Resin obtained from cyclic diol compound, and optical lens containing same

Abstract

The present invention can provide a resin that contains a constitutional unit (A) derived from a monomer represented by general formula (1) and that is a polycarbonate resin or a polyester carbonate resin. [Compound 1] [In the formula, each R1 is independently a hydrogen atom, a C1-4 alkyl group, or a phenyl group.　X is a direct bond or a divalent group that is represented by formula (Y). [Compound 2] [In the formula, each R2 and each R3 is independently a hydrogen atom, an alkyl group, or an aryl group, or each R2 and each R3 may bind to one another to form a ring together with an adjacent carbon atom, and the ring may be substituted by an alkyl group. n is 0 or 1. * represents a binding position.]]

Description

Resin obtained from cyclic diol compound and optical lens containing same

[0001] The present invention relates to a resin obtained from a cyclic diol compound and an optical lens containing the same.

[0002] Various cyclic diol compounds are known as resin raw materials for polyester resins and polycarbonate resins. Industrially available cyclic diol compounds include 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, and 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A). In addition to these, various other cyclic diol compounds have been reported depending on the intended use of the resin to be produced.

[0003] For example, with regard to polycarbonate resins used in optical applications (e.g., optical lenses), a method for producing the resin using a diol component containing a specific aromatic diol compound having a fluorene ring structure has been reported for the purpose of reducing coloration and improving the optical properties of the resin, such as transparency (Patent Document 1). Also, a method for producing the resin using a specific fluorene-containing dihydroxy compound and another dihydroxy compound in a specific ratio has been reported (Patent Document 2).

[0004] However, the properties of resins such as polyester resins and polycarbonate resins vary widely depending on the various application fields in which the resins are used, and a search is underway for cyclic diol compounds that can satisfy the resin properties required in those fields. In particular, when resins are used for optical applications, a cyclic diol compound that can improve the optical properties of the resins is required.

[0005] Patent Document 3 describes a diol compound having a diacetal structure (dispiro structure) of 1,4-cyclohexanedione. Patent Documents 4 and 5 describe that a diol compound having a dispiro structure can be used as a resin raw material, but do not describe that it can be used as a resin raw material for polycarbonate resin or polyester carbonate resin.

[0006] JP 2012-214803 A JP 2013-001867 A International Publication No. 2018 / 074305 JP 2021-134151 A JP 2019-014711 A

[0007] An object of the present invention is to provide a resin that has excellent heat resistance and optical properties such as refractive index and Abbe number, and an optical lens containing the resin.

[0008] The present inventors conducted extensive research to solve the above problems and found that by using a cyclic diol compound having a diacetal structure represented by general formula (1), it is possible to provide a resin that has excellent heat resistance, excellent optical properties such as refractive index and Abbe number, and also excellent partial dispersion ratio (θgF) and anomalous partial dispersion (ΔθgF), as well as an optical lens containing the same, and thus completed the present invention. That is, the present invention is as follows: <1> A resin containing a structural unit (A) derived from a monomer represented by the following general formula (1), the resin being a polycarbonate resin or a polyester carbonate resin: [In the formula, R １ are the same or different and are a hydrogen atom, a C1-4 alkyl group, or a phenyl group. X is a direct bond (single bond) or a divalent group represented by formula (Y). [In the formula, R ２ and R ３ are the same or different and are a hydrogen atom, an alkyl group, or an aryl group, or R ２ and R ３ may be bonded to each other to form a ring together with adjacent carbon atoms, and the ring may be substituted with an alkyl group. n is 0 or 1. * indicates the bonding position. ]] <2> In the divalent group represented by formula (Y), when n is 0, R ２ and R ３ are the same or different and are a hydrogen atom, a C1-6 alkyl group, or a phenyl group, or R ２ and R ３ may be bonded to each other to form a 5- to 12-membered ring together with adjacent carbon atoms, and the ring may be substituted with a C1-3 alkyl group; when n is 1, R ２ and R ３and R are the same or different and are a hydrogen atom or a C1-6 alkyl group. ２ and R ３ are the same or different and are a hydrogen atom, a C1-6 alkyl group, or a phenyl group, or R ２ and R ３ may be bonded to each other to form a 5- to 12-membered ring together with adjacent carbon atoms, and the ring may be substituted with a C1-3 alkyl group. １ are the same or different and are a hydrogen atom, a methyl group, or an ethyl group, and in the divalent group represented by formula (Y), n is 0 and R ２ and R ３ and R are the same or different and represent a hydrogen atom or a C1-4 alkyl group. １ are the same or different and are a hydrogen atom, a methyl group, or an ethyl group, and X is a direct bond (single bond). <6> The resin according to any one of <1> to <5> above, wherein the resin contains 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 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ R is selected from the group consisting of ｈrepresents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent; X represents a single bond or an optionally substituted fluorene group; A and B each independently represent an optionally substituted alkylene group having 1 to 5 carbon atoms; m and n each independently represent an integer of 0 to 6; and a and b each independently represent an integer of 0 to 10. (In general 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; １ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulae (8) to (14): (In formulas (8) to (14), R ６１ , R ６２ , R ７１ and R ７２ 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 ７２represent a carbon ring or hetero ring having 1 to 20 carbon atoms, which may have a substituent, formed by bonding together, and r and s each independently represent an integer of 0 to 5,000.) 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.) <7> The resin according to any one of <1> to <6> above, excluding a resin consisting of (consisting only of) a structural unit (A) derived from a monomer represented by general formula (1) and a structural unit derived from BPEF. <8> A resin containing a structural unit (A) derived from a monomer represented by the following general formula (1A): [In the formula, R １１ are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group. Ａ is a direct bond (single bond) or a divalent group represented by formula (Y1). [In the formula, R ２１ and R ３１ one of which is a hydrogen atom and the other is a hydrogen atom or a methyl group, or R ２１ and R ３１may be bonded to each other to form a 6-membered ring together with adjacent carbon atoms, and the ring may be substituted with 1 to 3 methyl groups. * indicates the bonding position. ]] <9> The resin according to <8> above, wherein the resin is a polycarbonate resin, a polyester carbonate resin, or a polyester resin. <10> The resin according to any one of <1> to <9> above, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the resin is 10,000 to 100,000. <11> The resin according to any one of <1> to <10> above, wherein the refractive index (nD) of the resin is 1.500 to 1.650. <12> The resin according to any one of <1> to <11> above, wherein the Abbe number (ν) of the resin is 24.0 to 40.0. <13> The resin according to any one of <1> to <12> above, wherein the glass transition temperature of the resin is 145 to 170°C. <14> The resin according to any one of <1> to <13> above, wherein the resin has a partial dispersion ratio (θgF) of 0.621 to 0.700. <15> The resin according to any one of <1> to <14> above, wherein the resin has an anomalous partial dispersion (ΔθgF) of 0.025 to 0.100. <16> An optical lens comprising the resin according to any one of <1> to <15> above.

