Thermoplastic resin and optical lens

Abstract

Provided are: a thermoplastic resin having sufficiently high optical properties and excellent physical properties such as excellent photoelastic coefficient and saturated water absorption; and an optical lens or the like containing such a thermoplastic resin.　The problem is solved by a thermoplastic resin containing a structural unit (A) derived from a bifunctional compound represented by general formula (1). In general formula (1), W represents a phenyl group or a cyclohexyl group, and n represents 0 or 1.

Description

Thermoplastic resins and optical lenses

[0001] The present invention relates to thermoplastic resins and optical lenses containing thermoplastic resins.

[0002] Thermoplastic resins have traditionally been used as optical materials. These thermoplastic resins are molded into products such as lenses and optical films through molding processes such as injection molding.

[0003] Thermoplastic resins used as optical materials are typically manufactured by polymerizing various monomer compounds. For example, bifunctional compounds having a norbornane skeleton are used as raw materials for thermoplastic resins (see, for example, Patent Documents 1-3).

[0004] Japanese Patent Publication No. 2001-10999, International Publication No. 2015-147242, International Publication No. 2016-153018

[0005] Thermoplastic resins used in optical applications require excellent properties tailored to their specific applications. However, conventional thermoplastic resins do not always possess optical properties that fully satisfy the requirements, and there is a demand for resins with even better properties.

[0006] The main objective of the present invention is to provide a thermoplastic resin that has sufficiently high optical properties and excellent physical properties such as photoelastic coefficient and saturation water absorption rate, and an optical lens containing such a thermoplastic resin.

[0007] The present invention includes the following: [1] A thermoplastic resin comprising a constituent unit (A) derived from a bifunctional compound represented by the following general formula (1). In general formula (1), W represents a phenyl group or a cyclohexyl group, and n represents 0 or 1. [2] The thermoplastic resin according to [1] above, wherein general formula (1) is the following formula (1-1) or formula (1-2). [3] The thermoplastic resin according to [1] or [2] above, for example, the thermoplastic resin according to [1] above, wherein the thermoplastic resin is a polycarbonate resin, a polyester carbonate resin, or a polyester resin. [4] The thermoplastic resin according to any of [1] to [3] above, for example, the thermoplastic resin according to [1] above, wherein the proportion of the constituent unit (A) in all constituent units is 1 to 100 mol%. [5] The thermoplastic resin according to any of [1] to [4] above, for example, the thermoplastic resin according to [1] above, wherein the thermoplastic resin further comprises a monomer-derived constituent unit (B) represented by the following general formula (6) and / or a monomer-derived constituent unit (C) represented by the following general formula (7). (In general formula (6), R ａ and R ｂ Each of these independently comprises a hydrogen atom, a halogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, an optionally substituted C5-C20 cycloalkoxyl group, an optionally substituted C6-C20 aryl group, an optionally substituted C6-C20 heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S, an optionally substituted C6-C20 aryloxy group, and -C≡C-R ｈ Selected from the group consisting of R ｈ (wherein is an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group having 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S; X is a single bond or a fluorene group that may have substituents; A and B each independently represent an alkylene group having 1 to 5 carbon atoms that may have substituents; m and n each independently represent an integer from 0 to 6; a and b each independently represent an integer from 0 to 10.) (In general formula (7), R ｃ and R ｄis 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, and Y １ is either a single bond, a fluorene group which may have a substituent, or any of the structural formulas represented by the following formulas (8) to (15), (In formulas (8) to (15), R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２ are bonded to each other to form a carbocyclic or heterocyclic ring having 4 to 20 carbon atoms which may have a substituent, and r and s each independently represent an integer of 0 to 5000. ) 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. ) [6] The thermoplastic resin according to [5] above, wherein in the general formulas (6) and (7), A and B each independently represent an alkylene group having 2 or 3 carbon atoms. [7] The thermoplastic resin according to [5] or [6] above, for example, the thermoplastic resin according to [5] above, wherein in the thermoplastic resin, the proportion of the structural unit (B) in all the structural units is 1 to 99 mol%, and the proportion of the structural unit (C) is 1 to 99 mol%. [8] The thermoplastic resin according to any one of [5] to [7] above, for example, the thermoplastic resin according to [5] above, wherein the thermoplastic resin contains at least a structural unit derived from any of BPEF, BNE, BNEF, DPBBHNA, BPM, and BCFL.

[0008] [9] The thermoplastic resin further comprises a monomer-derived constituent unit (D) represented by the following general formula (2), any of the above [1] to [8], for example, the thermoplastic resin according to [1]. In general formula (2), Z is H, CH ３ or C ２ H ５ This represents , where t represents 0 or 1.

[10] The thermoplastic resin according to [9] above, wherein the proportion of the constituent unit (D) in all constituent units is 1 to 99 mol%.

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

[10] above, for example, the thermoplastic resin according to [1] above, wherein the thermoplastic resin further comprises a constituent unit derived from at least one monomer selected from the group of monomers below. (In the above formula, R １ and R ２ Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ３ and R ４ Each independently represents an aryl group, a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. i and ii each independently represent an integer from 1 to 3.)

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

[11] above, for example, the thermoplastic resin according to [1] above, wherein the weight-average molecular weight (Mw) of the thermoplastic resin on a polystyrene basis is 10,000 to 100,000.

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

[12] above, for example, the thermoplastic resin according to [1] above, wherein the refractive index (nD) of the thermoplastic resin is 1.500 to 1.630.

[14] The thermoplastic resin according to any of [1] to

[13] above, for example, the thermoplastic resin according to [1] above, wherein the Abbe number (ν) of the thermoplastic resin is 20.0 to 60.0.

[15] The thermoplastic resin according to any of [1] to

[14] above, for example, the thermoplastic resin according to [1] above, wherein the glass transition temperature of the thermoplastic resin is 95 to 200°C.

[16] The photoelastic coefficient of the thermoplastic resin is 1.0 × 10 －１２ ・Pa －１ 50 x 10 －１２ ・Pa －１The following thermoplastic resins, any of the above [1] to

[15] , for example, the thermoplastic resin described in [1]:

[17] The thermoplastic resin described in any of the above [1] to

[16] , for example, the thermoplastic resin described in [1], having a saturated water absorption rate of 0.10 to 0.48%.

[18] The density of the thermoplastic resin is 1.00 to 1.30 (g / cm³) ３ ) any of the above [1] to

[17] , for example, the thermoplastic resin described in [1].

[19] An optical lens comprising any of the above [1] to

[18] , for example, the thermoplastic resin described in [1].

