Cyclic diol compound, resin modifier, resin using said resin modifier, and uses of said resin

Abstract

The present invention provides: a resin modifier that is used for a polycarbonate resin or a polyester carbonate resin; a resin using the resin modifier; and a use application of the resin. The present invention also provides: a cyclic diol compound that is useful as a resin modifier and a raw material for a polycarbonate resin, a polyester carbonate resin and the like; and a method for producing the cyclic diol compound. The present invention relates to: a resin modifier for a polycarbonate resin or a polyester polycarbonate resin, the resin modifier comprising a compound represented by formula (1); a resin using the resin modifier; and a use application of the resin. [In the formula, R1's are the same as or different from each other and each independently represent a hydrogen atom, a C1-4 alkyl group, or a phenyl group; and X represents a direct bond or a bivalent group represented by formula (Y) [wherein R2 and R3 are the same as or different from each other and independently represent a hydrogen atom, an alkyl group or an aryl group, or R2 and R3 may be bonded to each other to form a ring in conjunction with a carbon atom to which these residues are adjacent, in which the ring may be substituted by an alkyl group; n represents 0 or 1; and * indicates a bonding position].]

Description

[Technical field]

[0001] The present invention relates to a cyclic diol compound, a resin modifier, a resin using the resin modifier, and uses of the resin. [Background technology]

[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 cyclic diol compounds have been reported depending on the application of the resin to be produced.

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

[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 a cyclic diol compound that can satisfy the resin properties required in those fields. In particular, when a resin is used for optical purposes, a cyclic diol compound that can improve the optical properties of the resin 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 is used as a raw material for a resin, but do not describe that it can be used as a resin modifier for a polycarbonate resin or a polyester carbonate resin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2012-214803 A [Patent Document 2] JP 2013-001867 A [Patent Document 3] International Publication No. 2018 / 074305 [Patent Document 4] JP 2021-134151 A [Patent Document 5] JP 2019-014711 A Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to provide a resin modifier for use in polycarbonate resins or polyester carbonate resins, a resin using the resin modifier, and uses thereof. Another aim of the present invention is to provide a cyclic diol compound useful as a resin modifier and raw material for use in polycarbonate resins, polyester carbonate resins, etc., and a method for producing the same. [Means for solving the problem]

[0008] The present inventors have conducted intensive research to solve the above problems and have found that a cyclic diol compound having a diacetal structure represented by formula (1) can be incorporated as a structural unit into a polycarbonate resin or a polyester carbonate resin to modify the physical properties of the resin and produce a resin having new physical properties. Based on this finding, the present inventors have conducted further research and have completed the present invention.

[0009] That is, the present invention provides a resin modifier comprising the following cyclic diol compound, a resin using the resin modifier, and uses of the resin.

[0010] [Section 1] A resin modifier for polycarbonate resin or polyester polycarbonate resin, comprising a compound represented by formula (1). [ka] [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 the formula (Y). [ka] [In the formula, R 2 and R 3 are the same or different and each is 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. [Section 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 C 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 C 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. [Section 3] The resin modifier according to [Item 1] or [Item 2], wherein X is a direct bond (single bond). [Section 4] R 1 are the same or different and are C1-4 alkyl groups. [Section 5] X is a divalent group represented by formula (Y), n is 0, and R 2 and R3 The resin modifier according to [Item 1] or [Item 2], except when both are methyl groups. [Section 6] R 2 or R 3 or a phenyl group, and the other is a hydrogen atom or a C1-6 alkyl group (particularly a C1-3 alkyl group). [Section 7] The resin modifier according to any one of [Item 1] to [Item 6], which is a resin modifier for a polycarbonate resin or a polyester polycarbonate resin used in optical materials. [Section 8] A compound represented by formula (1B). [ka] [In the formula, R 11 are the same or different and each is a hydrogen atom, a methyl group, or an ethyl group. [Section 9] A resin modifier comprising the compound according to [Item 8]. [Section 10] The resin modifier according to [Item 9], wherein the resin modifier is a polyester resin, a polycarbonate resin, or a polyester polycarbonate resin. [Section 11] The resin modifier according to [Item 9] or [Item 10], wherein the resin modifier is a resin modifier for a resin used in an optical material. [Section 12] A method for producing a compound represented by formula (1B), comprising a step of reacting a compound represented by formula (3B) with a compound represented by formula (4A). [ka] [In the formula, R 11 are the same or different and each is a hydrogen atom, a methyl group, or an ethyl group. [Section 13] A method for modifying a polycarbonate resin or a polyester polycarbonate resin by using the resin modifier according to any one of [1] to