[0009] According to the present invention, it is possible to provide a resin that has excellent heat resistance, excellent optical properties such as refractive index and Abbe number, and further excellent partial dispersion ratio (θgF) and anomalous partial dispersion (ΔθgF), and an optical lens containing the same.

[0010] 1 is an IR spectrum of Compound 1 obtained in Production Example 1. １ 1 H-NMR spectrum.

[0011] Hereinafter, the present invention will be described in detail by way of examples and synthesis examples. However, the present invention is not limited to the synthesis examples and examples exemplified, and can be carried out by any method as long as it does not significantly deviate from the content of the present invention.

[0012] <Resin> One embodiment of the present invention is a resin that includes a structural unit (A) derived from a monomer represented by the following general formula (1), and the resin is a polycarbonate resin or a polyester carbonate resin. [In the formula, R １ are the same or different and are a hydrogen atom, a C1-4 alkyl group, or a phenyl group. X is a direct bond (single bond) or a divalent group represented by formula (Y). [In the formula, R ２ and R ３ are the same or different and are a hydrogen atom, an alkyl group, or an aryl group, or R ２ and R ３ may be bonded to each other to form a ring together with adjacent carbon atoms, and the ring may be substituted with an alkyl group. n is 0 or 1. * indicates the bonding position.

[0013] R １ are preferably the same or different and each is a C1-4 linear or branched alkyl group or a phenyl group. １ Examples of the C1-4 linear or branched alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group, an ethyl group, an isobutyl group, or a tert-butyl group is preferred. A methyl group or an ethyl group is more preferred. A methyl group is particularly preferred.

[0014] R ２ and R ３ Examples of the alkyl group represented by the formula (I) include a C1-12 alkyl group, a C1-6 alkyl group, and particularly a C1-4 linear or branched alkyl group. Examples of the C1-4 linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group, an ethyl group, an isobutyl group, or a tert-butyl group is preferred. A methyl group or an ethyl group is more preferred. A methyl group is particularly preferred.

[0015] R ２ and R ３ Examples of the aryl group represented by the formula (I) include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

[0016] R ２ and R ３ When these bond to each other to form a ring together with adjacent carbon atoms, examples of the ring include a 3- to 12-membered ring (e.g., a 3- to 12-membered cycloalkane), preferably a 6- to 12-membered ring (e.g., a 6- to 12-membered cycloalkane). Specific examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane. The ring may be substituted with 1 to 6 (preferably 1 to 3) alkyl groups. Examples of the alkyl groups include C1-4 (particularly C1-3) linear or branched alkyl groups, preferably methyl or ethyl groups. When there are multiple alkyl groups, they may be the same or different.

[0017] n is preferably 0. Specifically, the divalent group represented by formula (Y) is preferably a divalent group represented by formula (Y1). [In the formula, R ２１ and R ３１ one of which is a hydrogen atom and the other is a hydrogen atom or a methyl group, or R ２１ and R ３１ may be bonded to each other to form a 6-membered ring together with adjacent carbon atoms, and the ring may be substituted with 1 to 3 methyl groups. * indicates the bonding position.]

[0018] Examples of the divalent group represented by formula (Y) include divalent groups represented by the following formulas (Ya) to (Yc), of which the divalent group represented by formula (Yb) is preferred. [In the formula, R ２ , R ３ , n and * are the same as above.]

[0019] Among the compounds represented by general formula (1), preferred examples include those in which, in the divalent group represented by formula (Y), when n is 0, R ２and R ３ are the same or different and are a hydrogen atom, a C1-6 alkyl group, or a phenyl group, or R ２ and R ３ may be bonded to each other to form a 5- to 12-membered ring together with adjacent carbon atoms, and the ring may be substituted with a C1-3 alkyl group; when n is 1, R ２ and R ３ are the same or different and are a hydrogen atom or a C1-6 alkyl group.

[0020] Among the compounds represented by general formula (1), another preferred example is a compound represented by formula (Y) in which n is 0 and R ２ and R ３ are the same or different and are a hydrogen atom, a C1-6 alkyl group, or a phenyl group, or R ２ and R ３ may be bonded to each other to form a 5- to 12-membered ring together with adjacent carbon atoms, and the ring may be substituted with a C1-3 alkyl group.

[0021] Among the compounds represented by general formula (1), other preferred examples include compounds represented by R １ are the same or different and are a hydrogen atom, a methyl group, or an ethyl group; in the divalent group represented by formula (Y), n is 0; and R ２ and R ３ are the same or different and are a hydrogen atom or a C1-4 alkyl group.

[0022] Among the compounds represented by general formula (1), other preferred examples include compounds represented by R １ are the same or different and are a hydrogen atom, a methyl group, or an ethyl group, and X is a direct bond (single bond).