[0009] According to the present invention, it is possible to provide a thermoplastic resin that has excellent physical properties such as photoelastic coefficient and saturation water absorption rate, and is particularly suitable for optical applications, as well as an optical lens containing such a thermoplastic resin.

[0010] This is the proton NMR spectrum of the polycarbonate resin obtained in Example 1. This is the proton NMR spectrum of the polycarbonate resin obtained in Example 2. This is the proton NMR spectrum of the polycarbonate resin obtained in Example 4. This is a graph showing the saturated water absorption rate of the polycarbonate resins obtained in Examples 9-11, Comparative Examples 3, 4, and 6.

[0011] 1. Thermoplastic Resin 1-1. Types of Thermoplastic Resins The thermoplastic resin of the present invention has a constituent unit (A) derived from the compound of formula (1) above. As long as it has a predetermined constituent unit, there are no particular limitations on the type of thermoplastic resin, however, the thermoplastic resin is preferably a polycarbonate resin, a polyester carbonate resin, or a polyester resin. The thermoplastic resin may also be a mixture of two or more types, such as polycarbonate resin, polyester carbonate resin, and polyester resin.

[0012] The thermoplastic resin may be a homopolymer, or a copolymer such as a random copolymer or a block copolymer. Alternatively, the thermoplastic resin may be a mixture of copolymers such as a homopolymer, a random copolymer or a block copolymer. For example, a thermoplastic resin may be made by mixing a homopolymer consisting only of constituent unit (A) with another type of polymer. As an example of such a mixture, a homopolymer consisting only of constituent unit (A) may be mixed with at least one or more of the homopolymers consisting only of constituent unit (B), constituent unit (C), and constituent unit (D), which will be described in detail later.

[0013] 1-2. Constituent Units (A) of Thermoplastic Resins The thermoplastic resin contains at least one constituent unit (A) derived from a bifunctional diol compound represented by general formula (1). In general formula (1), W represents a phenyl group or a cyclohexyl group. These phenyl and cyclohexyl groups may each have substituents. Examples of substituents include C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 alkenyl groups, halogens, and hydroxyl groups. The phenyl and cyclohexyl groups may contain 0-5 substituents, for example, 1-3 substituents, or 1 or 2 substituents.

[0014] In general formula (1), n ​​represents 0 or 1, and n is preferably 1. Thus, preferred specific examples of constituent units (A) derived from compounds in general formula (1) where n is 1 include constituent units derived from compounds represented by the following formula (1-1) (hereinafter also referred to as D-NCDM) and compounds represented by formula (1-2) (hereinafter also referred to as D-NPDM).

[0015] In thermoplastic resins, the content of constituent unit (A) is preferably 1 to 100 mol%, based on the total number of moles of constituent units. The content of constituent unit (A) in thermoplastic resins based on the total number of moles is preferably 5 to 95 mol%, 5 to 100 mol%, or 10 to 100 mol%, more preferably 10 to 90 mol%, and even more preferably 15 to 80 mol%. The content of constituent unit (A) in thermoplastic resins may also be 30 to 90 mol%, 40 to 90 mol%, 45 to 90 mol%, 40 to 85 mol%, 45 to 85 mol%, 55 to 85 mol%, 60 to 85 mol%, 60 to 80 mol%, or 65 to 80 mol%, etc. Furthermore, all constituent units in the thermoplastic resin may be constituent unit (A). Furthermore, as described above, when a thermoplastic resin is obtained by mixing a homopolymer consisting only of constituent unit (A) with a homopolymer consisting only of constituent units (B), (C), or (D), respectively, it is preferable that the proportion of constituent unit (A) is as described above, based on the total number of moles of constituent units contained in the thermoplastic resin mixture.

[0016] 1-3. Constituent Units (B) of Thermoplastic Resins Thermoplastic resins may further contain constituent units (B) derived from diol compounds as monomers represented by general formula (6). In general formula (6), R ａ and R ｂ Each of these independently comprises a hydrogen atom, a halogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, an optionally substituted C5-C20 cycloalkoxyl group, an optionally substituted C6-C20 aryl group, an optionally substituted C6-C20 heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S, an optionally substituted C6-C20 aryloxy group, and -C≡C-R ｈ Selected from the group consisting of the above R ｈThis represents an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group having 6 to 20 carbon atoms that may have substituents and contains one or more heterocyclic atoms selected from O, N, and S.

[0017] R in general formula (6) ａ and R ｂ Preferably, the group is selected from a hydrogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, or an optionally substituted C6-C20 aryl group, and more preferably, from a hydrogen atom, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C20 aryl group. ａ and R ｂ More preferably, it is selected from a hydrogen atom and an aryl group having 6 to 20 carbon atoms, which may have substituents.

[0018] In general formula (6), X is a single bond or an alkylene group having 3 or fewer carbon atoms which may have substituents, preferably a single bond or an alkylene group having 2 or fewer carbon atoms which may have substituents, more preferably a single bond or an alkylene group having 1 carbon atom which may have substituents, and particularly preferably a single bond. In general formula (6), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have substituents, preferably an alkylene group having 1 to 3 carbon atoms which may have substituents, more preferably an alkylene group having 2 or 3 carbon atoms, an alkylene group having 1 or 2 carbon atoms, etc. In general formula (6), m and n each independently represent an integer from 0 to 6, preferably an integer from 0 to 3, and more preferably 0 or 1. In general formula (6), a and b each 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.

[0019] R in general formula (6) ａ and R ｂOf the options, the number of carbon atoms in the C1-C20 alkyl group which may have substituents and the C1-C20 alkoxyl group which may have substituents is preferably 1-10, more preferably 1-6, and even more preferably 1-3, or 1, respectively. R in general formula (6) ａ and R ｂ Of the options, the number of carbon atoms in the cycloalkyl group having 5 to 20 carbon atoms, which may have substituents, and the cycloalkoxyl group having 5 to 20 carbon atoms, which may have substituents, is preferably 5 to 10, more preferably 6 to 8, and even more preferably 6 or 7. In general formula (6), R ａ and R ｂ Among the options, the carbon number of the substituted heteroaryl group having 6 to 20 carbon atoms and the substituted aryloxy group having 6 to 20 carbon atoms, which include one or more heterocyclic atoms selected from O, N, and S, is preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 to 8 or 6, respectively.

[0020] The substituents that may be included in the constituent unit (B) of formula (6) above include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, cycloalkyloxy groups having 5 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups having 5 to 10 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, alkylcarbonyloxy groups having 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups having 5 to 10 carbon atoms, arylcarbonyloxy groups having 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups having 2 to 10 carbon atoms, and glycidyloxycarbonyl groups. The number of carbon atoms in general formula (1) also includes the number of carbon atoms in the substituents.