[11] . [Section 14] The method according to [Item 13], wherein the modifying method adjusts the content of the resin modifier according to any one of [Item 1] to [Item 11] in the total polyol raw material, thereby adjusting at least one property selected from the group consisting of the glass transition temperature, refractive index, and Abbe number of the polycarbonate resin or polyester polycarbonate resin obtained after copolymerization. [Section 15] A resin containing a structural unit represented by formula (2), the resin being a polycarbonate resin or a polyester carbonate resin. [ka] [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 or a divalent group represented by the formula (Y). [ka] [In the formula, R 2 and R 3 are the same or different and each is 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. [Section 16] A resin containing a constitutional unit represented by formula (2A). [ka] [In the formula, R 11 are the same or different and each is a hydrogen atom, a methyl group, or an ethyl group. A is a direct bond (single bond) or a divalent group represented by the formula (Y1). [ka] [In the formula, R 21 and R 31one 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. [Section 17] The resin according to [Item 16], which is a resin having at least one bond selected from the group consisting of an ester bond, a carbonate bond, and a urethane bond. [Section 18] An optical member comprising the resin according to any one of [Item 15] to [Item 17]. [Section 19] The optical member according to [Item 18], which is at least one selected from the group consisting of an optical lens, an optical film, and an optical sheet. Effect of the Invention

[0011] The compound represented by formula (1) (cyclic diol compound) is useful as a resin modifier for polycarbonate resin or polyester polycarbonate resin (i.e., a resin having a carbonate bond and, if necessary, an ester bond). Among them, the compound represented by formula (1B) is a novel compound and is useful as a resin modifier or monomer raw material for a wide range of resins including the above resins. The polycarbonate resin or polyester carbonate resin obtained by using the resin modifier of the present invention is characterized by a relatively small refractive index and a high glass transition temperature (Tg), and thus the properties (glass transition temperature, refractive index, Abbe number, etc.) of the obtained resin can be adjusted over a wide range by adjusting the content of the resin modifier in the monomer. In addition, the resin modifier of the present invention can be copolymerized with various dihydroxy compounds in an appropriate ratio to adjust the refractive index of the resulting resin, which can be suitably used for optical applications (optical lenses, optical films, optical sheets, etc.). [Brief description of the drawings]

[0012] [Figure 1] 1 is an IR spectrum of Compound 1 obtained in Example 1. [Diagram 2] 1 is a 1H-NMR spectrum of compound 1 obtained in Example 1. [Diagram 3] 1 is an IR spectrum of Compound 2 obtained in Example 2. [Figure 4] 1 is a 1H-NMR spectrum of compound 2 obtained in Example 2. [Diagram 5] 1 is an IR spectrum of compound 4 obtained in Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 1.Resin modifier The resin modifier of the present invention comprises a compound represented by formula (1), and the resin modifier is a resin modifier for polycarbonate resin or polyester polycarbonate resin. [ka] [In the formula, R 1 are the same or different and each is 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 the formula (Y). [ka] [In the formula, R 2 and R 3 are the same or different and each is 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.

[0014] R 1 are preferably the same or different and each is a C1-4 linear or branched alkyl group or a phenyl group. 1Examples 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. Among 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 alkyl group represented by the formula (I) include a C1-12 alkyl group, further 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, a tert-butyl group, and the like. Among these, preferred are a methyl group, an ethyl group, an isobutyl group, or a tert-butyl group. More preferred are a methyl group or an ethyl group. Particularly preferred is a methyl group.

[0016] 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.

[0017] R 2 and R 3When they are bonded to each other to form a ring together with the adjacent carbon atoms, the ring may be, for example, a 3- to 12-membered ring (e.g., a 3- to 12-membered cycloalkane, etc.), preferably a 5- to 12-membered ring (e.g., a 5- to 12-membered cycloalkane, etc.), more preferably a 6- to 12-membered ring (e.g., a 6- to 12-membered cycloalkane, etc.). Specific examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, etc. The ring may be substituted with 1 to 6 (preferably 1 to 3) alkyl groups. Examples of the alkyl group include, for example, a C1-4 (particularly C1-3) linear or branched alkyl group, preferably a methyl group or an ethyl group. When there are a plurality of alkyl groups, they may be the same or different.