[0023] Among the compounds represented by general formula (1), another preferred example is a compound represented by general formula (1A). [In the formula, R １１ are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group. Ａ is a direct bond (single bond) or a divalent group represented by formula (Y1). [In the formula, R ２１ and R ３１ one of which is a hydrogen atom and the other is a hydrogen atom or a methyl group, or R ２１ and R ３１ may be bonded to each other to form a 6-membered ring together with adjacent carbon atoms, and the ring may be substituted with 1 to 3 methyl groups. * indicates the bonding position.

[0024] R １１ are the same or different and are preferably a methyl group or an ethyl group.

[0025] Specific examples of the compound represented by general formula (1) include the following compounds (1a) to (1g). Among these, specific examples of the compound represented by formula (1A) include (1a) to (1d) and (1g).

[0026] The resin of the present invention refers to a resin having a repeating unit (structural unit) derived from a cyclic diol compound represented by general formula (1) (including a cyclic diol compound represented by general formula (1A); the same applies hereinafter.) In other words, it refers to a resin containing a divalent repeating unit obtained by removing a hydrogen atom from a hydroxyl group of a cyclic diol compound represented by general formula (1).

[0027] The method for producing the compound (monomer) represented by general formula (1) is not particularly limited, and for example, as shown in the following <Reaction Scheme 1>, the compound (monomer) can be produced via a step of reacting a compound represented by general formula (3) with a compound represented by general formula (4) (acetalization reaction). [In the formula, R １ and X are as defined above.] Specifically, the compound represented by general formula (1) can be produced by reacting a compound represented by general formula (3) with a compound represented by general formula (4) in the presence of an acid catalyst (acetalization reaction).

[0028] The reaction can usually be carried out in a solvent (e.g., toluene, etc.). The solvent can be heated to reflux and the resulting water can be removed azeotropically with the solvent while the reaction proceeds. The acidic catalyst is not particularly limited as long as it has catalytic activity, and known acidic catalysts can be used. Examples include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; solid acids such as cation exchange resins, zeolites, silica alumina, and heteropolyacids (e.g., phosphotungstic acid, phosphomolybdic acid, etc.); and various Lewis acids. The amount of the compound represented by general formula (4) used is usually about 0.5 to 3 moles, preferably about 0.8 to 2 moles, per mole of the compound represented by general formula (3).

[0029] The compound represented by general formula (1A), which is included in the compound represented by general formula (1), can also be produced in the same manner as in <Reaction Scheme 1>. Specifically, it is as shown in the following <Reaction Scheme 2>. [In the formula, R １１ and X Ａ is the same as above.]

[0030] The compound represented by general formula (1) (cyclic diol compound) can be used as a raw material monomer for producing a resin, and can be (co)polymerized alone or in combination with other monomers to produce a resin containing a structural unit represented by general formula (2) (structural unit (A)). [In the formula, R １ and X is the same as above.]

[0031] The resin containing the structural unit (A) derived from the monomer represented by general formula (1) is preferably a thermoplastic resin, more preferably a polycarbonate resin, a polyester carbonate resin, or a polyester resin, still more preferably a polycarbonate resin or a polyester carbonate resin, and particularly preferably a polycarbonate resin.

[0032] In general formula (2), R １ Specific and preferred examples of X are the same as those of R １The specific and preferred examples of X are the same as those of X.

[0033] A polycarbonate resin containing a structural unit represented by general formula (2) (structural unit (A)) can be produced by (polymerizing) a raw material monomer containing a compound represented by general formula (1) with a carbonyl precursor compound.

[0034] The compound represented by general formula (1) can be used alone as a raw material monomer for a polycarbonate resin. The resulting polycarbonate resin is a homopolymer obtained by polymerizing only the compound represented by general formula (1) with a carbonyl precursor compound, and is composed only of structural units represented by general formula (2).

[0035] The raw material monomers for polycarbonate resins may contain, in addition to the compound represented by general formula (1), a dihydroxy compound that is generally used as a structural unit of polycarbonate resins. Examples of the dihydroxy compound include aliphatic dihydroxy compounds and aromatic dihydroxy compounds.

[0036] That is, the polycarbonate resin may be a copolymer containing a structural unit derived from a general dihydroxy compound in addition to the structural unit represented by general formula (2) derived from the compound represented by general formula (1). A copolymer having multiple types of structural units may be either a block copolymer or a random copolymer.

[0037] Examples of aliphatic dihydroxy compounds include various compounds, particularly 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 1,3-adamantanedimethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-(5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol.

[0038] Examples of aromatic dihydroxy compounds include various compounds, particularly 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bisphenoxyethanolfluorene, etc. Other examples include hydroquinone, resorcinol, and catechol.

[0039] The proportion of the compound represented by general formula (1) in the raw material monomers used is not particularly limited and is, for example, 1 mol % or more, preferably 1 to 80 mol %, more preferably 5 to 70 mol %, even more preferably 15 to 65 mol %, and particularly preferably 25 to 65 mol % of the total amount of monomers. In other words, in the polycarbonate resin, the proportion of the structural units represented by general formula (2) derived from the compound represented by general formula (1) is not particularly limited and is, for example, 1 mol % or more, preferably 1 to 80 mol %, more preferably 5 to 70 mol %, even more preferably 15 to 65 mol %, and particularly preferably 25 to 65 mol % of the total structural units.

[0040] Examples of carbonyl precursor compounds include phosgene, triphosgene, and diphenyl carbonate.

[0041] Furthermore, the resin according to one embodiment of the present invention preferably contains a structural unit (B) derived from a monomer represented by the following general formula (6). In general formula (6), R ａ and R ｂeach independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ R ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent. ａ and R ｂ is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0042] In general formula (6), X represents a single bond or a fluorene group which may have a substituent. X is preferably a single bond or a fluorene group which may have a substituent and has a total of 12 to 20 carbon atoms. In general formula (6), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 2 or 3 carbon atoms. In general formula (6), m and n each independently represent an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1. In general formula (6), a and b each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0043] Specific examples of the structural unit (B) include those derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), DPBHBNA, and the like.