[0021] Preferred specific examples of monomers that form the above-mentioned constituent unit (B) include, for example, 2,2'-bis(hydroxy(poly)alkoxy)-diaryl-1,1'-binaphthalenes and 2,2'-bis(hydroxy(poly)alkoxy)-dinaphthyl-1,1'-binaphthalenes. 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 monomer compounds described above may be used individually or in combination of two or more to form a constituent unit (B).

[0022] Specific examples of monomer compounds of constituent unit (B) include compounds having the following molecular structures.

[0023] The thermoplastic resin may be a copolymer having both the constituent unit (A) and the constituent unit (B) described above. In such a copolymer thermoplastic resin, the content of constituent unit (B) is, for example, 1 to 99 mol% or 10 to 80 mol%, preferably 20 to 70 mol% or 25 to 60 mol%, and more preferably 30 to 50 mol%, based on the total number of moles of constituent units. Furthermore, as described above, when a thermoplastic resin is made by mixing a homopolymer consisting only of constituent unit (A) and a homopolymer consisting only of constituent unit (B), it is preferable that the proportion of constituent unit (B) is as described above, based on the total number of moles of constituent units contained in the thermoplastic resin mixture.

[0024] 1-4. Constituent Units (C) of Thermoplastic Resins Thermoplastic resins may further contain constituent units (C) derived from diol compounds as monomers represented by general formula (7). In general formula (7), R ｃ and R ｄ Each of these is independently selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, an optionally substituted C5-C20 cycloalkoxyl group, and an optionally substituted C6-C20 aryl group.

[0025] R in general formula (7) ｃ and R ｄ Preferably, each is independently selected from a hydrogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C20 alkoxyl group, an optionally substituted C5-C20 cycloalkyl group, and an optionally substituted C6-C20 aryl group, and more preferably, each is selected from a hydrogen atom, an optionally substituted C1-C20 alkyl group, and an optionally substituted C6-C20 aryl group. ｃ and R ｄ More preferably, it is selected from a hydrogen atom and an aryl group having 6 to 20 carbon atoms, which may have substituents.

[0026] R in general formula (7) ｃ and R ｄ Of the options, the number of carbon atoms in the C1-C20 alkyl group which may have substituents and the C1-C20 alkoxyl group which may have substituents is preferably 1-10, more preferably 1-6, and even more preferably 1-3, or 1, respectively. R in general formula (7) ｃ and R ｄOf the options, the number of carbon atoms in the cycloalkyl group having 5 to 20 carbon atoms, which may have substituents, and the cycloalkoxyl group having 5 to 20 carbon atoms, which may have substituents, is preferably 5 to 10, more preferably 6 to 8, and even more preferably 6 or 7. R in general formula (7) ｃ and R ｄ Of these options, the number of carbon atoms in the aryl group having 6 to 20 carbon atoms, which may have substituents, is preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 to 8, or 6.

[0027] In general formula (7), Y １ is a single bond, a fluorene group which may have substituents, or any of the structural formulas represented by the following formulas (8) to (15), preferably Y １ It is either a single bond or a fluorene group. In equations (8), (14), and (15), R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R ６１ and R ６２ , or R ７１ and R ７２ It represents a carbon ring or heterocycle having 4 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to each other. In formulas (12) and (14), r and s each independently represent an integer from 0 to 5000. Note that Y in formula (7) １ In the above equations (8) to (15) which show the options, R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ The straight lines at both ends that are not bonded to any substituents represent single bonds that are bonded to either of the two benzene rings in formula (7) above.

[0028] R in equations (8), (14), and (15)６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ Among the options of R, R, R, R, R, R, and R, the number of carbon atoms of the optionally substituted alkyl group having 1 to 20 carbon atoms is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3, or 1. R, R, R, R, R, R, and R in formulas (8), (14), and (15) ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ Among the options of R, R, R, R, R, R, and R, the number of carbon atoms of the optionally substituted aryl group having 6 to 30 carbon atoms is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10. R, R, R, R, R, R, and R in formulas (8), (14), and (15) ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ Among the options of R, R, R, R, R, R, and R, the number of carbon atoms of the optionally substituted carbocyclic or heterocyclic ring having 4 to 20 carbon atoms is preferably 5 to 12, more preferably 6 to 10, still more preferably 6 to 8, or 6.

[0029] In general formula (7), A and B each independently represent an optionally substituted alkylene group having 1 to 5 carbon atoms, preferably an optionally substituted alkylene group having 1 to 3 carbon atoms, still more preferably an alkylene group having 2 or 3 carbon atoms, an alkylene group having 1 or 2 carbon atoms, etc. In general formula (7), p and q each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, still more preferably 0 or 1. In general formula (7), a and b each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, still more preferably an integer of 0 to 3, and particularly preferably 0 or 1.

[0030] The substituents that may be included in the constituent unit (C) of formula (7) above include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, cycloalkyloxy groups having 5 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups having 5 to 10 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, alkylcarbonyloxy groups having 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups having 5 to 10 carbon atoms, arylcarbonyloxy groups having 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups having 2 to 10 carbon atoms, and glycidyloxycarbonyl groups. The number of carbon atoms in general formula (7) also includes the number of carbon atoms in the substituents.

[0031] Preferred examples of monomers that form the above-mentioned structural unit (C) include BNEF (9,9-bis(6-(2-hydroxyethoxy)naphthalene-2-yl)fluorene), BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), BCFL (biscresol fluorene), and BPM (bisphenol M). The above-mentioned monomer compounds may be used individually or in combination of two or more to form structural unit (C). Specific examples of monomer compounds for structural unit (C) include compounds having the following molecular structures.

[0032] The thermoplastic resin may be, for example, a copolymer having both the constituent unit (A) and the constituent unit (C) described above. In such a copolymer thermoplastic resin, the content of constituent unit (C) is, for example, 1 to 99 mol% or 10 to 80 mol%, preferably 20 to 70 mol% or 25 to 60 mol%, and more preferably 30 to 50 mol%, based on the total number of moles of constituent units. Furthermore, as described above, when a thermoplastic resin is made by mixing a homopolymer consisting only of constituent unit (A) and a homopolymer consisting only of constituent unit (C), it is preferable that the proportion of constituent unit (C) is as described above, based on the total number of moles of constituent units contained in the thermoplastic resin mixture.

[0033] 1-5. Constituent Units (D) of Thermoplastic Resins Thermoplastic resins may further contain constituent units (D) derived from diol compounds as monomers represented by general formula (2). In general formula (2), Z is H, CH ３ or C ２ H ５ Z represents H or CH, where Z is preferably H or CH. ３ It is H, and more preferably H. In general formula (2), t represents 0 or 1, and preferably 2.