[0018] n is preferably 0. Specifically, the divalent group represented by formula (Y) is preferably a divalent group represented by formula (Y1). [ka] [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.]

[0019] 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. [ka] [In the formula, R 2 , R 3 , n and * are as defined above.]

[0020] Among the compounds represented by formula (1), preferred examples of the resin modifier include compounds in which X is a direct bond (single bond). 1 are the same or different and are a C1-4 alkyl group.

[0021] Among the compounds represented by formula (1), another preferred example of a resin modifier is 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).

[0022] Among the compounds represented by formula (1), another preferred example of a compound as a resin modifier is a compound represented by formula (Y), in which X is a divalent group represented by formula (Y), n is 0, and R 2 and R 3 In addition, compounds in which R 2 or R 3 and the other is a hydrogen atom or a C1-6 alkyl group (further, a C1-3 alkyl group, particularly a methyl group).

[0023] Among the compounds represented by formula (1), another preferred example of a resin modifier is a divalent group represented by formula (Y), in which, when n is 0, R 2 and R 3 are the same or different and are a hydrogen atom, a C 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 C 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.

[0024] Among the compounds represented by formula (1), another example of a compound preferred as a resin modifier is a compound represented by formula (Y), in which n is 0 and R 2 and R 3are the same or different and are a hydrogen atom, a C 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.

[0025] Among the compounds represented by formula (1), another preferred example of a resin modifier is 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; R 2 and R 3 are the same or different and are a hydrogen atom or a C1-4 alkyl group.

[0026] Among the compounds represented by formula (1), another preferred example of the resin modifier is a compound represented by formula (1A). [ka] [In the formula, R 11 are the same or different and each is a hydrogen atom, a methyl group, or an ethyl group. A is a direct bond (single bond) or a divalent group represented by the formula (Y1). [ka] [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.

[0027] In the divalent group represented by formula (Y1), R 21 and R 31 Of these, it is preferred that one of them is a hydrogen atom or a C1-3 alkyl group, and the other is an aryl group.

[0028] R 21 or R 31 Examples of the C1-3 alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Of these, a methyl group is preferred.

[0029] R 31 or R 31 Examples of the aryl group represented by the formula (I) include a phenyl group, a toluyl group, a xylyl group, a naphthyl group, etc. Among these, a phenyl group is preferred.

[0030] R 11 are the same or different and are preferably a methyl group or an ethyl group.

[0031] Specific examples of the compound represented by 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). [ka]

[0032] Among the compounds represented by formula (1), another preferred example of the resin modifier is a compound represented by formula (1B). [ka] [In the formula, R 11 Same as above.]

[0033] R 11 are the same or different and are preferably a methyl group or an ethyl group.

[0034] Among the compounds represented by formula (1), another preferred example of the resin modifier is the compound represented by formula (1C). [ka] [In the formula, R22 is a hydrogen atom or a C1-3 alkyl group, R 32 is an aryl group. 11 Same as above.]

[0035] R 22 Examples of the C1-3 alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Of these, a methyl group is preferred.

[0036] R 32 Examples of the aryl group represented by the formula (I) include a phenyl group, a toluyl group, a xylyl group, a naphthyl group, etc. Among these, a phenyl group is preferred.

[0037] The resin modifier used in the present invention is used to mean a reagent that can modify the properties of a resin by being introduced into the resin. The modified resin has a structural unit derived from the resin modifier. Specifically, the resin of the present invention means a resin having a structural unit derived from a cyclic diol compound represented by formula (1) (including cyclic diol compounds represented by formulas (1A), (1B) and (1C). The same applies below.) In other words, it means a resin containing a divalent structural unit obtained by removing hydrogen atoms of hydroxyl groups from a cyclic diol compound represented by formula (1).

[0038] The resin modifier consisting of the cyclic diol compound represented by formula (1) can be used as a resin modifier for polycarbonate resin or polyester polycarbonate resin, that is, it can be used as a resin modifier for resins having a carbonate bond in the molecule.

