplastic resins, good properties such as refractive index and Abbe number are generally required.

[0003] In addition, thermoplastic resins are usually molded into products such as lenses and optical films through molding processes such as injection molding.

[0004] Existing technical documents Patent documents Patent Document 1: International Publication No. 2014 / 073496 Patent Document 2: International Publication No. 2015 / 166951 Summary of the Invention

[0005] The technical problem that the invention aims to solve Existing thermoplastic resins, such as those primarily used for optical applications, cannot be said to possess sufficiently satisfactory properties. For instance, a thermoplastic resin has yet to be achieved that combines good formability, thermal stability, and other properties, in addition to refractive index, Abbe number, and birefringence.

[0006] Furthermore, molding processes such as injection molding of thermoplastic resins often result in more than just finished products. Typically, the thermoplastic resin injected into the mold gaps (sprues, runners, gates, etc.) generates scrap beyond the finished product. Since these scraps are not easily reused, most are considered waste. Therefore, existing thermoplastic resin molding processes may result in insufficient yield rates, necessitating measures to reduce the environmental impact of thermoplastic resin molding processes and expand recycling.

[0007] Technical solutions for solving technical problems In order to solve the above-mentioned technical problems, the inventors of the present invention conducted careful research and found that the thermoplastic resin composition obtained by mixing a variety of specified thermoplastic resins can not only achieve good performance mainly for optical applications, but also the thermoplastic resin is easy to reuse and can reduce environmental impact.

[0008] The present invention includes the following methods.

[0009] [1] A thermoplastic resin composition comprising, in the form of a mixture, a first thermoplastic resin having a structural unit (A) derived from a monomer represented by general formula (1) below and a second thermoplastic resin having a structural unit (B) derived from a monomer represented by any one of general formulas (2a) to (2c) below, 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) described above. Based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin, the content of the structural unit (A) is 5-95 mol%, and the content of the structural unit (B) is 5-95 mol%. In general formula (1), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. X represents a single bond or an alkylene group with 3 or fewer carbon atoms that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b independently represent integers from 0 to 10. In general formulas (2a) to (2c), R c and R dThe groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. Y represents a fluorene group that can have substituents, A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b represent integers from 0 to 10 independently.

[0010] [2] The thermoplastic resin composition as described in [1] above, wherein the first thermoplastic resin and the second thermoplastic resin are both copolymers having the above structural unit (A) and structural unit (B).

[0011] [3] The thermoplastic resin composition as described in [1] above, wherein the second thermoplastic resin has only the above-described structural unit (B).

[0012] [4] The thermoplastic resin composition as described in [1] above, wherein, based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin, 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%.

[0013] [5] The thermoplastic resin composition as described in [1] above, wherein at least one of the first thermoplastic resin and the second thermoplastic resin further has a structural unit (C) derived from the monomer shown in the following formula (3). In formula (3), R1 to R4 are independently hydrogen atoms, alkyl groups, or aryl groups, respectively. Z is a single bond or a group represented by the following general formula (4). In formula (4), R5 and R6 are independently hydrogen atoms, alkyl groups, or aryl groups, respectively. c is an integer from 1 to 3.

[0014] [6] The thermoplastic resin composition as described in [1] above, wherein the thermoplastic resin composition comprises two or more thermoplastic resins having the above structural unit (A).

[0015] [7] The thermoplastic resin composition as described in [1] above, wherein the thermoplastic resin composition comprises two or more thermoplastic resins having the above-described structural unit (B).

[0016] [8] The thermoplastic resin composition as described in [1] above, wherein the thermoplastic resin contains a release agent and / or an antioxidant.

[0017] [9] The thermoplastic resin composition as described in any one of [1] to [8] above, wherein the average value of the birefringence in the lens surface of the thermoplastic resin composition is 50 nm or less.

[0018]

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

[0019]

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

[10] above.

[0020] Invention Effects By utilizing this invention, various specified types of thermoplastic resins can be incorporated in the form of a mixture, enabling the creation of thermoplastic resin compositions that are particularly useful and possess excellent properties for optical applications. The thermoplastic resin compositions of this invention exhibit high refractive index, low Abbe number, and low in-plane birefringence, and also possess excellent moldability and thermal stability. Furthermore, by utilizing this invention, the thermoplastic resins are readily reusable during the formation of the thermoplastic resin compositions, enabling expanded recycling and reduced environmental impact. Detailed Implementation

[0021] 1. Components of the thermoplastic resin composition 1-1. Thermoplastic resin composition The thermoplastic resin composition of the present invention comprises, in the form of a mixture, at least a first thermoplastic resin having a structural unit (A) derived from a monomer of the above general formula (1) and a second thermoplastic resin having a structural unit (B) derived from a monomer of any one of the above general formulas (2a) to (2c). The structural unit (A) of the monomer derived from general formula (1) has a binaphthalene ring, and is therefore referred to as the binaphthalene structural unit below. In addition, the structural unit (B) of the monomer derived from general formula (2) has a fluorene ring, and is therefore referred to as the fluorene structural unit below.

[0022] It should be noted that the details of the first thermoplastic resin and the second thermoplastic resin are as follows.

[0023] In the thermoplastic resin composition, 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, the content of the naphthalene structural unit of structural unit (A) is 5 to 95 mol, and the content of the fluorene structural unit of structural unit (B) is 5 to 95 mol.

[0024] The content of structural unit (A) based on the total molar number of the first thermoplastic resin and the second thermoplastic resin is preferably 5-85 mol% or 10-80 mol%, more preferably 15-70 mol% or 20-65 mol%, further preferably 30-70 mol%, 30-65 mol%, 35-70 mol% or 35-65 mol%, particularly preferably 40-60 mol%, 40-55 mol%, 45-55 mol%, or 45-50 mol%.

[0025] Furthermore, the content of structural unit (A) based on the total molar number of structural units in the thermoplastic resin composition is preferably 5-85 mol% or 10-80 mol%, more preferably 15-70 mol% or 20-65 mol%, further preferably 30-70 mol%, 30-65 mol%, 35-70 mol% or 35-65 mol%, particularly preferably 40-60 mol%, 40-55 mol%, 45-55 mol%, or 45-50 mol%.