[0034] The monomer compound of formula (2) above may have substituents, and examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, amide groups having 1 to 10 carbon atoms, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, cycloalkyloxy groups having 5 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups having 5 to 10 carbon atoms, aryloxycarbonyl groups having 7 to 15 carbon atoms, alkylcarbonyloxy groups having 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups having 5 to 10 carbon atoms, arylcarbonyloxy groups having 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups having 2 to 10 carbon atoms, and glycidyloxycarbonyl groups.

[0035] As a preferable specific example of the monomer forming the above-described structural unit (D), D-NDM represented by the following formula can be mentioned.

[0036] The thermoplastic resin may be, for example, a copolymer having both the above-described structural unit (A) and structural unit (D). In such a thermoplastic resin which is a copolymer, based on the total number of moles of the structural units, the content of the structural unit (D) is, for example, 1 to 99 mol% or 10 to 95 mol%, preferably 30 to 90 mol% or 50 to 85 mol%, and more preferably 70 to 85 mol% or the like. Also, as described above, when a homopolymer consisting only of the structural unit (A) and homopolymers each consisting only of the structural unit (D) are mixed to form a thermoplastic resin, it is preferable that the ratio of the structural unit (D) is as described above based on the total number of moles of the structural units contained in the thermoplastic resin as a mixture.

[0037] 1-6. Other Structural Units In the thermoplastic resin, structural units other than the above-described structural units (A) to (D) may be included. For example, in the thermoplastic resin, a structural unit derived from a monomer represented by the following formula may be further included. In the above formula, R １ and R ２ each independently represent a hydrogen atom, a methyl group or an ethyl group. R １ and R ２ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In the above formula, R ３ and R ４ each independently represent an aryl group, a hydrogen atom, a methyl group, an ethyl group or an alkylene glycol having 2 to 5 carbon atoms. R ３ and R ４ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In the above formula, i and ii each independently represent an integer of 1 to 3. i and ii are preferably 1 or 2, and more preferably 1.

[0038] In thermoplastic resins, the content of the other constituent units mentioned above, based on the total number of moles of constituent units, is, for example, 1 to 99 mol% or 10 to 80 mol%, preferably 20 to 70 mol% or 25 to 60 mol%, and more preferably 30 to 50 mol%.

[0039] Thermoplastic resins may contain a certain amount of impurities. For example, alcohol compounds such as phenolic compounds that may be produced as by-products during the manufacture of polycarbonate resins, unreacted diol components, or diester carbonates may be present as impurities in thermoplastic resins. However, since alcohol compounds such as phenolic compounds and diester carbonates, which are impurities, can reduce the strength of the thermoplastic resin when it is molded and can cause odor generation, it is preferable to keep their content as low as possible.

[0040] The content of residual phenolic compounds in the thermoplastic resin is preferably 3,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, and particularly preferably 300 ppm by mass or less, based on 100% by mass of the thermoplastic resin. The content of residual diol components is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by mass of the thermoplastic resin. The content of residual diester carbonate is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by mass of the thermoplastic resin. In particular, it is preferable that the content of compounds such as phenol and t-butylphenol be low, and it is preferable that these compounds be within the above ranges.

[0041] The content of phenolic compounds remaining in thermoplastic resins can be measured by analyzing phenolic compounds extracted from the thermoplastic resin using gas chromatography. Similarly, the content of alcoholic compounds remaining in thermoplastic resins can be measured by analyzing alcoholic compounds extracted from the thermoplastic resin using gas chromatography. The content of diol components and diester carbonates remaining in thermoplastic resins can also be measured by extracting these compounds from the thermoplastic resin and analyzing them using gas chromatography.

[0042] The content of by-product alcohol compounds such as phenolic compounds, diol components, and diester carbonates may be reduced to an undetectable level, but from a productivity standpoint, they may be present in small amounts as long as they do not impair the effect. Furthermore, small amounts can improve plasticity during resin melting.

[0043] The content of each of the remaining phenolic compounds, diol components, or diester carbonates may be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more, based on 100% by mass of the thermoplastic resin. The content of the remaining alcoholic compounds may be, for example, 0.01 ppm or more, 0.1 ppm or more, or 1 ppm or more, based on 100% by mass of the thermoplastic resin.

[0044] The content of by-product alcohol compounds such as phenolic compounds, diol components, and diester carbonates in thermoplastic resins can be adjusted to fall within the above range by appropriately adjusting the polycondensation conditions and equipment settings. It can also be adjusted by the conditions of the extrusion process after polycondensation.

[0045] For example, the residual amount of by-product alcohol compounds, such as phenolic compounds, is related to the type of diester carbonate used in the polymerization of thermoplastic resins, as well as the polymerization reaction temperature and polymerization pressure. By adjusting these factors, the residual amount of by-product alcohol compounds, such as phenolic compounds, can be reduced.

[0046] For example, when thermoplastic resins such as polycarbonate are manufactured using dialkyl carbonates such as diethyl carbonate, the molecular weight does not increase easily, resulting in a low molecular weight thermoplastic resin, and the content of by-product alkyl alcohol compounds tends to increase. Such alkyl alcohols are highly volatile, and if they remain in the thermoplastic resin, the moldability of the resin tends to deteriorate. In addition, if a large amount of by-product alcohol compounds such as phenolic compounds remain, there is a possibility of odor problems during resin molding, and a cleavage reaction of the resin skeleton may proceed during compounding, leading to a decrease in molecular weight. Therefore, it is preferable that the content of residual by-product alcohol compounds in the obtained thermoplastic resin is 3000 ppm by mass or less relative to the thermoplastic resin (100% by mass). The content of residual alcohol compounds is preferably 3000 ppm by mass or less, more preferably 1000 ppm by mass or less, and particularly preferably 300 ppm by mass or less, relative to 100% by mass of the thermoplastic resin.

[0047] 2. Thermoplastic Resin Composition The thermoplastic resin described above may be used as a thermoplastic resin composition containing components other than the thermoplastic resin. The thermoplastic resin composition may contain, for example, at least one additive selected from mold release agents, antioxidants, etc. 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. Furthermore, the content of secondary components such as additives other than the thermoplastic resin in the thermoplastic resin composition is, for example, 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more or 1% by weight or more, based on the total weight of the thermoplastic resin composition.

[0048] Specific examples of additives included in thermoplastic resin compositions are as follows:

[0049] Antioxidants Examples of antioxidants include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants.