[0044] Furthermore, the resin according to one embodiment of the present invention preferably contains a structural unit (C) derived from a monomer represented by the following general formula (7). In general formula (7), R ｃ and R ｄ are each independently selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent. ｃ and R ｄ is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0045] In the general formula (7), Y １ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulas (8) to (14), and is preferably a single bond or the structural formula represented by the following formula (8): In formulas (8) to (14), R ６１ , R ６２ , R ７１ and R ７２ 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 ７２are bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms, which may have a substituent. In formulas (8) to (14), r and s each independently represent an integer of 0 to 5,000. r is preferably an integer of 1 to 20, and more preferably an integer of 1 to 9. s is preferably an integer of 1 to 5,000, and more preferably an integer of 1 to 500.

[0046] In the general formula (7), A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms. In the general formula (7), p and q each independently represent an integer of 0 to 4, and preferably 0 or 1. In the general formula (7), a and b each independently represent an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2, for example, 0 or 1.

[0047] Specific examples of the structural unit (C) include BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1-phenylethylidene)bisphenol), bisphenol P-CDE (4,4'-cyclododecylidenebisphenol), bisphenol Bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol), bisphenol P-MIBK (4,4'-(1,3-dimethylbutylidene)bisphenol), bisphenol PEO-FL (bisphenoxyethanolfluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol OC-FL (4,4'-[1-[ Examples of structural unit (C) include those derived from BPEF (4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)bisethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol), TrisP-HAP (4,4',4''-ethylidene trisphenol), etc. Among these, preferred structural unit (C) is one derived from BPEF or BNEF.

[0048] A resin according to one embodiment of the present invention essentially contains the structural unit (A), but may also be a polymer containing the structural unit (B) but not the structural unit (C), a polymer containing the structural unit (C) but not the structural unit (B), a copolymer containing the structural unit (B) and the structural unit (C), a mixture of a polymer containing the structural unit (B) and a polymer containing the structural unit (C), or a combination thereof. Examples of polymers containing the structural unit (C) but not the structural unit (B) include those having structural units represented by the following formulas (I-1) to (I-3), and examples of copolymers having the structural unit (B) and the structural unit (C) include those having structural units represented by the following formulas (II-1) to (II-4). (In formula (I-1), m and n each represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1; the number of repeating units in formula (I-3) is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.) Furthermore, as the polymer having multiple types of structural units, either a block copolymer in which the values ​​of m and n are large, for example, 100 or more, or a random copolymer can be used, but a random copolymer is preferred, and more preferably a random copolymer in which the values ​​of m and n are 1 is used. (In formulas (II-1) to (II-4), m and n each independently represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.) Furthermore, as the polymer having multiple types of structural units, either a block copolymer in which the values ​​of m and n are large, for example, 100 or greater, or a random copolymer can be used, although a random copolymer is preferred, and more preferably a random copolymer in which the values ​​of m and n are 1. In the copolymer, the molar ratio of structural unit (B) to structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30. Furthermore, in the mixture, the mass ratio of the polymer having the structural unit (B) to the polymer having the structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.

[0049] The resin according to one embodiment of the present invention preferably further contains a structural unit derived from at least one monomer selected from the group of monomers below. (In the above formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４ each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms.

[0050] In a preferred embodiment of the polycarbonate resin of the present invention, impurities such as alcohol compounds such as phenolic compounds that may be generated as by-products during production, and diol components or carbonate diesters that remain unreacted may be present. The impurities, such as alcohol compounds such as phenolic compounds and carbonate diesters, may cause a decrease in strength or the generation of odor when molded into a product, so it is preferable that the content of these impurities is as small as possible.

[0051] The content of residual phenolic compounds 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 polycarbonate 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 polycarbonate resin. The content of residual carbonate diesters 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 polycarbonate resin. In particular, it is preferable that the contents of compounds such as phenol and t-butylphenol are low, and it is preferable that the contents of these compounds are within the above ranges.

[0052] The content of phenolic compounds remaining in the polycarbonate resin can be measured by a method of analyzing phenolic compounds extracted from the polycarbonate resin using gas chromatography. The content of alcoholic compounds remaining in the polycarbonate resin can also be measured by a method of analyzing alcoholic compounds extracted from the polycarbonate resin using gas chromatography. The content of diol components and carbonate diesters remaining in the polycarbonate resin can also be measured by a method of extracting these compounds from the polycarbonate resin and analyzing them using gas chromatography.

[0053] The contents of by-produced alcohol compounds such as phenolic compounds, diol components, and carbonate diesters may be reduced to an undetectable level, but from the viewpoint of productivity, they may be contained in small amounts within a range that does not impair the effects. Furthermore, small amounts can improve the plasticity of the resin when it is melted.

[0054] The content of each of the remaining phenolic compounds, diol components, and carbonate diesters may be, for example, 0.01 ppm by mass or more, 0.1 ppm by mass or more, or 1 ppm by mass or more, relative to 100% by mass of the polycarbonate resin. The content of the remaining alcoholic compounds may be, for example, 0.01 ppm by mass or more, 0.1 ppm by mass or more, or 1 ppm by mass or more, relative to 100% by mass of the polycarbonate resin.

[0055] The contents of by-produced alcohol compounds such as phenolic compounds, diol components, and carbonate diesters in the polycarbonate resin can be adjusted to fall within the above ranges by appropriately adjusting the polycondensation conditions and apparatus settings, and can also be adjusted by the conditions of the extrusion step after polycondensation.

[0056] For example, the amount of residual by-produced alcohol compounds such as phenolic compounds is related to the type of carbonate diester used in the polymerization of the polycarbonate resin, the polymerization reaction temperature, the polymerization pressure, etc. By adjusting these factors, the amount of residual by-produced alcohol compounds such as phenolic compounds can be reduced.