[0026] The content of structural unit (B) based on the total molar number of the first thermoplastic resin and the second thermoplastic resin is preferably 10-90 mol% or 15-85 mol%, more preferably 20-75 mol% or 20-70 mol%, further preferably 35-75 mol%, 35-70 mol%, 40-75 mol% or 40-70 mol%, particularly preferably 45-65 mol%, 45-60 mol%, 50-60 mol%, or 50-55 mol%.

[0027] Furthermore, the content of structural unit (B), based on the total molar number of structural units in the thermoplastic resin composition, is preferably 10-90 mol% or 15-85 mol%, more preferably 20-75 mol% or 20-70 mol%, even more preferably 35-75 mol%, 35-70 mol%, 40-75 mol% or 40-70 mol%, particularly preferably 45-65 mol%, 45-60 mol%, 50-60 mol%, or 50-55 mol%.

[0028] In the thermoplastic resin composition, based on the total weight of all thermoplastic resins, the content of the first thermoplastic resin having structural unit (A) is preferably 5-95% by weight, 5-85% by weight or 10-80% by weight, more preferably 15-70% by weight or 20-65% by weight, further preferably 30-70% by weight, 30-65% by weight, 35-70% by weight or 35-65% by weight, particularly preferably 40-60% by weight, 40-55% by weight, 45-55% by weight or 45-50% by weight.

[0029] Furthermore, in the thermoplastic resin composition, based on the total weight of all thermoplastic resins, the content of the second thermoplastic resin having structural unit (B) is preferably 5-95% by weight, 10-90% by weight or 15-85% by weight, more preferably 20-75% by weight or 20-70% by weight, further preferably 35-75% by weight, 35-70% by weight, 40-75% by weight or 40-70% by weight, particularly preferably 45-65% by weight, 45-60% by weight, 50-60% by weight or 50-55% by weight.

[0030] In the thermoplastic resin composition, based on the total weight of all thermoplastic resins, the total content of the first thermoplastic resin having structural unit (A) and the second thermoplastic resin having structural unit (B) is preferably 40% by weight or more, more preferably 50% by weight or more or 60% by weight or more, further 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. Furthermore, it is particularly preferred that all the thermoplastic resins contained in the thermoplastic resin composition are substantially either the first thermoplastic resin or the second thermoplastic resin.

[0031] In the thermoplastic resin composition, based on its total weight, the total content of the first thermoplastic resin having structural unit (A) and the second thermoplastic resin having structural unit (B) is preferably 40% by weight or more, more preferably 50% by weight or more or 60% by weight or more, further 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.

[0032] Thus, the thermoplastic resin composition may also contain components other than the first thermoplastic resin and the second thermoplastic resin. For example, the thermoplastic resin composition may also contain thermoplastic resins other than the first thermoplastic resin and the second thermoplastic resin, as detailed below, such as additives.

[0033] The type of thermoplastic resin contained in the thermoplastic resin composition is not particularly limited, but polycarbonate resin, polyester resin, or polyester-carbonate resin is preferred, and polycarbonate resin is more preferred. The thermoplastic resin contained in the thermoplastic resin composition may have the structure of random copolymer, block copolymer, and alternating copolymer, or it may be a homopolymer.

[0034] 1-2. First thermoplastic resin The first thermoplastic resin has at least one structural unit (A) derived from the monomer shown in general formula (1). In general formula (1), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , Moreover, the aforementioned R h It is an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N and S.

[0035] R in general formula (1) a and R b Preferably, the groups are selected from hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. More preferably, the groups are selected from hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. R a and R b Further preferred are aryl groups selected from hydrogen atoms and aryl groups with 6 to 20 carbon atoms that may have substituents.

[0036] In general formula (1), X is a single bond or an alkylene group with 3 or fewer carbon atoms that may have substituents, preferably a single bond or an alkylene group with 2 or fewer carbon atoms that may have substituents, more preferably a single bond or an alkylene group with 1 carbon atom that may have substituents, and particularly preferably a single bond.

[0037] In general formula (1), A and B independently represent alkylene groups having 1 to 5 carbon atoms that may have substituents, preferably alkylene groups having 1 to 3 carbon atoms that may have substituents, and more preferably alkylene groups having 1 or 2 carbon atoms that may have substituents.

[0038] In general formula (1), m and n are independent integers from 0 to 6, preferably integers from 0 to 3, and more preferably 0 or 1.

[0039] In general formula (1), a and b are independent integers from 0 to 10, preferably integers from 0 to 5, more preferably integers from 0 to 3, and particularly preferably 0 or 1.

[0040] R in general formula (1) a and R b In the options, the alkyl group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms or 1 carbon atom, respectively.

[0041] R in general formula (1) a and R b In the options, the cycloalkyl group having 5 to 20 carbon atoms and the cycloalkoxy group having 5 to 20 carbon atoms preferably have 5 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, and even more preferably 6 or 7 carbon atoms, respectively.

[0042] R in general formula (1) a and R b Among the options, the number of carbon atoms in the aryl group having 6 to 20 substituents, the number of carbon atoms in the heteroaryl group having 6 to 20 substituents containing one or more heterocyclic atoms selected from O, N and S, and the number of carbon atoms in the aryloxy group having 6 to 20 substituents are preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 to 8 or 6.

[0043] It should be noted that the substituents that can be included in the structural unit (A) of formula (1) above can include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups with 1 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyloxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyloxy groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, etc. It should be noted that the number of carbon atoms involved in general formula (1) also includes the number of carbon atoms of the substituents.

[0044] Preferred examples of monomers forming the above-mentioned structural unit (A) include 2,2′-bis(hydroxy(poly)alkoxy)-diaryl-1,1′-binaphthylenes, 2,2′-bis(hydroxy(poly)alkoxy)-dinaphthyl-1,1′-binaphthylenes, etc. Among these monomeric compounds, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthyl-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-bis(naphthyl-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthyl, and 2,2'-bis(2-hydroxypropoxy)-6,6'-bis(naphthyl-1-yl)-1,1'-binaphthyl are preferred. These monomeric compounds can be used alone or in combination of two or more to form structural unit (A). The first thermoplastic resin is preferably a copolymer having both the above-described structural unit (A) and the structural unit (B) described in detail later. In this first thermoplastic resin, based on the total molar number of the binatene structural unit (A) and the fluorene structural unit (B), the content of structural unit (A) is preferably 5–85 mol% or 10–80 mol%, more preferably 15–70 mol% or 20–65 mol%, further preferably 30–70 mol%, 30–65 mol%, 35–70 mol% or 35–65 mol%, particularly preferably 40–60 mol%, 40–55 mol%, 35–55 mol%, or 45–50 mol%.