[0050] 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-ter [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, pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N' -Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphoate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxy Examples include 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, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol.Examples of phenolic antioxidants include "Irganox 1010" (registered trademark, hereinafter the same) and "Irganox 1076" manufactured by BASF, and "Adeka Stab AO-50" and "Adeka Stab AO-60" manufactured by Adeka.

[0051] The amount of antioxidant added is preferably 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, per 100 parts by mass of the thermoplastic resin composition. The antioxidant may contain only one type or two or more types. If two or more types are included, it is preferable that the total amount is within the above range.

[0052] Examples of mold release agents include carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin-based). Specifically, 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 can be mentioned. Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and more preferably aliphatic saturated monovalent 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, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid. The same aliphatic carboxylic acids as those mentioned above can be used as the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid with an alcohol. On the other hand, saturated or unsaturated monohydric or polyhydric alcohols can be used as the alcohol. These alcohols may have substituents such as fluorine atoms or aryl groups. Among these, 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. Here, alicyclic compounds are also included in the term aliphatic. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol.

[0053] The ester compounds described above may contain aliphatic carboxylic acids and / or alcohols as impurities, and may be mixtures of multiple compounds. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly 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. Examples of aliphatic hydrocarbons with a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Here, alicyclic hydrocarbons are also included in aliphatic hydrocarbons. Furthermore, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxided 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 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.

[0054] The proportion of the release agent added 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, per 100 parts by mass of the thermoplastic resin composition. 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.

[0055] Thermoplastic resin compositions may contain deactivators. Deactivators may be used to remove or deactivate polymerization catalysts after the completion of the polymerization reaction for the production of the thermoplastic resin contained in the thermoplastic resin composition, in order to maintain the thermal stability and hydrolysis stability of the resin. Typically, known acidic substances can be used as deactivators. For example, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, organic halides such as stearate chloride, benzoyl chloride, and p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzyl chloride can be used as deactivators.

[0056] The amount of inactivator added 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, and more preferably 1 part by mass or less, per 100 parts by mass of the thermoplastic resin composition. Only one type of inactivator 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.

[0057] 3. Methods for Manufacturing Thermoplastic Resins and Thermoplastic Resin Compositions The following describes methods for manufacturing thermoplastic resins and the like. The thermoplastic resins described above can be manufactured by known methods. For example, thermoplastic resins can be manufactured by carrying out a polymerization reaction in a reaction system containing a monomer compound and a catalyst under conditions of a polymerization temperature of 200 to 250°C and a pressure of 760 mmHg to 200 mmHg. For example, a thermoplastic resin such as polycarbonate resin can be manufactured by melt polycondensation using monomer compounds that form the above-mentioned constituent units such as constituent unit (A) and carbonate precursors such as diester carbonate 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.

[0058] Thermoplastic resin compositions can be produced, for example, by melt-kneading one or more types of thermoplastic resins with the aforementioned secondary components, such as additives. Alternatively, they may be produced by dissolving the thermoplastic resins and additives in a solvent, blending them, and then volatilizing the solvent. Suitable solvents include, for example, halogenated organic solvents and THF. Thermoplastic resin compositions can be produced by a manufacturing method that includes such a mixing step. In the mixing step, additives may be mixed with the thermoplastic resins using known methods.

[0059] 4. Properties of Thermoplastic Resins and Thermoplastic Resin Compositions The preferred properties of thermoplastic resins are as follows. The properties of thermoplastic resin compositions are the same as those of thermoplastic resins.

[0060] 4-1. The refractive index (nD) value of the thermoplastic resin in accordance with JIS B 7071-2:2018 is, for example, 1.500 to 1.630 or 1.520 to 1.630, preferably 1.500 to 1.600, and can be appropriately adjusted depending on the application. A more preferred range of refractive index (nD) for the thermoplastic resin is, for example, 1.505 to 1.590 or 1.505 to 1.585, 1.510 to 1.580 or 1.510 to 1.580, 1.515 to 1.580 or 1.515 to 1.575, 1.520 to 1.575 or 1.520 to 1.570, 1.525 to 1.570 or 1.525 to 1.565, etc.

[0061] The preferred range of refractive index (nD) for thermoplastic resins may be 1.500 or higher, 1.505 or higher, 1.510 or higher, 1.515 or higher, 1.520 or higher, 1.525 or higher, or 1.530 or higher. Furthermore, the refractive index (nD) value for thermoplastic resins may be, for example, 1.650 or lower, 1.6300 or lower, 1.620 or lower, 1.600 or lower, 1.590 or lower, 1.585 or lower, 1.580 or lower, 1.575 or lower, 1.570 or lower, 1.565 or lower, and so on.

[0062] 4-2. Abbe Number (νd) The Abbe number (νd) value of a thermoplastic resin, as measured by the method described below, is, for example, 10 to 60 or 15 to 70. The Abbe number (νd) of a thermoplastic resin is preferably 15 to 65 or 18 to 60, more preferably 18 to 65 or 20 to 60. Also, the value of the Abbe number (νd) is, for example, 25 to 60 or 30 to 60, preferably 40 to 60, more preferably 41 to 59, even more preferably 42 to 58, and particularly preferably 43 to 57. Furthermore, the Abbe number (νd) of a thermoplastic resin may be, for example, 70 or less, 66 or less, 62 or less, 60 or less, 58 or less, or 56 or less. However, the value of the Abbe number (νd) of a thermoplastic resin can be appropriately adjusted depending on the application.

[0063] 4-3. Photoelastic coefficient (Pa －１ The photoelastic coefficient measured by the method described later for thermoplastic resins is, for example, 50 × 10⁻⁶. －１２ ・Pa －１ Preferably 40 x 10 －１２ ・Pa －１ The following or 35 x 10 －１２ ・Pa －１ The following, more preferably 30 × 10 －１２ ・Pa －１ The following or 25 x 10 －１２ ・Pa －１ The following, and more preferably 20 × 10 －１２ ・Pa －１ The following or 15 x 10 －１２ ・Pa －１ The following, and particularly preferably 10 × 10 －１２ ・Pa －１ The following or 8 x 10 －１２ ・Pa －１ The following applies:

[0064] The range of the photoelastic coefficient in thermoplastic resins is preferably 1.0 × 10⁻⁶. －１２ ・Pa －１ The above 10 x 10 －１２ ・Pa －１ Less than or equal to 1.0 x 10 －１２ ・Pa －１ The above 9.0. × 10－１２ ・Pa －１ Less than or equal to, or 1.0 × 10 －１２ ・Pa －１ The above 8.0 x 10 －１２ ・Pa －１ Less than or equal to, more preferably 1.5 × 10 －１２ ・Pa －１ The above 7.5 x 10 －１２ ・Pa －１ The following, and more preferably 1.5 × 10 －１２ ・Pa －１ The above 7.0 x 10 －１２ ・Pa －１ The following applies:

[0065] 4-4. Saturated Water Absorption Rate (%) The saturated water absorption rate (%) of thermoplastic resins, as measured by the method described below, is preferably 4.0% or less or 3.0% or less, more preferably 2.0% or less or 1.0% or less, even more preferably 0.8% or less or 0.6% or less, and particularly preferably 0.5% or less or 0.4% or less. The saturated water absorption rate (%) of thermoplastic resins is, for example, 0.01% or more, preferably 0.03% or more, more preferably 0.05% or more, even more preferably 0.07% or more, and particularly preferably 1.00% or more. The saturated water absorption rate (%) of thermoplastic resins is, for example, 0.05 to 0.50%, preferably 0.07 to 0.48% or 0.10 to 0.48%, and more preferably 0.10 to 0.40% or 0.10 to 0.33%.