[0057] For example, when a polycarbonate resin is produced using a dialkyl carbonate such as diethyl carbonate, the molecular weight is difficult to increase, resulting in a low-molecular-weight polycarbonate, and the content of by-product alkyl alcohol compounds tends to be high. Such alkyl alcohols are highly volatile, and if they remain in the polycarbonate resin, the moldability of the resin tends to deteriorate. Furthermore, if a large amount of by-product alcohol compounds such as phenolic compounds remain, odor problems may occur during resin molding, or the cleavage reaction of the resin skeleton may progress during compounding, resulting in a decrease in molecular weight. Therefore, it is preferable that the content of by-product alcohol compounds remaining in the obtained polycarbonate resin be 3,000 ppm by mass or less relative to 100% by mass of the polycarbonate resin. The content of the remaining alcohol compounds 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, relative to 100% by mass of the polycarbonate resin.

[0058] In addition to the compound represented by general formula (1), the raw material monomers for the polyester carbonate resin may contain dihydroxy compounds, dicarboxylic acid compounds, dicarboxylic anhydride compounds, hydroxycarboxylic acid compounds, hydroxycarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc., which are generally used as structural units for polyester carbonate resins. Examples of the dihydroxy compounds include the aliphatic dihydroxy compounds and aromatic dihydroxy compounds described above.

[0059] That is, the polyester carbonate resin may contain, in addition to the constituent unit represented by general formula (2) derived from the compound represented by general formula (1), constituent units derived from general dihydroxy compounds, dicarboxylic acid compounds, dicarboxylic anhydride compounds, hydroxycarboxylic acid compounds, hydroxycarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc. Copolymers having multiple types of constituent units may be either block copolymers or random copolymers.

[0060] The polycarbonate resin or polyester carbonate resin containing the structural unit represented by general formula (2) has a number average molecular weight (Mn) of about 4,000 to 100,000, preferably about 10,000 to 50,000, a weight average molecular weight (Mw) of about 10,000 to 100,000, preferably about 12,000 to 80,000, and a polydispersity index (Mw / Mn) of about 1 to 5, preferably about 1.5 to 4.5. The glass transition temperature (Tg) is preferably 145 to 170°C, more preferably 150 to 165°C.

[0061] The refractive index (nD) of the polycarbonate resin or polyester carbonate resin containing the structural unit represented by general formula (2) is relatively high, preferably 1.500 to 1.650, and more preferably 1.520 to 1.630. The refractive index is a value measured by the method described in the examples.

[0062] The Abbe number of birefringence (ν ｄ) is preferably 24.0 to 40.0, more preferably 24.5 to 38.0. The Abbe number is a value measured by the method described in the examples.

[0063] The partial dispersion ratio (θgF) of the polycarbonate resin or polyester carbonate resin containing the structural unit represented by general formula (2) is preferably 0.621 to 0.700, more preferably 0.625 to 0.695. The anomalous partial dispersity (ΔθgF) of the resin is preferably 0.025 to 0.100, more preferably 0.030 to 0.095. The partial dispersion ratio and anomalous partial dispersity are values ​​measured by the methods described in the examples.

[0064] The compound represented by general formula (1A), which is included in the compound represented by general formula (1), can also be polymerized alone or in combination with other monomers in the same manner as above to produce a resin containing a structural unit represented by the following general formula (2A) (structural unit (A)). [In the formula, R １１ and X Ａ is the same as above.]

[0065] In general formula (2A), R １１ and X Ａ Specific and preferred examples of R １１ and X Ａ The specific examples and preferred examples are the same as those of the above.

[0066] The compound represented by general formula (1) can be used as a sole monomer or as a copolymerizable monomer and polymerized to modify the properties of the resin. For example, by adjusting the amount of the compound represented by general formula (1) added and copolymerizing it with other monomers, the properties of the resin, such as the refractive index, glass transition temperature, and birefringence, can be adjusted.

[0067] <Optical Members> The resin of the present invention can be suitably used for optical members. In one embodiment of the present invention, an optical member containing the resin of the present invention is provided. In one embodiment of the present invention, optical members include, but are not limited to, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, and the like. The resin of the present invention can be molded by a casting method with high flow, and is therefore particularly suitable for producing thin optical members. In a preferred embodiment of the present invention, the optical member produced using the resin of the present invention may be an optical lens. In another preferred embodiment of the present invention, the optical member produced using the resin of the present invention may be an optical film.

[0068] When an optical component containing the resin of the present invention is produced by injection molding, molding is preferably performed under conditions of a cylinder temperature of 260 to 350°C and a mold temperature of 90 to 170°C. More preferably, molding is performed under conditions of a cylinder temperature of 270 to 320°C and a mold temperature of 100 to 160°C. If the cylinder temperature is higher than 350°C, the resin will decompose and discolor, and if it is lower than 260°C, the melt viscosity will be high, making molding difficult. Furthermore, if the mold temperature is higher than 170°C, it will be difficult to remove a molded piece made of the resin from the mold. On the other hand, if the mold temperature is lower than 90°C, the resin will harden too quickly in the mold during molding, making it difficult to control the shape of the molded piece and making it difficult to sufficiently transfer the shape applied to the mold.

[0069] <Optical Lens> In one embodiment of the present invention, the resin can be suitably used for optical lenses. Optical lenses produced using the resin of the present invention have a high refractive index and excellent heat resistance, and are therefore extremely useful in fields where expensive high refractive index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors. For example, in the case of smartphone lenses, a lens molded from a resin containing the structural unit (A) and a resin containing any one of the structural units of formulas (II-1) to (II-4), or (In the above formula, R １ and R ２each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４ each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms.) A lens molded from a resin containing a structural unit derived from any one of the monomers of the above formulas can be superimposed on the resin to be used as a lens unit.

[0070] The optical lens of the present invention is preferably implemented as an aspherical lens, if necessary. Since an aspherical lens can substantially eliminate spherical aberration with a single lens, it is not necessary to eliminate spherical aberration by combining multiple spherical lenses, which allows for weight reduction and reduced molding costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses.