[0039] In addition, the resin modifiers made of the cyclic diol compounds represented by formula (1A), formula (1B) and formula (1C) can be widely used as modifiers for resins having, for example, ester bonds, carbonate bonds, urethane bonds, etc. in the molecule. Examples of such resins include polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic acid ester resins, polymethacrylic acid ester resins, polyester polyol resins, etc. Preferred are polyester resins, polyester carbonate resins, polycarbonate resins, and polyurethane resins, and more preferred are polyester carbonate resins and polycarbonate resins.

[0040] 2. Manufacturing method of resin modifier The method for producing the compound represented by formula (1) is not particularly limited, and for example, the compound represented by formula (1) can be produced through a step of reacting a compound represented by formula (3) with a compound represented by formula (4) (acetalization reaction) as shown in the following <Reaction Scheme 1>. The compounds represented by formula (1A), formula (1B) and formula (1C), which are included in the compound represented by formula (1), can also be produced in the same manner. [ka] [In the formula, R 1 and X is as above.] Specifically, the compound represented by formula (1) can be produced by reacting a compound represented by formula (3) with a compound represented by formula (4) in the presence of an acid catalyst (acetalization reaction).

[0041] The reaction can usually be carried out in a solvent (e.g., toluene, etc.). The solvent can be heated and refluxed, and the reaction can be carried out while removing the generated water by azeotropic distillation with the solvent. The acid catalyst is not particularly limited as long as it has a catalytic effect, and a known acid catalyst can be used. For example, 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.

[0042] The amount of the compound represented by formula (4) used is usually about 0.5 to 3 mol, and preferably about 0.8 to 2 mol, per 1 mol of the compound represented by formula (3).

[0043] The compounds represented by formula (1A), formula (1B) and formula (1C), which are included in the compound represented by formula (1), can be specifically prepared according to the following <Reaction Scheme 2>, <Reaction Scheme 3> and <Reaction Scheme 4>, respectively.

[0044] [ka] [In the formula, R 11 and X A Same as above.]

[0045] [ka] [In the formula, R 11 Same as above.]

[0046] [ka] [In the formula, R 11 , R 22 and R 32 Same as above.]

[0047] 3. Manufacturing resin using resin modifier The compound represented by 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 formula (2). [ka] [In the formula, R 1 and X is as above.]

[0048] Resins obtained by using a resin modifier containing a compound represented by formula (1) include polycarbonate resins and polyester carbonate resins having carbonate bonds.

[0049] In formula (2), R 1 Specific and preferred examples of X are the same as those described in the formula (1). 1 The specific and preferred examples are the same as those of X and X.

[0050] A polycarbonate resin containing a constitutional unit represented by formula (2) can be produced by (polymerizing) a raw material monomer containing a compound represented by formula (1) with a carbonyl precursor compound.

[0051] The compound represented by formula (1) can be used alone as a raw material monomer for polycarbonate resin. The resulting polycarbonate resin is a homopolymer obtained by polymerizing only the compound represented by formula (1) with a carbonyl precursor compound, and is composed of only the constitutional unit represented by formula (2).

[0052] The raw material monomer of the polycarbonate resin may contain a dihydroxy compound generally used as a structural unit of the polycarbonate resin in addition to the compound represented by formula (1). Examples of the dihydroxy compound include an aliphatic dihydroxy compound and an aromatic dihydroxy compound.

[0053] 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 formula (2) derived from the compound represented by formula (1). The copolymer having multiple types of structural units may be either a block copolymer or a random copolymer.

[0054] Aliphatic dihydroxy compounds include a variety of 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, 1,6-hexanediol, and the like.

[0055] 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 (BPEF), etc. In addition, examples include hydroquinone, resorcinol, and catechol.

[0056] Another embodiment of the dihydroxy compound is a dihydroxy compound represented by formula (5): The dihydroxy compound represented by formula (5) may contain one or more kinds. [ka] [In the formula, R 4 and R 5 are each independently a hydrogen atom, a C1-10 alkyl group, a C5-10 cycloalkyl group, or a C6-10 aryl group. Each W is independently a C2-6 alkylene group, a C5-10 cycloalkylene group, or a C6-10 arylene group. p and m are each independently an integer of 0 to 5.]