[0045] In the first thermoplastic resin, the content of structural unit (A) in all structural units is preferably 40 mol% or more, more preferably 50 mol% or more or 60 mol% or more, further preferably 70 mol% or more or 80 mol% or more, and particularly preferably 90 mol% or more or 95 mol% or more.

[0046] In addition, although the first thermoplastic resin may also contain structural units other than structural unit (A) and structural unit (B), the content of structural unit (A) and structural unit (B) in all structural units is preferably 40 mol% or more, more preferably 50 mol% or more or 60 mol% or more, further preferably 70 mol% or more or 80 mol% or more, and particularly preferably 90 mol% or more or 95 mol% or more.

[0047] The thermoplastic resin composition preferably comprises, for example, a first thermoplastic resin in the form of a mixture of multiple thermoplastic resins having the above-described structural unit (A). In thermoplastic resin compositions comprising a first thermoplastic resin and a second thermoplastic resin in the form of a mixture, and more preferably comprising multiple thermoplastic resins having structural unit (A) in the form of a mixture, preferred properties can be expected, as described later.

[0048] 1-3. Second thermoplastic resin The second thermoplastic resin has at least one structural unit (B) derived from a monomer represented by any one of the general formulas (2a) to (2c). In general formulas (2a) to (2c), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. R in general formulas (2a) to (2c) c and R dPreferably, the groups are independently selected from hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents; more preferably, the groups are selected from hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. R c and R d Further preferred are aryl groups selected from hydrogen atoms and aryl groups with 6 to 20 carbon atoms that may have substituents.

[0049] In general formulas (2a) to (2c), Y is independently a fluorene group that can have substituents.

[0050] In general formulas (2a) to (2c), A and B independently represent alkylene groups having 1 to 5 carbon atoms that may have substituents, preferably alkylene groups having 1 to 3 carbon atoms that may have substituents, and more preferably alkylene groups having 1 or 2 carbon atoms that may have substituents.

[0051] In general formulas (2a) to (2c), p and q independently represent integers from 0 to 4, preferably integers from 0 to 3, and more preferably 0 or 1.

[0052] In addition, in general formulas (2a) to (2c), a and b independently represent integers from 0 to 10, preferably integers from 0 to 5, more preferably integers from 0 to 3, and particularly preferably 0 or 1.

[0053] R in general formulas (2a) to (2c) c and R d In the options, the alkyl group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms or 1 carbon atom, respectively.

[0054] R in general formulas (2a) to (2c) c and R d In the options, the cycloalkyl group having 5 to 20 carbon atoms and the cycloalkoxy group having 5 to 20 carbon atoms preferably have 5 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, and even more preferably 6 or 7 carbon atoms, respectively.

[0055] R in general formulas (2a) to (2c) c and R d In the options, the aryl group having 6 to 20 carbon atoms of substituents preferably has 6 to 12 carbon atoms, more preferably 6 to 10, and even more preferably 6 to 8 or 6.

[0056] It should be noted that the substituents that can be included in structural unit (B) of formulas (2a) to (2c) above include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups with 1 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyloxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyloxy groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, etc. It should also be noted that the number of carbon atoms involved in general formulas (2a) to (2c) includes the number of carbon atoms of the substituents.

[0057] Preferred examples of monomers forming the aforementioned structural unit (B) include BNEF (9,9-bis[6-(2-hydroxyethoxy)naphthyl-2-yl]fluorene), BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), and BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene). The aforementioned monomeric compounds can be used alone or in combination of two or more to form structural unit (B). Furthermore, the second thermoplastic resin is preferably a copolymer having the above-described structural unit (B) and structural unit (A). In the second thermoplastic resin, which is such a copolymer, based on the total molar number of fluorene structural units (B) and binaphthalene structural units (A), the content of structural unit (B) is preferably 5–90 mol%, 10–90 mol%, or 15–85 mol%, more preferably 20–75 mol%, or 20–70 mol%, further preferably 35–75 mol%, 35–70 mol%, 40–75 mol%, or 40–70 mol%, particularly preferably 45–65 mol%, 45–60 mol%, 50–60 mol%, or 50–55 mol%.

[0058] In the second thermoplastic resin, the content of structural unit (B) in all structural units is preferably 40 mol% or more, more preferably 50 mol% or more or 60 mol% or more, further preferably 70 mol% or more or 80 mol% or more, and particularly preferably 90 mol% or more or 95 mol% or more.

[0059] In the thermoplastic resin composition, it is preferred that at least either the second thermoplastic resin or the first thermoplastic resin is a copolymer having both structural unit (A) and structural unit (B). Moreover, in the thermoplastic resin composition, both the second thermoplastic resin and the first thermoplastic resin can be copolymers having both structural unit (A) and structural unit (B).

[0060] The thermoplastic resin composition preferably comprises, for example, a second thermoplastic resin in the form of a mixture of multiple thermoplastic resins having the above-described structural unit (B). In thermoplastic resin compositions comprising a second thermoplastic resin and a first thermoplastic resin in the form of a mixture, and more preferably comprising multiple thermoplastic resins having structural unit (B) in the form of a mixture, preferred properties can be expected, as described later.

[0061] 1-4. Other thermoplastic resins The thermoplastic resin composition may also contain thermoplastic resins other than the first and second thermoplastic resins described above (other thermoplastic resins). For example, as a specific example of other thermoplastic resins, structural units (C) derived from the monomers shown in the following formula (3) can be cited. In formula (3), R1 to R4 are each independently a hydrogen atom, an alkyl group, or an aryl group. R1 to R4 are preferably selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or aryl groups having 6 to 20 carbon atoms; more preferably, they are selected from hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, or aryl groups having 6 to 12 carbon atoms; and even more preferably, they are selected from hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, or aryl groups having 6 to 8 carbon atoms. R1 to R4 may also all be alkyl groups with substituents or aryl groups with substituents.