[0071] Furthermore, because the optical lens of the present invention has high molding fluidity, it is particularly useful as a material for optical lenses that are thin, small, and have complex shapes. Specifically, the lens size preferably has a central thickness of 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and even more preferably 0.1 to 2.0 mm. The diameter is preferably 1.0 to 20.0 mm, more preferably 1.0 to 10.0 mm, and even more preferably 3.0 to 10.0 mm. Furthermore, the lens preferably has a meniscus shape, with one side convex and the other concave. The optical lens of the present invention can be molded by any method, such as mold molding, cutting, polishing, laser machining, electrical discharge machining, or etching. Among these, mold molding is more preferred in terms of production costs.

[0072] <Optical Film> In one embodiment of the present invention, the resin can be suitably used for optical films. In particular, optical films produced using the polycarbonate resin of the present invention have excellent transparency and heat resistance, and are therefore suitable for use as films for liquid crystal substrates, optical memory cards, and the like. The term "sheet" generally refers to a thin, flat product whose thickness is small relative to its length and width, while the term "film" refers to a thin, flat product whose thickness is extremely small relative to its length and width and whose maximum thickness is arbitrarily limited, and which is usually supplied in roll form. However, in this specification, there is no clear distinction between "sheet" and "film," and both terms are used interchangeably.

[0073] Optical films formed from the resin of the present invention have good heat resistance and color, and are suitable for use, for example, by dissolving such a resin composition in an organic solvent such as methylene chloride, tetrahydrofuran, or dioxane to form a casting film, and then attaching a gas barrier film or a solvent-resistant film to both sides of the film, or as a film for liquid crystal displays such as a liquid crystal substrate film (plastic cell substrate) or a retardation film together with a transparent conductive film or a polarizing plate, and specifically for use in tablets, smartphones, handheld terminals, various display elements, etc. To minimize the inclusion of foreign matter in the optical film, the molding environment must naturally be a low-dust environment, preferably class 6 or less, and more preferably class 5 or less.

[0074] The optical film of the present invention is preferably transparent, with a haze value of 3% or less and a total light transmittance of 85% or more. The stretching ratio in the stretching process can be any condition, but is preferably 1.1 to 5 times, more preferably 1.2 to 3 times. The stretching temperature is preferably in the range of Tg-30°C to Tg+50°C, more preferably Tg-20°C to Tg+30°C, relative to the glass transition temperature (Tg). The thickness of the optical film is preferably in the range of 1 to 200 μm, preferably 10 to 150 μm, and even more preferably 15 to 100 μm. When the optical film of the present invention is used as a retardation film, the viewing angle can be improved by controlling the refractive index in the X-axis, Y-axis, and Z-axis directions by uniaxial stretching, biaxial stretching, or the like. It is also possible to obtain desired optical properties by using multiple films.

[0075] The optical film of the present invention may be used in any field in which its properties can be utilized, and is not particularly limited. For example, the optical film may be suitably used in optical devices such as liquid crystal display devices, organic or inorganic electroluminescence elements, plasma displays, CRTs, liquid crystal projectors, optical pickup optical systems in optical recording and reproducing devices, touch panels, and antireflection films.

[0076] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In these examples, various measurements of cyclic diol compounds were performed by the following methods. Reagents were used for compounds not specifically mentioned.

[0077] - Synthesis of Cyclic Diol Compound - <Analysis by Gas Chromatography (GC)> The purity of the cyclic diol compound was determined by area percentage analysis by gas chromatography (GC) under the following conditions and method: 50 ml of methanol was added to 0.5 g of the cyclic diol compound and the mixture was shaken at room temperature to prepare a methanol solution of the cyclic diol compound, which was used as a sample for analysis.

[0078] [Measurement conditions] Instrument: GC-2020 manufactured by Shimadzu Corporation Column: DB-1 30 m x 0.25 mm x 0.25 μm manufactured by Agilent Technologies Inc. Column temperature: 80°C (holding time 5 min) - heating rate 10°C / min - 320°C (holding time 5 min) Injection temperature / detector temperature: 300°C / 325°C Split ratio: 30 Column flow rate 1.17 ml / min Purge flow rate 10.0 ml / min Detector: FID Carrier gas: Helium Gas linear velocity: 30 cm / sec Injection amount: 1 μl

[0079] <Infrared absorption spectrum (IR spectrum)> The IR spectrum of the cyclic diol compound was measured by the ATR method (attenuated total reflection method) using an infrared spectrometer (Spectrum 400 manufactured by PerkinElmer Japan Co., Ltd.).

[0080] <Proton nuclear magnetic resonance spectrum ( １ H-NMR) > Cyclic diol compound １ H-NMR was performed using a nuclear magnetic resonance spectrometer (AVIII-400 manufactured by Bruker) after dissolving the sample in a deuterated solvent (deuterated chloroform or deuterated dimethyl sulfoxide). １ The measurement was carried out using H-NMR (400 MHz). １ Solvents used in H-NMR measurements may exhibit water peaks. The peak derived from water contained in deuterated chloroform is located around 1.56 ppm, and the peak derived from water contained in deuterated dimethyl sulfoxide is located around 3.33 ppm. Furthermore, the peak derived from residual protons contained in deuterated chloroform is located around 7.27 ppm, and the peak derived from residual protons contained in deuterated dimethyl sulfoxide is located around 2.50 ppm.

[0081] Synthesis Example 1: 25.2 g (0.1 mol) of 4,4'-bicyclohexanone, 0.63 g of p-toluenesulfonic acid monohydrate (Nacalai Tesque, Inc.), 32.8 g (0.27 mol) of trimethylolethane (Tokyo Chemical Industry Co., Ltd.), 300 ml of xylene, and 100 g of N-methyl-2-pyrrolidone were added to a 1000 ml four-neck flask equipped with a stirrer, thermometer, and condenser. The mixture was then heated and stirred under reflux for approximately 3 hours while removing the generated water. After completion of the reaction, approximately 250 g of xylene was distilled under reduced pressure. The reaction mixture was cooled to 90°C and neutralized with 10.35 g of a 3.4 wt % aqueous sodium carbonate solution. 250 g of 90°C ion-exchanged water was then added and the mixture was cooled to 25°C. The resulting crystals were filtered off, and the obtained crystals were first rinsed once with 200 g of ion-exchanged water, and then rinsed once with 50 g of isopropyl alcohol. The wet crystals were dried at 100°C under reduced pressure to obtain 40.1 g (0.10 mol) of 4,4'-bicyclohexanone trimethylolethane diacetal with a purity of 98.1% (GC area percentage). Hereinafter, 4,4'-bicyclohexanone trimethylolethane diacetal will be referred to as Compound 1. The IR spectrum and １ The H-NMR spectrum was measured, and the results are shown in FIGS. 1 and 2.