[0057] R 4 or R 5 The C1-10 alkyl group represented by the formula (I) may be either linear or branched, and is preferably a C1-3 alkyl group, more preferably a methyl group. R 4 or R 5 Examples of the C5-10 alkyl group represented by the formula (I) include a cyclopentyl group, a cyclohexyl group, and the like. R 4 or R 5 Examples of the C6-10 aryl group represented by the formula (I) include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group. R 4 and R 5 and R are preferably both hydrogen atoms. The C2-6 alkylene group represented by W may be either linear or branched, and is preferably a C2-4 alkylene group, more preferably an ethylene group (-CH2CH2-), a propylene group (-CH2CH(CH3)-, -CH2CH2CH2-), etc. W is preferably an ethylene group. p is preferably an integer of 1 to 3, and is preferably 1. m is preferably an integer of 1 to 3, and is preferably 1.

[0058] Among the dihydroxy compounds represented by formula (5), R 4 and R 5are each independently a hydrogen atom, a C1-3 alkyl group (particularly a methyl group), or a phenyl group, X is a C2-3 alkylene group (particularly an ethylene group), and p and m are 1. BPEF is particularly preferred.

[0059] The ratio of the compound represented by formula (1) in the raw material monomer used is not particularly limited, and is, for example, 1 mol% or more, preferably 1 to 80 mol%, more preferably 1 to 60 mol%, even more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total amount of monomers. That is, in the polycarbonate resin, the ratio of the constitutional unit represented by formula (2) derived from the compound represented by formula (1) is not particularly limited, and is, for example, 1 mol% or more, preferably 1 to 80 mol%, more preferably 1 to 60 mol%, even more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total constitutional units.

[0060] Examples of carbonyl precursor compounds include phosgene, triphosgene, diphenyl carbonate, and the like.

[0061] In addition to the compound represented by formula (1), the raw material monomer of the polyester carbonate resin may contain a dihydroxy compound, a dicarboxylic acid compound, a dicarboxylic anhydride compound, a hydroxycarboxylic acid compound, a hydroxycarboxylic acid ester compound, a dicarboxylic acid ester compound, etc., which are generally used as a structural unit of a polyester carbonate resin. Examples of the dihydroxy compound include the above-mentioned aliphatic dihydroxy compound, aromatic dihydroxy compound, and dihydroxy compound represented by formula (5). As the raw material monomer, for example, one containing a structural unit derived from at least one monomer selected from the following monomer group is also preferred. [ka] [In the formula, R 6 and R 7 each independently represents a hydrogen atom, a methyl group, or an ethyl group; R8 and R 9 each independently represents a hydrogen atom, a methyl group, an ethyl group, or a monovalent group obtained by removing one hydroxyl group from a C2-5 alkylene glycol.

[0062] That is, the polyester carbonate resin may contain, in addition to the structural unit represented by formula (2) derived from the compound represented by formula (1), structural units derived from general dihydroxy compounds, dicarboxylic acid compounds, dicarboxylic anhydride compounds, hydroxycarboxylic acid compounds, hydroxycarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc. The copolymer having multiple types of structural units may be either a block copolymer or a random copolymer.

[0063] The carbonate resin and polyester carbonate resin containing the constitutional unit represented by formula (2) each preferably contain a constitutional unit derived from a dihydroxy compound represented by formula (5) (particularly BPEF) and a constitutional unit derived from a compound represented by formula (1). The molar ratio of the two constitutional units in the resin is, for example, 99:1 to 1:99, preferably 95:5 to 20:80, more preferably 90:10 to 30:70, further preferably 85:15 to 40:60, and particularly preferably 85:15 to 45:55.

[0064] Another embodiment of the carbonate resin and polyester carbonate resin is a resin consisting of (consisting only of) a dihydroxy compound (particularly BPEF)-derived structural unit represented by formula (5) and a compound (1)-derived structural unit. In this case, the molar ratio of the two structural units in the resin can be preferably within the range described above.

[0065] The number average molecular weight (Mn) of the polycarbonate resin or polyester carbonate resin containing the constitutional unit represented by formula (2) is about 4000 to 100,000, preferably about 10000 to 50000, the weight average molecular weight (Mw) is about 5000 to 100,000, preferably about 6000 to 80000, and the polydispersity (Mw / Mn) is about 1 to 5, preferably about 1.5 to 4.5. The glass transition temperature (Tg) is about 100 to 200°C, preferably about 120 to 160°C.