[0066] The range of saturated water absorption in thermoplastic resins is, for example, 0.001% to 2.0%, preferably 0.01% to 1.0%, more preferably 0.03% to 0.6%, even more preferably 0.05% to 0.5%, and particularly preferably 0.10% to 0.48%, 0.10% to 0.40%, 0.10% to 0.33%, or 0.15% to 0.30%.

[0067] 4-5. Glass transition temperature (Tg) The glass transition temperature (Tg) value for thermoplastic resins in accordance with JIS K7121-1987 is, for example, 95 to 200°C, preferably 97 to 185°C or 100 to 190°C, more preferably 100 to 180°C or 105 to 185°C, and more preferably 110 to 175°C or 115 to 180°C.

[0068] 4-6. Molecular Weight (Weight-Average Molecular Weight and Number-Average Molecular Weight) The weight-average molecular weight of thermoplastic resins 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. The weight-average molecular weight of thermoplastic resins is measured, for example, as polystyrene-equivalent weight-average molecular weight (Mw) as follows.

[0069] The number-average molecular weight of the thermoplastic resin is preferably 8,000 to 200,000, more preferably 8,000 to 150,000, even more preferably 8,000 to 80,000, for example, more preferably 9,000 to 50,000, even more preferably 12,000 to 40,000, and particularly preferably 15,000 to 30,000.

[0070] 4-7. Total Light Transmittance (TT (%)) The total light transmittance (%) of thermoplastic resins in accordance with JIS K 7361-1:1997 is preferably 60% or more, more preferably 70% or more or 80% or more, more preferably 85% or more or 88% or more, and particularly preferably 90% or more or 92% or more. 4-8. YI Value The YI value of thermoplastic resins in accordance with JIS K 7373:2006 is preferably 20 or less, more preferably 16 or less or 14 or less, more preferably 12 or less, 10 or less, 9.0 or less or 8.0 or less, and particularly preferably 7.0 or less, 6.0 or less or 5.0 or less. In addition, since a smaller YI value is generally preferred for thermoplastic resins, the lower limit is not particularly important, but the range of YI values ​​for thermoplastic resins in accordance with the above standards is, for example, 1 to 15, 3 to 12, 5 to 10, 6 to 7, etc.

[0071] 4-9. Haze The haze value for thermoplastic resins in accordance with JIS K-7136:2000 is preferably 2.0 or less or 1.6 or less, more preferably 1.2 or less or 1.0 or less, more preferably 0.8 or less or 0.6 or less, and particularly preferably 0.4 or less or 0.3 or less. 4-10. Melt Volume Rate (MVR) The MVR value for thermoplastic resins in accordance with JIS K7210 (unit: cm) ３ The MVR (molecular strength / 10 min) is preferably 15 or higher, more preferably 20 or higher, more preferably 25 or higher, and particularly preferably 30 or higher. The range of MVR values ​​for thermoplastic resins conforming to the above standards is, for example, 10 to 50, 20 to 40, 25 to 35, etc. A resin with a high MVR value can be said to have high fluidity.

[0072] 4-11. Density values ​​for thermoplastic resins in accordance with JIS K 7112 are, for example, 1.00 to 1.30 (g / cm³). ３ Preferably, the density of the thermoplastic resin is 1.05 to 1.27 (g / cm³). ３ ) and more preferably 1.07 to 1.25 (g / cm³) ３) and more preferably 1.10 to 1.24 (g / cm³) ３ )

[0073] 5. Optical Lenses (Molded Articles Containing Thermoplastic Resin) The thermoplastic resin of the present invention can be used in extrusion molding, blow molding, injection molding, etc. Products (molded articles) obtained as molded articles by processing the thermoplastic resin include extruded articles, hollow molded articles, precision parts and thin injection molded articles. Specific examples of molded articles using the thermoplastic resin of the present invention as an optical material and containing the thermoplastic resin of the present invention include optical components such as optical lenses, optical films, liquid crystal displays, light guide plates, various films such as optical disc substrates, and housings for electronic devices such as smartphones.

[0074] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

[0075] (Production Example 1: Synthesis of D-NCDM) 1700 g (12.67 mol) of cinnamon alcohol and 433 g (3.27 mol) of dicyclopentadiene were charged into a 3 L stainless steel reactor, and the reaction was carried out at 185°C for 6.5 hours. As a result of the above reaction, a reaction solution containing 178 g of the compound represented by the following formula (3a) was obtained, and this was purified by distillation. This operation was repeated several times to obtain 774 g of the compound represented by the following formula (3a).

[0076] Using a 3L stainless steel reactor, CO and H ２ CO / H mixed ２ Gas (CO / H ２ Using a molar ratio of 1), the hydroformylation reaction of the compound represented by the following formula (3a), which was purified by distillation, was carried out as follows: 774 g of the compound represented by the following formula (3a), 774 g of 2-octanol, 2.70 g of triphenyl phosphite, and separately prepared Rh(acac)(CO) were added to the reactor. ２ One mL of 2-octanol solution (concentration 0.009 mol / L) was added. Nitrogen and CO / H ２ After performing gas substitution three times each, CO / H ２The system was pressurized with gas, and the reaction was carried out at 125°C and 2 MPa for 6 hours. After the reaction was complete, gas chromatography analysis of the reaction solution was performed, and it was confirmed that the reaction solution contained 766 g of the compound represented by formula (2a) (conversion rate > 99%, selectivity 89%). Subsequently, a portion was used in the following reaction.

[0077] 1400 g of the above reaction solution (including 700 g of the compound represented by formula (2a) below) and 20 g of sponge nickel catalyst (manufactured by Nikko Rica Co., Ltd.: R-200M) were added to a 3 L stainless steel reactor. The system was then pressurized with hydrogen gas and the reaction was carried out at 2 MPa and 120°C for 12 hours. After the reaction, the obtained slurry was filtered through a membrane filter with a pore size of 0.45 μm to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed that it contained 662 g of the compound represented by formula (1'a) below with a molecular weight of 298 (main product yield 95%).