[0062] 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), R5 and R6 are hydrogen atoms, alkyl groups, or aryl groups, respectively. R5 and R6 are preferably selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 20 carbon atoms, more preferably selected from hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms, and even more preferably selected from hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and aryl groups having 6 to 8 carbon atoms. R5 and R6 may also both be alkyl groups with substituents or aryl groups with substituents.

[0063] In addition, the subscript c in equation (4), i.e., the lowercase c that does not mean C of carbon atoms when combined with R5 and R6, represents an integer from 1 to 3. c is preferably 1 or 2, and more preferably 1.

[0064] It should be noted that the substituents that can be included in the structural unit (C) of formulas (3) and (4) above include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups with 1 to 10 carbon atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyloxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyloxy groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, etc. It should be noted that the number of carbon atoms involved in general formulas (3) and (4) also includes the number of carbon atoms of the substituents.

[0065] 1-5. Secondary components Thermoplastic resin compositions may also contain components other than thermoplastic resins. For example, at least one additive selected from mold release agents, antioxidants, etc. Preferably, the thermoplastic resin composition contains either or both of mold release agents and antioxidants.

[0066] In the thermoplastic resin composition, based on the total weight, the content of minor components such as additives other than thermoplastic resin is preferably 20% by weight or less, more preferably 15% by weight or less or 10% by weight or less, further 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.

[0067] Specific examples of additives contained in thermoplastic resin compositions include the following additives.

[0068] Release agent Examples of release agents include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin-based). Specifically, at least one compound selected from aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200-15000, and polysiloxane-based silicone oils can be used. Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Preferred aliphatic carboxylic acids are mono- or di-carboxylic acids with 6-36 carbon atoms, and more preferably, saturated aliphatic mono-carboxylic acids with 6-36 carbon atoms. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, hexanoic acid, decanoic acid, lauric acid, arachidic acid, benzyl acid, ceric acid, ceric acid, beeswax acid, tetradecanoic acid, linalic acid, glutaric acid, adipic acid, and azelaic acid. The same compound as the aforementioned aliphatic carboxylic acids can be used as the aliphatic carboxylic acid in the ester 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 substituents such as fluorine atoms or aryl groups. Among them, monohydric or polyhydric saturated alcohols with 30 or fewer carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols with 30 or fewer carbon atoms are more preferred. Aliphatic compounds also include alicyclic compounds. Specific examples of alcohols include octanol, decanol, dodecanoyl alcohol, stearyl alcohol, betaine alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentyl glycol, di(trimethylol)propane, and dipentaerythritol.

[0069] The aforementioned ester compounds may contain aliphatic carboxylic acids and / or alcohols as impurities, or they may be mixtures of various compounds. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture with beeswax palmitate as the main component), stearate stearate, benzyl benzyl acid, benzyl stearate, glyceryl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tripearate, and pentaerythritol tetrastearate. Examples of aliphatic hydrocarbons with a number-average molecular weight of 200–15000 include liquid paraffin, solid paraffin, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers with 3–12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. Furthermore, these hydrocarbon compounds may be partially oxidized. The preferred components are solid paraffin wax, polyethylene wax, or partial oxides of polyethylene wax, more preferably solid paraffin wax or polyethylene wax. The number-average molecular weight is preferably 200 to 5000. These aliphatic hydrocarbons can be a single substance or a mixture of 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 fluoroalkyl organosilicones. Two or more of these can also be used in combination.

[0070] The proportion of the release agent added relative to 100 parts by weight of the thermoplastic resin is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, and preferably 2 parts by weight or less, more preferably 1 part by weight or less.

[0071] A single type of release agent may be used, or two or more may be used. When using two or more, it is preferable that the total amount is within the range described above.

[0072] antioxidants Examples of antioxidants include phenolic antioxidants, hindered phenolic antioxidants, bisphenol antioxidants, and polyphenol antioxidants.

[0073] Specifically, examples include 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, tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4'-butylenebis-(3-methyl-6-tert-butylphenol), bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]triethylene glycol ester, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Pentaerythritol ester, thiodiethylidene 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-methylpentadecanyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(trimethylbenzene-2,4,6-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, etc.

[0074] Examples of phenolic antioxidants include BASF's "Irganox1010" (registered trademark, hereinafter the same) and "Irganox1076", and ADEKA's "ADK STAB AO-50" and "ADK STAB AO-60".

[0075] The proportion of antioxidant added relative to 100 parts by weight of thermoplastic resin is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, and preferably 1 part by weight or less, more preferably 0.5 parts by weight or less.

[0076] The antioxidant may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the range described above.

[0077] 2. Method for manufacturing thermoplastic resin composition The following describes a method for manufacturing thermoplastic resin compositions. Thermoplastic resins such as first thermoplastic resin and second thermoplastic resin can be manufactured by known methods. For example, a polymerization reaction can be carried out in a reaction system containing monomer compounds and a catalyst under conditions of a polymerization temperature of 200 to 250°C and a pressure of 760 mmHg to 200 mmHg, thereby manufacturing thermoplastic resins. For example, thermoplastic resins as polycarbonate resins can be manufactured by melt polycondensation using monomer compounds shown in the above general formulas (1) to (3) and carbonate precursors such as diesters as raw materials, in the presence of an alkaline compound catalyst, an ester exchange catalyst, or a mixed catalyst containing both, or in the absence of a catalyst.

[0078] A thermoplastic resin composition can be manufactured by melt-blending various thermoplastic resins obtained from polymerization reactions and the aforementioned minor components, or by dissolving them separately in a solvent and then allowing the solvent to evaporate. Halogenated organic solvents, THF, etc., are suitable when a solvent is intended to be used.

[0079] 3. Properties of the thermoplastic resin composition and the thermoplastic resin The preferred properties of the thermoplastic resin composition and the thermoplastic resin are described below.