[0066] The refractive index (n D ) is relatively large, and is usually 1.500 to 1.750, and preferably 1.520 to 1.650. The refractive index is a value measured by the method described in the Examples.

[0067] The Abbe number (ν d ) is usually 20.0 to 55.0, and preferably 24.0 to 45.0. The Abbe number is a value measured by the method described in the examples.

[0068] The compounds represented by formula (1A), formula (1B) and formula (1C) included in the compound represented by formula (1) can be produced in the same manner as above. They can be polymerized alone or in combination with other monomers to produce resins containing structural units represented by the following formulas (2A), (2B) and (2C), respectively. [ka] [In the formula, R 11 and X A Same as above.]

[0069] [ka] [In the formula, R 11 Same as above.]

[0070] [ka] [In the formula, R 11 , R 22 and R 32 Same as above.]

[0071] Resins obtained by using resin modifiers containing compounds represented by formula (1A), formula (1B) and formula (1C) include resins having ester bonds, carbonate bonds, urethane bonds, etc. in the molecule. Specific examples include polyester resins, polyester carbonate resins, polycarbonate resins, polyurethane resins, polyester polyol resins, etc. Preferred examples include polyester resins, polyester carbonate resins, polycarbonate resins, and polyurethane resins, and more preferred examples are polyester carbonate resins and polycarbonate resins.

[0072] In addition, the resins containing the structural units represented by formula (2A), formula (2B), and formula (2C) may contain structural units derived from raw material monomers other than the compounds represented by formula (1A), formula (1B), and formula (1C) in the molecule. The structural units may contain ether bonds, amide bonds, urethane bonds, urea bonds, etc.

[0073] In formula (2A), R 11 and X A Specific and preferred examples of R 11 and X A The specific and preferred examples are the same as those of the above.

[0074] In formula (2B), R 11 Specific and preferred examples of R 11 The specific and preferred examples are the same as those of the above.

[0075] In formula (2C), R 11 , R 22 , R 32 and X ASpecific and preferred examples of R 11 , R 22 , R 32 and X A The specific and preferred examples are the same as those of the above.

[0076] Resins containing structural units represented by formula (2A), formula (2B), and formula (2C) are widely applicable to resins other than the above-mentioned polycarbonate resins or polyester carbonate resins, and therefore, in addition to the above-mentioned properties, various properties (optical properties, mechanical properties, dimensional stability, etc.) can be imparted to the resin depending on the purpose.

[0077] 4. Applications of modified resins The compound represented by formula (1) can be polymerized as a single monomer or as a copolymerization monomer to modify the properties of the resin. For example, by adjusting the amount of the compound represented by formula (1) added and copolymerizing it with other monomers, the properties of the resin obtained after copolymerization, such as the refractive index, glass transition temperature, Abbe number, and birefringence, can be adjusted.

[0078] Therefore, the resin obtained by using the resin modifier of the present invention can be suitably used for optical members, for example. 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, etc. The resin of the present invention can be molded by a casting method with high flow, and is therefore particularly suitable for the manufacture of thin optical members. In a preferred embodiment of the present invention, optical members manufactured by using the resin of the present invention include optical lenses, optical films, optical sheets, etc.

[0079] The resin of the present invention can be suitably used for optical lenses. Optical lenses manufactured using the resin of the present invention (particularly, polycarbonate resin) have a high refractive index and excellent heat resistance, and therefore can be used in fields where expensive high refractive index glass lenses have been used in the past, such as telescopes, binoculars, and television projectors, and are extremely useful.

[0080] Furthermore, by adjusting the content of the structural unit derived from the compound represented by formula (1) in the resin of the present invention, the refractive index of the resin can be adjusted over a wide range in accordance with the design of various optical lenses.

[0081] The resin of the present invention can be suitably used for optical films. Optical films produced using the resin of the present invention (particularly, polycarbonate resin) have excellent transparency and heat resistance, and are therefore suitably used for liquid crystal substrate films, optical memory cards, and the like.

[0082] There are various resins commonly used for optical components, among which polyester resins, polyester carbonate resins, polycarbonate resins, etc. can be mentioned. In particular, polyester carbonate resins and polycarbonate resins are excellent in transparency, impact resistance, heat resistance, dimensional stability, etc.