[0078] Further, 450 g of this mixture (including 215 g of the compound represented by formula (1'a) below) and 92 g of Ru / Al catalyst (manufactured by N.E. Chemcat Co., Ltd.) were added to a 1 L stainless steel reactor. The system was then pressurized with hydrogen gas, and the reaction was carried out at 5 MPa and 130°C for 5.5 hours. After the reaction, the resulting slurry was filtered through a 0.45 μm pore size membrane filter to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed the presence of 202 g of the main product with a molecular weight of 304 represented by formula (1a) (main product yield 92%). This was further purified by distillation to obtain the main product (D-NCDM).

[0079]

[0080] (Production Example 2: Synthesis of D-NPDM) The compound represented by formula (1'a) in quantity 298 obtained as an intermediate in the reaction of Production Example 1 above was further purified by distillation to obtain the main product (D-NPDM).

[0081] (Production Example 3: Synthesis of NCDM) 1700 g (12.67 mol) of cinnamon alcohol and 433 g (3.27 mol) of dicyclopentadiene were charged into a 3 L stainless steel reactor, and the reaction was carried out at 185°C for 6.5 hours. From the above reaction, a reaction solution containing 603 g of monoolefin represented by the following formula (3b) was obtained, and this was purified by distillation. This operation was repeated several times to obtain 641 g of the compound represented by the following formula (3b).

[0082] Using a 3L stainless steel reactor, CO and H ２ CO / H mixed ２ Gas (CO / H ２ Using a molar ratio of 1), the hydroformylation reaction of the compound represented by the following formula (3b), which was purified by distillation, was carried out as follows: 641 g of the compound represented by formula (3b), 455 g of 2-octanol, 1.50 g of triphenyl phosphite, and separately prepared Rh(acac)(CO) were placed in the reactor. ２ 1.2 mL of 2-octanol solution (concentration 0.008 mol / L) was added. Nitrogen and CO / H ２ After performing gas substitution three times each, CO / H ２ The system was pressurized with gas, and the reaction was carried out at 120°C and 2 MPa for 6 hours. After the reaction was complete, gas chromatography analysis of the reaction solution was performed, and it was confirmed that the reaction solution contained 669 g of the compound represented by the following formula (2b) (conversion rate > 99%, selectivity 91%). Subsequently, a portion was used in the following reaction.

[0083] 1400 g of the above reaction solution (including 669 g of the compound represented by formula (2b) below) and 16 g of sponge nickel catalyst (manufactured by Nikko Rica Co., Ltd.: R-200M) were added to a 3 L stainless steel reactor. The system was then pressurized with hydrogen gas and the reaction was carried out at 2 MPa and 105°C for 7 hours. After the reaction, the obtained slurry was filtered through a membrane filter with a pore size of 0.45 μm to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed that it contained 679 g of the compound represented by formula (1'b) with a molecular weight of 232 (main product yield 92%).

[0084] Further, 690 g of this mixture (including 363 g of the compound represented by formula (1'b) below) and 19 g of nickel diatomaceous earth catalyst (manufactured by Nikkei Catalysis Chemicals Co., Ltd.) were added to a 1 L stainless steel reactor. The system was then pressurized with hydrogen gas, and the reaction was carried out at 5 MPa and 200°C for 8 hours. After the reaction, the resulting slurry was filtered through a membrane filter with a pore size of 0.45 μm to remove the catalyst. Analysis by gas chromatography and GC-MS confirmed that it contained 262 g of the main product with a molecular weight of 238 represented by formula (1b) (main product yield 92%). This was further purified by distillation to obtain the main product (NCDM).

[0085]

[0086] (Production Example 4: Synthesis of NPDM) The compound represented by formula (1'b) in quantity 238 obtained as an intermediate in the reaction of Production Example 3 above was further purified by distillation to obtain the main product (NPDM).

[0087] (Example 1) The raw materials obtained in Production Example 1 described above consisted of D-NCDM as a bifunctional compound: 272.90 g (0.896 mol), DPC: 195.85 g (0.914 mol), and sodium bicarbonate as a catalyst: 0.8 mg (9.0 × 10⁻¹⁴) －６ The raw materials were placed in a 500 mL reactor equipped with a stirrer and distillation device, and dissolved under a nitrogen atmosphere of 101.3 kPa at a heat transfer temperature of 200°C for 20 minutes while stirring. Then, the heat transfer temperature was increased to 240°C over 1 hour while the system pressure was reduced to 17.3 kPa, and the generated phenol was removed from the reaction system. Then, the system pressure was reduced to 0.2 kPa or less over 30 minutes, and the generated phenol was removed from the reaction system. After that, the reaction system was maintained at 0.2 kPa or less for 30 minutes to obtain polycarbonate resin. The physical properties of the obtained resin are shown in Table 1.

[0088] (Examples 2-12, Comparative Examples 1-6) Polycarbonate resins were obtained in the same manner as in Example 1, except that the raw materials were changed as shown in Table 1. For example, in Example 2, D-NPDM obtained in Production Example 2 was used as the raw material instead of D-NCDM used in Example 1. In Example 5, NCDM obtained in Production Example 3 was used as the raw material, and in Example 6, NPDM obtained in Production Example 4 was used as the raw material. In Examples 7 and 8, D-NCDM used in Example 1 and NCDM used in Example 5 were used as raw materials. The physical properties of the obtained resins are shown in Tables 1 and 2 below. In Tables 1 and 2, "-" in the "Resin Composition" column indicates that the component is not contained in the resin, and "-" in the "Physical Property Value" column indicates that the physical property value could not be measured.