[0080] 3-1. Total light transmittance (TT (%)) The total light transmittance (%) of the thermoplastic resin composition, as measured by the method described later according to JIS K 7361-1:1997, is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 85% or more.

[0081] 3-2. YI value The YI value of the thermoplastic resin composition, as measured by the method described below according to JIS K 7373:2006, is preferably 20 or less, more preferably 16 or less, further preferably 14 or less, and particularly preferably 13.5 or less.

[0082] 3-3. Haze The haze value of the thermoplastic resin composition, measured by the method described below according to JIS K-7136:2000, is preferably 2.0 or less, more preferably 1.0 or less, further preferably 0.8 or less, and particularly preferably 0.6 or less.

[0083] 3-4. Refractive Index The thermoplastic resin composition has a refractive index (nD) of 1.630 or more, more preferably 1.640 or more, further preferably 1.650 or more, and particularly preferably 1.660 or more or 1.670 or more, in accordance with JIS B 7071-2:2018.

[0084] 3-5. Abbe number (νd) The Abbe number (νd) of the thermoplastic resin composition, as measured by the method described later, is preferably 24 or less, more preferably 22 or less, further preferably 21 or less, particularly preferably 20 or less or 19 or less.

[0085] 3-6. Melt Volumetric Rate (MVR) Thermoplastic resin compositions according to the MVR value (unit: cm) of JIS K7210 3 The value of ( / 10min) is preferably 30 or more, more preferably 40 or more, further preferably 45 or more or 50 or more, and particularly preferably 55 or more or 65 or more.

[0086] It can be assumed that resins or resin compositions with higher MVR values ​​have higher flowability. As will be discussed later, it can be confirmed that thermoplastic resins in mixtures with essentially the same type and content of structural units tend to have higher MVR values ​​compared to thermoplastic resins in copolymers.

[0087] Thus, the thermoplastic resin composition of the present invention, which contains a mixture of thermoplastic resins, can be considered to have good flowability and moldability.

[0088] 3-7. In-plane birefringence (average and maximum values) The average value of the in-plane birefringence of the thermoplastic resin composition, measured by the method described later, is preferably 50 nm or less or 40 nm or less, more preferably 30 nm or less, further preferably 15 nm or less, and particularly preferably 13 nm or less or 11 nm or less.

[0089] Furthermore, the maximum value of the intra-lens birefringence of the thermoplastic resin composition measured by the method described later is preferably 90 nm or less or 80 nm or less, more preferably 70 nm or less or 60 nm or less, further preferably 50 nm or less or 35 nm or less, and particularly preferably 30 nm or less or 20 nm or less.

[0090] As can be seen from the results of the examples and comparative examples described later, the thermoplastic resin of the mixture with basically the same type and content of structural units tends to have a lower in-plane birefringence value (mm) compared with the thermoplastic resin of the copolymer.

[0091] Thus, the thermoplastic resin composition of the present invention, which contains a mixture of thermoplastic resins, can be considered to have excellent birefringence.

[0092] 3-8. Weight-average molecular weight 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, even more preferably 10,000 to 100,000, for example, more preferably 20,000 to 80,000, even more preferably 30,000 to 70,000, and particularly preferably 40,000 to 65,000.

[0093] The weight-average molecular weight of thermoplastic resins, for example as the converted weight-average molecular weight (Mw) of polystyrene, is determined as follows.

[0094] GPC (gel permeation chromatography) was used with chloroform as the developing solvent. A calibration curve was constructed using a standard polystyrene (Shodex STANDARD, SM-105) with a known molecular weight (molecular weight distribution = 1). Based on the measured dissolution time and molecular weight values ​​of the standard polystyrene, a plot was plotted and fitted with a cubic equation to obtain the calibration curve.

[0095] Then, based on the obtained calibration curve, the weight-average molecular weight (Mw) is calculated using the polystyrene equivalent value according to the following formula.

[0096] [Calculation formula] Mw=Σ(W i ×M i ) / Σ(W i ) In the above formula, i represents the i-th segmentation point when dividing molecular weight M, and W i M represents the weight of the i-th element. i This represents the molecular weight of the i-th element. Furthermore, the molecular weight M represents the molecular weight of polystyrene converted from the calibration curve at the same dissolution time.

[0097] 3-9. Glass transition temperature (Tg) The thermoplastic resin composition preferably has a glass transition temperature (Tg) of 100–200 °C, more preferably 110–180 °C, further preferably 120–160 °C, and particularly preferably 130–150 °C, according to JIS K7121-1987.

[0098] 4. Molded body comprising a thermoplastic resin composition The thermoplastic resin composition of the present invention can be used in extrusion molding, blow molding, injection molding, etc. Molded articles obtained from the thermoplastic resin composition include extruded articles, hollow articles, precision parts, and injection-molded articles of thin materials.

[0099] 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, optical disc substrates and other films, and housings of electronic devices such as smartphones.

[0100] The present invention will be described in more detail below with reference to embodiments, but the present invention is not limited thereto.

[0101] Example The methods for determining the properties of the thermoplastic resins or thermoplastic resin compositions obtained in the examples and comparative examples described later are as follows.

[0102] (1) In-plane birefringence of the lens (average value) Molding of test pieces The obtained resin or resin composition was injection molded to obtain a concave lens test piece with a diameter of 4.5 mm and a center thickness of 0.2 mm.

[0103] Molding machine: SUMITOMO SHI DEMAG SE50EV Molding conditions: Barrel temperature 260℃, mold temperature: glass transition temperature (Tg) -15℃, injection speed 30mm / s, VP pressure 65MPa (position 2.3mm), holding pressure 65MPa for 1 second + 55MPa for 1.5 seconds. Measurement of in-plane birefringence of a lens The delay of the concave lens test piece obtained by the above method was measured.

[0104] Measuring apparatus: Photonic Lattice Co., Ltd. WPA-100 Data processing method: The average delay was obtained using the software "PA / WPA View" manufactured by Photonic Lattice Co., Ltd., and used as the in-plane birefringence (average value).

[0105] (2) Birefringence within the lens plane (maximum value) The retardation value of the test piece was determined in the same manner as described in (1) above, and the maximum value of the obtained measurement was taken as the in-plane birefringence (maximum value).