[0083] The resin can be suitably used in applications requiring adjustment of the refractive index, particularly as optical members such as optical lenses, optical films, optical sheets, etc. Applicable optical members are not particularly limited, but examples thereof include smartphone camera lenses, vehicle-mounted camera lenses, goggle lenses for VR (virtual reality) or MR (mixed reality), and security camera lenses.

[0084] In this specification, the expressions "comprise" and "contain" encompass the meanings of "consisting essentially of" and "consisting only of". EXAMPLES

[0085] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, various measurements of the cyclic diol compound were performed by the following methods. Reagents were used for compounds not specifically mentioned.

[0086] <Compound used> 4,4'-Bicyclohexanone: Tokyo Chemical Industry Co., Ltd. p-Toluenesulfonic acid monohydrate: Nacalai Tesque, Inc. Trimethylolethane and trimethylolpropane: Tokyo Chemical Industry Co., Ltd. Bisphenoxyethanolfluorene (BPEF): manufactured by Tokyo Chemical Industry Co., Ltd. Diphenyl carbonate: Tokyo Chemical Industry Co., Ltd.

[0087] <Analysis by gas chromatography (GC)> The purity of the cyclic diol compound was determined by gas chromatography (GC) analysis under the following conditions and method, and the purity was determined by the area percentage method. (Sample preparation) To 10 mg of the cyclic diol compound, 1 g of pyridine was added, and N,O-bis(trimethylsilyl)trifluoroacetamide (containing 1% trimethylchlorosilane) was further added and shaken at room temperature to prepare a pyridine solution of the cyclic diol compound, which was used as the sample for analysis.

[0088] [Measurement conditions] Equipment: Shimadzu GC-2020 Column: Agilent Technologies DB-1 30m x 0.25mm x 0.25μm Column temperature: 80℃ (holding time 5 min) - heating rate 10℃ / min - 320℃ (holding time 5 min) Injection temperature / detector temperature: 300℃ / 325℃ 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: 30cm / sec Injection volume: 1μl

[0089] <Infrared absorption spectrum (IR spectrum)> The IR spectrum of the cyclic diol compound was measured by the ATR (attenuated total reflection) method using an infrared spectrometer (Spectrum 400 manufactured by PerkinElmer Japan Co., Ltd.).

[0090] <Proton nuclear magnetic resonance spectrum ( 1 H-NMR) Cyclic diol compounds 1 H-NMR was performed by dissolving the sample in a deuterated solvent (deuterated chloroform or deuterated dimethyl sulfoxide) and then measuring the sample with a nuclear magnetic resonance spectrometer (Bruker AVIII-400, 1 H-NMR (400 MHz) was used for measurement. In addition, 1 Solvents used in H-NMR measurements may show water peaks. The peak due to water contained in deuterated chloroform is around 1.56 ppm, and the peak due to water contained in deuterated dimethyl sulfoxide is around 3.33 ppm. In addition, the peak due to residual protons contained in deuterated chloroform is around 7.27 ppm, and the peak due to residual protons contained in deuterated dimethyl sulfoxide is around 2.50 ppm.

[0091] <Glass transition temperature (Tg)> The glass transition temperature of the obtained polycarbonate resin was measured using a differential calorimeter DSC6220 manufactured by SII NanoTechnology Co., Ltd. 6.7 mg of the sample was placed in an aluminum pan manufactured by the same company and sealed, and heated from 30°C to 220°C at a heating rate of 10°C / min under a nitrogen gas flow of 50 ml / min, cooled from 220°C to 30°C at a heating rate of 10°C / min, and heated from 30°C to 220°C at a heating rate of 10°C / min. The inflection point (maximum value of the differential of DSC) in the 2nd run was taken as the glass transition temperature.