[0089] The molecular structures and abbreviations of the monomer compounds used in the above-described examples are as follows:

[0090] <Analysis Method> The methods for measuring the properties of the resins in the above-mentioned examples and comparative examples are as follows: 1) Weight-average molecular weight (Mw) and number-average molecular weight (Mn) The weight-average molecular weight and number-average molecular weight of the obtained resins were measured by gel permeation chromatography (GPC) and calculated on a standard polystyrene basis. The equipment, column, and measurement conditions used are as follows. • GPC instrument: Tosoh Corporation, HLC-8420GPC • Columns: Tosoh Corporation, TSKgel SuperHM-M x 3, Tosoh Corporation, TSKgel guardcolumn SuperH-H x 1, Tosoh Corporation, TSKgel SuperH-RC x 1 • Detector: RI detector • Standard polystyrene: Tosoh Corporation, Standard polystyrene kit PStQuick C • Sample solution: 0.2% by mass tetrahydrofuran solution • Eluent: Tetrahydrofuran • Eluent flow rate: 0.6 mL / min • Column temperature: 40°C

[0091] 2) Glass transition temperature (Tg) Measured using a differential thermal scanning calorimetry analyzer based on JIS K7121-1987 with a heating program of 10°C / min. Differential thermal scanning calorimetry analyzer: TA Instruments DSC2500 3) Refractive index (nD) A V-block was obtained by molding polycarbonate resin based on JIS B 7071-2:2018 and used as a test specimen. The refractive index was measured at 23°C using a refractometer (Shimadzu KPR-3000). 4) Abbe number (ν) Using the same test specimen (V-block) as 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 refractometer, and the Abbe number was calculated using the following formula. Refractometer: Shimadzu KPR-3000 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

[0092] 5) Photoelastic coefficient The obtained resin was dissolved in dichloromethane to obtain a resin solution. This resin solution was spread on a tray, the solvent was evaporated, and a film with a thickness of 0.1 mm was obtained and used as a sample piece. The photoelastic coefficient was measured using an ellipsometer. Measurement method: The photoelastic coefficient was calculated by measuring the change in birefringence in response to a change in load at a wavelength of 633 nm. Ellipsometer: Ellipsometer M-220 manufactured by JASCO Corporation 6) Saturated water absorption The obtained resin was press-molded into a disc with a diameter of 40 mm and a thickness of 3 mm (molding conditions: Tg + 50°C, 100 kgf / cm2, 5 min) to obtain a test sample. The saturated water absorption was measured using this sample in accordance with JIS-K-7209.

[0093] 7) Density The density of the obtained resin was measured using the test specimen prepared in 3) above, in accordance with JIS K7112, using an electronic hydrometer (SD-200L manufactured by Alpha Mirage).

[0094] As illustrated by the results of the above-described examples and comparative examples, the thermoplastic resin composition of this embodiment has a low photoelastic coefficient and saturation water absorption rate, and exhibits particularly excellent physical properties in these areas. Furthermore, the thermoplastic resin of this embodiment, which also has excellent other properties, can be particularly suitably used in optical applications. For example, comparing the results of the polycarbonate resins of Examples 9 to 11, which contain BPEF-derived constituent units (C), with the results of the polycarbonate resins of Comparative Examples 6, 4, and 3, which contain approximately the same amount of BPEF-derived constituent units (C) as in these examples, it can be seen that Examples 9 to 11 achieve lower saturation water absorption rates (%) than the comparative examples (see Table 2 and Figure 4).

Claims

1. A thermoplastic resin containing a constituent unit (A) derived from a bifunctional compound represented by the following general formula (1). In general formula (1), W represents a phenyl group or a cyclohexyl group, and n represents 0 or 1.

2. The thermoplastic resin according to claim 1, wherein the general formula (1) is the following formula (1-1) or formula (1-2).

3. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is a polycarbonate resin, a polyester carbonate resin, or a polyester resin.

4. The thermoplastic resin according to claim 1, wherein the proportion of the constituent unit (A) in all constituent units is 1 to 100 mol%.

5. The thermoplastic resin according to claim 1, further comprising a structural unit (B) derived from a monomer represented by the following general formula (6) and / or a structural unit (C) derived from a monomer represented by the following general formula (7). (In general formula (6), R ａ and R ｂ are each independently 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 may have a substituent and contains one or more hetero ring atoms selected from O, N and S, 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 may have a substituent and contains one or more hetero ring atoms selected from O, N and S, X represents a single bond or 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, m and n each independently represent an integer of 0 to 6, a and b each independently represent an integer of 0 to 10.) (In general formula (7), 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, Y １ is a single bond, a fluorene group which may have a substituent, or any one of the structural formulas represented by the following formulas (8) to (15), (In formulas (8) to (15), R ６１ , R ６２ , R ７１ , R ７２ , R ８１ and R ８２ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents, or R ６１ and R ６２ , or R ７１ and R ７２ (These represent a carbon ring or heterocycle having 4 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms. r and s each independently represent an integer from 0 to 5000.) A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have substituents. p and q each independently represent an integer from 0 to 4. a and b each independently represent an integer from 0 to 10.) 6. The thermoplastic resin according to claim 5, wherein in general formulas (6) and (7), A and B each independently represent an alkylene group having 2 or 3 carbon atoms.

7. The thermoplastic resin according to claim 5, wherein the proportion of constituent unit (B) in all constituent units is 1 to 99 mol%, and the proportion of constituent unit (C) is 1 to 99 mol%.

8. The thermoplastic resin according to claim 5, wherein the thermoplastic resin comprises at least one constituent unit derived from BPEF, BNE, BNEF, DPBHBNA, BPM, and BCFL.

9. The thermoplastic resin according to claim 1, wherein the thermoplastic resin further comprises a monomer-derived constituent unit (D) represented by the following general formula (2). In general formula (2), Z is H, CH ３ or C ２ H ５ This represents , where t represents 0 or 1.

10. The thermoplastic resin according to claim 9, wherein the proportion of the constituent unit (D) in all constituent units is 1 to 99 mol%.

11. The thermoplastic resin according to claim 1, wherein the thermoplastic resin further comprises a constituent unit derived from at least one monomer selected from the group of monomers described below. (In the above formula, R １ and R ２ Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ３ and R ４ Each of these independently represents an aryl group, a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. i and ii each independently represent an integer from 1 to 3.

12. The thermoplastic resin according to claim 1, wherein the weight-average molecular weight (Mw) of the thermoplastic resin on a polystyrene basis is 10,000 to 100,000.

13. The thermoplastic resin according to claim 1, wherein the refractive index (nD) of the thermoplastic resin is 1.500 to 1.

630.

14. The thermoplastic resin according to claim 1, wherein the Abbe number (ν) of the thermoplastic resin is 20.0 to 60.

0.

15. The thermoplastic resin according to claim 1, wherein the glass transition temperature of the thermoplastic resin is 95 to 200°C.

16. The photoelastic coefficient of the thermoplastic resin is 1.0 × 10 －１２ ・Pa －１ 50 x 10 －１２ ・Pa －１ The thermoplastic resin according to claim 1, which is as follows:

17. The thermoplastic resin according to claim 1, wherein the saturated water absorption rate is 0.10 to 0.48%.

18. The density of the thermoplastic resin is 1.00 to 1.30 (g / cm³) ３ The thermoplastic resin according to claim 1, wherein the resin is as described in claim 1.

19. An optical lens comprising the thermoplastic resin described in claim 1.

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