[0106] (3) Total light transmittance (TT), YI and haze The obtained resin was molded to a thickness of 3 mm, and the total light transmittance (TT), YI, and haze were measured using a spectrophotometer. The total light transmittance (TT) was obtained according to JIS K 7361-1:1997, the YI was obtained according to JIS K 7373:2006, and the haze was obtained according to JIS K-7136:2000.

[0107] Measurement equipment: SH 7000 manufactured by Nippon Denshoku Kogyo Co., Ltd. (4) Refractive index (nD) According to JIS B 7071-2:2018, the obtained resin or resin composition was molded into a V-shaped block of a specified shape, which served as a test piece. The refractive index was measured at 23°C using a refractometer (Shimadzu KPR-3000).

[0108] (5) Abbe number (νd) Using the same test piece (V-block) as the test piece used for refractive index measurement, the refractive index at wavelengths of 486 nm, 589 nm, and 656 nm at 23 °C was measured using a refractive index meter, and the Abbe number was calculated using the following formula.

[0109] Refractometer: Shimadzu KPR-3000 ν=(nD-1) / (nF-nC) nD: Refractive index at a wavelength of 589nm nC: Refractive index at a wavelength of 656nm nF: Refractive index at a wavelength of 486nm (6) Glass transition temperature (Tg) According to JIS K7121-1987, the measurements were performed using a differential scanning calorimeter, following a heating program of 10℃ / min.

[0110] Differential scanning calorimeter: Hitachi High Technology Corporation X-DSC7000 (7) Melt volumetric rate (MVR) The obtained resin or resin composition was vacuum dried at 120°C for 4 hours and measured according to JIS K7210.

[0111] Measuring apparatus: T-111 melt indexer manufactured by Toyo Seiki Co., Ltd.

[0112] Measurement conditions: The measurement was performed at a temperature of 260℃ and a load of 2160g.

[0113] Operation: MVR (unit: cm) is calculated based on the amount of resin extruded every 10 minutes from a standard die set at the bottom of the barrel. 3 / 10min).

[0114] In addition, MVR is an indicator of resin flowability; the higher the value, the higher the flowability of the resin or resin composition.

[0115] (Example 1) 7.67 kg (20.48 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (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 × 10⁻⁶ sodium bicarbonate were added to a 50-liter reactor equipped with a stirrer and distillation apparatus. -2 g (2.86×10 - 4 (mol). After nitrogen replacement inside the reaction system, the temperature was raised to 205°C over 20 minutes at a nitrogen atmosphere of 760 Torr. Then, the pressure was reduced to 700 Torr over 10 minutes to melt the raw materials. This state was maintained for 10 minutes followed by stirring, and then maintained for 100 minutes. Afterward, the pressure was reduced to 205 Torr over 20 minutes. This state was maintained for 60 minutes, and then the pressure was adjusted to 180 Torr over 10 minutes, maintaining the conditions of 215°C and 180 Torr for 20 minutes. Then, the pressure was adjusted to 150 Torr over 10 minutes, maintaining the conditions of 230°C and 150 Torr for 30 minutes. Finally, the pressure was reduced to 120 Torr and the temperature was raised to 235°C. Then, the pressure was reduced to 100 Torr over 10 minutes and maintained for 10 minutes. After another 50 minutes, the pressure in the reaction system was adjusted to below 1 Torr, and maintained at 235°C and 1 Torr for 40 minutes. After the reaction was completed, nitrogen was blown into the reactor to pressurize it, and the generated polycarbonate resin was granulated and discharged.

[0116] Using a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machinery Co., Ltd., rotating in the same direction), 0.2 parts by weight of glyceryl monostearate (RIKEMAL S-100A manufactured by Riken Vitamin Co., Ltd.), 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60 manufactured by ADEKA Co., Ltd.), and 0.03 parts by weight of 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphospiro[5.5]undecane (ADK STAB PEP-36 manufactured by ADEKA Co., Ltd.) were mixed in as additives to 100 parts by weight of the discharged polycarbonate resin granules, thus obtaining a polycarbonate resin mixed with additives.

[0117] The extrusion conditions are: output rate of 15 kg / h, screw speed of 300 rpm, vacuum degree of 3 kPa at the exhaust port, and extrusion temperature from the first feed port to the die section is 200℃, 220℃, 240℃, 260℃, 260℃, 260℃, 260℃, 260℃, 255℃, 255℃.

[0118] (Recycling of waste resin 1) Optical lenses were formed using the polycarbonate resin obtained in Polymerization Example 1, and the resulting molded body, including the sprue and runner (recycled product 1), was recycled.

[0119] (Example 2) The following raw materials were added to a 50-liter reactor equipped with a stirrer and distillation apparatus: 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 × 10⁻⁶) of sodium bicarbonate. -4 After nitrogen replacement of the reaction system (mol), it was heated to 180°C under a nitrogen atmosphere of 760 mmHg. After 30 minutes of heating to confirm complete dissolution of the raw materials, it was stirred for 120 minutes under these conditions. The pressure was then adjusted to 200 mmHg, and the temperature was increased to 200°C at a rate of 60°C / hr. At this point, the byproduct phenol was confirmed to begin distilling out. The reaction system was then maintained at 200°C for 40 minutes. The temperature was then increased to 230°C at a rate of 75°C / hr. After the heating was completed, the pressure was adjusted to below 1 mmHg and maintained at this temperature for 2 hours. The reaction system was then heated to 245°C at a rate of 60°C / hr and stirred for another 50 minutes. After the reaction was complete, nitrogen was introduced into the reactor to restore atmospheric pressure, and the generated polycarbonate resin was granulated and discharged.

[0120] The discharged polycarbonate resin was processed in the same manner as in polymerization example 1 to obtain polycarbonate resin mixed with additives.

[0121] (Recycling of waste resin 2) In the same manner as described above (recycling of waste resin 1), recycled material (recycling material 2) including the sprue and the runner was recovered from the polycarbonate resin obtained in polymerization example 2.