[0082] (Compound 1) IR (cm -１ ): 674, 901, 932, 987, 1005, 1026, 1047, 1086, 1097, 1207, 1371, 2860, 2939, 3390

[0083] [Synthesis Example 2] (Method for producing compound 2) 2,2-bis(4-oxocyclohexyl)propane-bis(trimethylolethane acetal) (compound 2) was synthesized according to Example 1 of JP-A-2019-14711 (Patent Document 5).

[0084] - Synthesis of Polycarbonate Resin - <Refractive Index (nD)> A test specimen was prepared by molding a polycarbonate resin into a V-shaped block according to JIS B 7071-2:2018. The refractive index was measured at 23°C using a refractometer (Shimadzu KPR-3000).

[0085] <Abbe number (ν)> Using the same test piece (V-block) as used in the refractive index measurement, the refractive indexes at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C were measured using a refractometer, and the Abbe number was calculated using the following formula: ν=(nD−1) / (nF−nC) Formula (a), where nD: refractive index at wavelength 589 nm, nC: refractive index at wavelength 656 nm, and nF: refractive index at wavelength 486 nm.

[0086] <Partial dispersion ratio (θgF)> In addition to the above-mentioned nC, nD, and nF (refractive index values ​​for the D-line, C-line, and F-line), the refractive index value for the g-line was also measured in the same manner. The partial dispersion ratio θgF was calculated from the following formula (b): θgF=(ng-nF) / (nF-nC) formula (b) In formula (b), nC represents the measured refractive index value for the C-line, nF represents the measured refractive index value for the F-line, and ng represents the measured refractive index value for the g-line.

[0087] <Anomalous partial dispersion (ΔθgF)> The value of anomalous partial dispersion (ΔθgF) was calculated based on the Abbe number (ν) and the partial dispersion ratio (θgF) calculated from the above formula (a) and formula (b), respectively. First, a graph was created with the Abbe number (ν) value on the X axis and the partial dispersion ratio (θgF) value on the Y axis. Then, a straight line connecting two points having coordinates (ν, θgF) for the optical glass: a point for NSL7 (ν=60.5, θgF=0.5436: manufactured by Ohara Inc.), which is a standard dispersion glass selected from normal optical glasses that do not exhibit anomalous dispersion, and another point for PBM2 (ν=36.3, θgF=0.5828: manufactured by Ohara Inc.), which is another standard dispersion glass selected from normal optical glasses that do not exhibit anomalous dispersion, was added to the graph. Finally, a point for the polycarbonate resin having coordinates (ν, θgF) was also added to the graph, and the difference between the θgF value of the polycarbonate resin point in the Y-axis direction and the above-mentioned straight line was calculated as the anomalous partial dispersion (or ΔθgF value). Specifically, the value of ΔθgF was calculated as follows. The line connecting the points for the two standard dispersion glasses described above is represented by the following formula (c), where ν represents the Abbe number of the point on the line, and θgF represents the partial dispersion ratio of the point on the line: θgF = 0.001618 × ν + 0.6415 ... formula (c) Then, the value of ΔθgF for the polycarbonate resin was calculated based on the following formula (d). In formula (d), the Abbe number of the polycarbonate resin calculated from the above formula (a) is represented as ν, and the partial dispersion ratio of the polycarbonate resin calculated from the above formula (b) is represented as θgF. ΔθgF = θgF - θgF0 = θgF - (-0.001618 × ν + 0.6415) ... equation (d) As mentioned above, the ΔθgF value for a resin is an index of anomalous dispersion, corresponding to the distance between the line connecting the NSL7 and PBM2 points and the plotted point for that resin, and indicates how much blue light (or short-wavelength light) is refracted by the resin. The larger the value of ΔθgF, the more blue light the resin refracts, and when a resin has a large value of ΔθgF, an optical element containing such a resin can efficiently correct chromatic aberration and achieve clear images.

[0088] <Glass Transition Temperature (Tg)> Measurement was carried out according to JIS K7121-1987 using a differential scanning calorimeter (X-DSC7000 manufactured by Hitachi High-Tech Science Corporation) with a temperature increase program of 10°C / min.

[0089] Example 1 Raw materials included 21.9326 g (0.0500 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF: manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula, 8.5445 g (0.0214 mol) of 4,4′-bicyclohexanone trimethylolethane diacetal (also known as (3,3′-dimethyl-1,1′,5,5′-tetraoxa[9,9′-bisspiro[5.5]undecane]-3,3′-diyl)dimethanol) which is Compound 1 obtained in Synthesis Example 1 above, 15.6891 g (0.0732 mol) of diphenyl carbonate (DPC: manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.6003×10 sodium hydrogen carbonate. －４ g(0.7146×10 －６ (mol) was placed in a 300 mL reactor equipped with a stirrer and a distillation device, and the system was set to a nitrogen atmosphere of 101.3 kPa. The reactor was immersed in an oil bath heated to 200 ° C to initiate the transesterification reaction. Stirring was started 5 minutes after the start of the reaction, and after 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over 10 minutes. The temperature was heated to 210 ° C while reducing the pressure, and the temperature was raised to 220 ° C over 60 minutes after the start of the reaction. After 80 minutes, the pressure was reduced to 20.00 kPa over 10 minutes, and the temperature was raised to 240 ° C while reducing the pressure to 0 kPa and maintained for 30 minutes. Nitrogen gas was then introduced into the reaction system, and the pressure was returned to 101.3 kPa, and a polycarbonate resin was obtained. The physical properties of the resulting resin are shown in Table 1.