[0122] (Example 1) A resin composition was obtained by melt mixing 100 parts by weight of a thermoplastic resin containing 85% by weight of the above-mentioned recycled product 1 and 15% by weight of the above-mentioned recycled product 2, 0.2 parts by weight of glyceryl monostearate (RIKEMAL S-100A manufactured by Riken Vitamin Co., Ltd.) as an additive, and 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADKSTAB AO-60 manufactured by ADEKA Co., Ltd.). In addition, the extruder used for melt mixing is a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machinery Co., Ltd., rotating in the same direction). The extrusion conditions are: output rate of 15 kg / h, screw speed of 300 rpm, vacuum degree of 3 kPa at the vent, and extrusion temperature from the first feed port to the die section is 200℃, 220℃, 240℃, 260℃, 260℃, 260℃, 260℃, 260℃, 255℃, 255℃.

[0123] The physical properties of the obtained composition are shown in Table 1 below.

[0124] (Examples 2-3, Comparative Examples 1 and 2) Except for the melt mixing according to the proportions shown in Table 1, the same procedure as in Example 1 was followed to obtain the resin composition.

[0125] The physical properties of the obtained composition are shown in Table 1 below.

[0126] [Table 1] (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 × 10⁻⁶ sodium bicarbonate were added to a 50-liter reactor equipped with a stirrer and distillation apparatus. -2 g (2.86×10 -4(mol). After nitrogen replacement in the reaction system, the temperature was raised to 205°C over 20 minutes at a nitrogen atmosphere of 760 Torr. Then, the pressure was reduced to 700 Torr over 10 minutes, and the raw materials were melted. This state was maintained for 10 minutes, followed by stirring, and then maintained for another 100 minutes. The pressure was then reduced to 205 Torr over 20 minutes. Then, the pressure in the reaction system was adjusted to 180 Torr over 10 minutes and maintained at 215°C and 180 Torr for 20 minutes. The pressure was then adjusted to 150 Torr over another 10 minutes and maintained at 230°C and 150 Torr for 30 minutes. The pressure was then reduced to 120 Torr and the temperature was raised to 235°C. Then, the pressure was reduced to 100 Torr over 10 minutes and maintained for 10 minutes. Finally, the pressure was adjusted to below 1 Torr over 50 minutes and maintained at 235°C and 1 Torr for 40 minutes. After the reaction is complete, nitrogen gas is blown into the reactor to pressurize it, and the generated polycarbonate resin is granulated and discharged.

[0127] Using a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machinery Co., Ltd., rotating in the same direction), 0.2 parts by weight of glyceryl 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] (ADK STAB AO-60 manufactured by ADEKA Co., Ltd.) were mixed in as additives to 100 parts by weight of the discharged polycarbonate resin granules, thus obtaining a polycarbonate resin mixed with additives.

[0128] The extrusion conditions are: output rate of 15 kg / h, screw speed of 300 rpm, vacuum degree of 3 kPa at the exhaust port, and extrusion temperature from the first feed port to the die section is 200℃, 220℃, 240℃, 260℃, 260℃, 260℃, 260℃, 260℃, 255℃, 255℃.

[0129] (Recycling of waste resin 3) The polycarbonate resin obtained in Polymerization Example 3 was used to mold an optical lens, and the sprue and runner of the resulting molded body were recycled (Recycled Product 3).

[0130] (Example 4) 7.84 kg (20.96 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE), 10.03 kg (18.63 mol) of 9,9-[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 × 10⁻⁶ sodium bicarbonate were added to a 50-liter reactor equipped with a stirrer and distillation apparatus. -2 g (2.86×10 -4 (mol). After nitrogen replacement in the reaction system, the temperature was raised to 205°C over 20 minutes at a nitrogen atmosphere of 760 Torr. Then, the pressure was reduced to 700 Torr over 10 minutes to melt the raw materials. This state was maintained for 10 minutes, followed by stirring, and then maintained for another 100 minutes. The pressure was then reduced to 205 Torr over 20 minutes. This state was maintained for 60 minutes, and then the pressure was adjusted to 180 Torr over 10 minutes. This state was maintained at 215°C and 180 Torr for 20 minutes. The pressure was then adjusted to 150 Torr over another 10 minutes, and maintained at 230°C and 150 Torr for 30 minutes. The pressure was then reduced to 120 Torr and the temperature was raised to 235°C. Finally, the pressure was reduced to 100 Torr over 10 minutes and maintained for 10 minutes. After another 50 minutes, the pressure in the reaction system was adjusted to below 1 Torr, and maintained at 235°C and 1 Torr for 40 minutes. After the reaction was completed, nitrogen was blown into the reactor to pressurize it, and the generated polycarbonate resin was granulated and discharged.

[0131] Using a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machinery Co., Ltd., rotating in the same direction), 0.2 parts by weight of glyceryl monostearate (RIKEMAL S-100A manufactured by Riken Vitamin Co., Ltd.), 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60 manufactured by ADEKA Co., Ltd.), and 0.03 parts by weight of 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphospiro[5.5]undecane (ADK STAB PEP-36 manufactured by ADEKA Co., Ltd.) were mixed in as additives to 100 parts by weight of the discharged polycarbonate resin granules, thus obtaining a polycarbonate resin mixed with additives.

[0132] The extrusion conditions are: output rate of 15 kg / h, screw speed of 300 rpm, vacuum degree of 3 kPa at the exhaust port, and extrusion temperature from the first feed port to the die section is 200℃, 220℃, 240℃, 260℃, 260℃, 260℃, 260℃, 260℃, 255℃, 255℃.

[0133] (Example 4) A resin composition was obtained by melt mixing 100 parts by weight of a thermoplastic resin containing 90% by weight of the above-mentioned recycled product 3 and 10% by weight of the above-mentioned recycled product 2, 0.2 parts by weight of glyceryl monostearate (RIKEMAL S-100A manufactured by Riken Vitamin Co., Ltd.) as an additive, and 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADKSTAB AO-60 manufactured by ADEKA Co., Ltd.). In addition, the extruder used for melt mixing is a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machinery Co., Ltd., rotating in the same direction). The extrusion conditions are: output rate of 15 kg / h, screw speed of 300 rpm, vacuum degree of 3 kPa at the vent, and extrusion temperature from the first feed port to the die section is 200℃, 220℃, 240℃, 260℃, 260℃, 260℃, 260℃, 260℃, 255℃, 255℃.

[0134] The physical properties of the obtained composition are shown in Table 1.

[0135] (Examples 5 and 6) Except for the melt mixing according to the proportions shown in Table 2, the same procedure as in Example 4 was followed to obtain the resin composition.

[0136] The physical properties of the obtained composition are shown in Table 2.

[0137] [Table 2] (Example 7) Using an extruder, 100 parts by weight of a thermoplastic resin containing 70% by weight of the above-mentioned recycled product 2 and 30% by weight of the above-mentioned recycled product 4, 0.2 parts by weight of glyceryl monostearate (RIKEMAL S-100A manufactured by Riken Vitamin Co., Ltd.) as an additive, and 0.1 parts by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADKSTAB AO-60 manufactured by ADEKA Co., Ltd.) were melt-mixed to obtain a resin composition. In addition, the extruder used for melt mixing is a vented twin-screw extruder (TEM-26SX manufactured by Shibaura Machinery Co., Ltd., rotating in the same direction). The extrusion conditions are: output rate of 15 kg / h, screw speed of 300 rpm, vacuum degree of 3 kPa at the vent, and extrusion temperature from the first feed port to the die section is 200℃, 220℃, 240℃, 260℃, 260℃, 260℃, 260℃, 260℃, 255℃, 255℃.

[0138] The physical properties of the obtained composition are shown in Table 3.

[0139] (Examples 8 and 9) Except for the melt mixing according to the proportions shown in Table 2, the same procedure as in Example 7 was followed to obtain the resin composition.

[0140] The physical properties of the obtained composition are shown in Table 3.

[0141] [Table 3] The molecular structures and abbreviations of the monomer compounds used in the above polymerization examples are shown below. The results from the above examples and comparative examples confirm the following tendency: the thermoplastic resin mixtures have lower in-plane birefringence values ​​(mm) compared to thermoplastic resins of copolymers with essentially the same type and content of structural units (especially 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.). Therefore, the thermoplastic resin compositions of the present invention comprising mixtures of thermoplastic resins can be considered to have excellent birefringence.

[0142] Furthermore, it can be considered that the thermoplastic resin mixture tends to have a larger MVR value and higher flowability compared to the thermoplastic resin of copolymers with essentially the same type and content of structural units (especially Examples 7-9 and Comparative Example 4, etc.). Thus, the thermoplastic resin composition of the present invention containing a mixture of thermoplastic resins has good flowability and moldability.

[0143] Furthermore, it can be considered that the in-plane birefringence value is lower, or the MVR value is increased, i.e., the flowability is improved, compared with the thermoplastic resin composition of the reused embodiment, which can be regarded as a reference example, i.e., the freshly manufactured thermoplastic resin or resin composition that is not reused.

[0144] Furthermore, since the thermoplastic resin composition of the present invention contains the necessary thermoplastic resin in the form of a mixture, it is possible not only to reuse scraps of thermoplastic resin generated in the gaps of, for example, the sprues, runners, and gates of the injection mold, but also to utilize them easily and effectively. Therefore, the thermoplastic resin composition of the present invention can be manufactured by a simple method that includes reuse, and can achieve excellent performance for optical applications particularly easily.

Claims

1. A thermoplastic resin composition, characterized in that: The mixture comprises a first thermoplastic resin having structural unit A derived from a monomer represented by general formula (1) below and a second thermoplastic resin having structural unit B derived from a monomer represented by any of general formulas (2a) to (2c) below. At least one of the first thermoplastic resin and the second thermoplastic resin is a copolymer having both structural unit A and structural unit B. Based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin, the content of structural unit A is 5-95 mol%, and the content of structural unit B is 5-95 mol%. In general formula (1), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups having 6 to 20 carbon atoms that may have substituents containing one or more heterocyclic atoms selected from O, N, and S, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group with 6 to 20 carbon atoms that may have substituents, or a heteroaryl group with 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S. X represents a single bond or an alkylene group with 3 or fewer carbon atoms that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b independently represent integers from 0 to 10. In general formulas (2a) to (2c), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. Y represents a fluorene group that can have substituents, A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b represent integers from 0 to 10 independently.

2. The thermoplastic resin composition according to claim 1, characterized in that: Both the first thermoplastic resin and the second thermoplastic resin are copolymers having the structural unit A and the structural unit B.

3. The thermoplastic resin composition according to claim 1, characterized in that: The second thermoplastic resin has only the structural unit B.

4. The thermoplastic resin composition according to claim 1, characterized in that: Based on the total number of structural units of the first thermoplastic resin and the second thermoplastic resin, the content of structural unit A is 30-65 mol%, and the content of structural unit B is 35-70 mol%.

5. The thermoplastic resin composition according to claim 1, characterized in that: At least one of the first thermoplastic resin and the second thermoplastic resin further has a structural unit C derived from a monomer shown in formula (3) below. In formula (3), R1 to R4 are independently hydrogen atoms, alkyl groups, or aryl groups, respectively. Z is a single bond or a group represented by the following general formula (4). In formula (4), R5 and R6 are independently hydrogen atoms, alkyl groups, or aryl groups, respectively. c is an integer from 1 to 3.

6. The thermoplastic resin composition according to claim 1, characterized in that: The thermoplastic resin composition comprises two or more thermoplastic resins having the structural unit A.

7. The thermoplastic resin composition according to claim 1, characterized in that: The thermoplastic resin composition comprises two or more thermoplastic resins having the structural unit B.

8. The thermoplastic resin composition according to claim 1, characterized in that: The thermoplastic resin contains a release agent and / or an antioxidant.

9. The thermoplastic resin composition according to any one of claims 1 to 8, characterized in that: The average value of the birefringence within the lens surface of the thermoplastic resin composition is less than 50 nm.

10. The thermoplastic resin composition according to any one of claims 1 to 8, characterized in that: The maximum value of the birefringence within the lens surface of the thermoplastic resin composition is below 60 nm.

11. An optical lens, characterized in that: The thermoplastic resin composition comprising any one of claims 1 to 10.

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