[0090] (Examples 2 to 8, Comparative Examples 1 and 2) Polycarbonate resins were obtained in the same manner as in Example 1, except that the materials shown in Table 1 were used as raw materials in the amounts shown in Table 1. The compositions and physical properties of the obtained resins are shown in Table 1.

[0091] Comparing the results in Table 1 between Example 1 and Example 2, Example 3 and Example 4, Example 5 and Example 6, and Example 7 and Example 8, it can be seen that the resin obtained from the monomer represented by general formula (1) and a compound other than BPEF has larger θgF and ΔθgF than the resin obtained from the monomer represented by general formula (1) and BPEF. Therefore, in the present invention, an embodiment excluding a resin consisting of (consisting only of) the structural unit (A) derived from the monomer represented by general formula (1) and a structural unit derived from BPEF is more preferred.

[0092] According to the present invention, it is possible to provide a resin that has excellent heat resistance, excellent optical properties such as refractive index and Abbe number, and further excellent partial dispersion ratio (θgF) and anomalous partial dispersion (ΔθgF), and is therefore suitable for use in optical components such as optical lenses, optical films, and optical sheets.

Claims

1. A resin comprising a monomer-derived constituent unit (A) represented by the following general formula (1), wherein the resin is a polycarbonate resin or a polyester carbonate resin. 【Chemistry 1】 [In the formula, R １ These are, either identical or different, a hydrogen atom, a C1-4 alkyl group, or a phenyl group. X is a divalent group represented by a direct bond or formula (Y). 【Chemistry 2】 [In the formula, R ２ and R ３ are the same or different hydrogen atom, alkyl group, or aryl group, or R ２ and R ３ The atoms may be bonded to each other, forming a ring with adjacent carbon atoms, and this ring may be substituted with an alkyl group. n is 0 or 1. * indicates the bond position.

2. In a divalent group represented by formula (Y), When n is 0, R ２ and R ３ are the same or different and are a hydrogen atom, a C1-6 alkyl group, or a phenyl group, or R ２ and R ３ may be bonded to each other to form a 5- to 12-membered ring together with adjacent carbon atoms, and the ring may be substituted with a C1-3 alkyl group. When n is 1, R ２ and R ３ The resin according to claim 1, wherein the hydrogen atom or C1-6 alkyl group is the same or different.

3. In a divalent group represented by formula (Y), n is 0, R ２ and R ３ However, they are the same or different hydrogen atom, C1-6 alkyl group, or phenyl group, or R ２ and R ３ The resin according to claim 2, wherein the atoms are bonded to each other to form a 5- to 12-membered ring with adjacent carbon atoms, and the ring is substituted with a C1- to C3 alkyl group.

4. R １ However, they are the same or different hydrogen atom, methyl group, or ethyl group. In a divalent group represented by formula (Y), n is 0, R ２ and R ３ The resin according to claim 3, wherein the hydrogen atom or C1-4 alkyl group is the same or different.

5. R １ However, they are the same or different hydrogen atom, methyl group, or ethyl group. The resin according to claim 4, wherein X is a direct bond.

6. The resin according to claim 1, wherein the resin 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). 【Transformation 3】 (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 This represents an aryl group having 6 to 20 carbon atoms which may have substituents, or a heteroaryl group having 6 to 20 carbon atoms which may have substituents and include one or more heterocyclic atoms selected from O, N, and S. X represents a fluorene group that is either a single bond or may have substituents. A and B each independently represent an alkylene group having 1 to 5 carbon atoms, which may have substituents. m and n each independently represent integers from 0 to 6. a and b each independently represent integers between 0 and 10. 【Chemistry 4】 (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. Y １ This is a single bond, a fluorene group which may have substituents, or any of the structural formulas represented by the following formulas (8) to (14): 【Transformation 5】 (In formulas (8) to (14), R ６１ , R ６２ , R ７１ and R ７２ 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 This represents a carbon ring or heterocycle having 1 to 20 carbon atoms, which may have substituents, formed by the bonding of these atoms to one another. r and s each independently represent integers between 0 and 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 integers from 0 to 4. a and b each independently represent integers between 0 and 10.

7. A resin containing a monomer-derived constituent unit (A) represented by the following general formula (1A). 【Transformation 6】 [In the formula, R １１ These are, either identical or different, a hydrogen atom, a methyl group, or an ethyl group. X Ａ This is a divalent group represented by a direct bond or formula (Y1). 【Transformation 7】 [In the formula, R ２１ and R ３１ Either one is a hydrogen atom and the other is a hydrogen atom or a methyl group, or R ２１ and R ３１ These atoms may be bonded to each other, forming a six-membered ring with adjacent carbon atoms, and this ring may be substituted with one to three methyl groups. * indicates the bond position.

8. The resin according to claim 7, wherein the resin is a polycarbonate resin, a polyester carbonate resin, or a polyester resin.

9. The resin according to claim 1 or 7, wherein the weight-average molecular weight (Mw) of the resin on a polystyrene basis is 10,000 to 100,000.

10. The resin according to claim 1 or 7, wherein the refractive index (nD) of the resin is 1.500 to 1.

650.

11. The resin according to claim 1 or 7, wherein the Abbe number (ν) of the resin is 24.0 to 40.

0.

12. The resin according to claim 1 or 7, wherein the glass transition temperature of the resin is 145 to 170°C.

13. The resin according to claim 1 or 7, wherein the partial dispersion ratio (θgF) of the resin is 0.621 to 0.

700.

14. The resin according to claim 1 or 7, wherein the degree of abnormal partial dispersion (ΔθgF) of the resin is 0.025 to 0.

100.

15. An optical lens comprising the resin described in claim 1 or 7.

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