[0092] <Number average molecular weight, weight average molecular weight and polydispersity index> Approximately 30 mg of polycarbonate resin was dissolved in 8 ml of tetrahydrofuran to prepare a sample solution for molecular weight measurement. The polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the polycarbonate resin contained in this sample solution were determined using gel permeation chromatography (GPC) under the following measurement conditions. (Measurement conditions) Equipment: Pump (Shimadzu Corporation LC-20AD type) Autosampler (Shimadzu Corporation SIL-20A HT type) Detector RI (Shimadzu Corporation RID-10A type) Column oven (Shimadzu Corporation CTO-20A model) Column: Shodex LF-802, 2 columns (Showa Denko K.K.) Eluent: Tetrahydrofuran (THF) manufactured by Nacalai Tesque, Inc., containing approximately 0.025% BHT Column temperature: 40℃ Flow rate: 1.0mL / min Injection volume: 100μl Analysis method: PS equivalent molecular weight Standard polymer used: Shodex STANDARD SM-105

[0093] <Refractive index> The polycarbonate resin obtained in each of the production examples described below was heated for 3 minutes at 200°C under a pressure of 10 MPa in an amount of 0.8 g of resin in an IMC-48IE manual hydraulic heating and cooling press manufactured by Imoto Manufacturing Co., Ltd. Then, the resin was cooled for 3 minutes to obtain a polycarbonate film having a thickness of 0.1 mm. A rectangular test piece 40 mm long and 8 mm wide was cut out from this 0.1 mm thick film to serve as a measurement sample. The refractive index n was measured using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. according to the method of JIS-K-7142, using an interference filter with a wavelength of 589 nm (D line). D The measurement was performed using diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) as an intermediate solution.

[0094] <Total light transmittance> The 0.1 mm thick film prepared by the method described above in "Refractive Index" was used as the measurement sample, and the total light transmittance was measured using a Nippon Denshoku HazeMater NDH7000SPII according to the method of JIS-K-7136. The measurement was performed on three pieces of film, and the average of the actual values ​​obtained in these measurements was used as the measured value.

[0095] <Abbe number> A rectangular test piece 40 mm long and 8 mm wide was cut out from the 0.1 mm thick film prepared by the method described above for refractive index, and used as a measurement sample. The refractive index n of each wavelength was measured using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd., using interference filters with wavelengths of 656 nm (C line), 589 nm (D line), and 486 nm (F line) according to the method of JIS-K-7142. C , n D , n F The Abbe number ν d asked for. vD = (nD-1) / (nF-nC) In the measurements, diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the intermediate liquid.

[0096] <Production of Cyclic Diol Compound> [Example 1] (Production of cyclic diol compound 1) 25.2 g (0.13 mol) of 4,4'-bicyclohexanone, 0.63 g of p-toluenesulfonic acid monohydrate, 32.8 g (0.27 mol) of trimethylolethane, 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, a thermometer, and a Dean-Stark condenser, and the mixture was heated and stirred under reflux conditions for approximately 3 hours while removing the generated water. After the reaction was completed, about 250 g of xylene was distilled out under reduced pressure. The reaction product was cooled to 90°C and neutralized with 10.35 g of 3.4 wt% aqueous sodium carbonate solution, after which 250 g of 90°C ion-exchanged water was added and cooled to 25°C. The generated 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). 4,4'-bicyclohexanone trimethylolethane diacetal is hereinafter referred to as Compound 1. The obtained compound 1 was analyzed by IR spectrum and 1 The H-NMR spectrum was measured and the results are shown in FIG. 1 and FIG. 2.

[0097] (Compound 1) IR(cm -1 ):674,901,932,987,1005,1026,1047,1086,1097,1207,1371,2860,2939,3390

[0098] [Example 2] (Production of cyclic diol compound 2) 21.2 g (0.11 mol) of 4,4'-bicyclohexanone, 0.53 g of p-toluenesulfonic acid monohydrate, 26.4 g (0.20 mol) of trimethylolpropane, 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, a thermometer, and a Dean-Stark condenser, and the mixture was heated and stirred under reflux conditions for approximately 6 hours while removing the generated water. After the reaction was completed, about 250 g of xylene was distilled out under reduced pressure conditions. The reaction product was cooled to 60°C, neutralized with 10.35 g of 3.4 wt% aqueous sodium carbonate solution, and then 250 g of 60°C ion-exchanged water was added and cooled to 25°C. The generated 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 obtained wet crystals were placed in a 1000ML four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark with a cooling tube, and 200 g of isopropyl alcohol was added, and the mixture was heated to 80°C, stirred for about 30 minutes, cooled to 25°C, and the precipitated crystals were filtered off. The obtained crystals were rinsed once with 35 g of isopropyl alcohol. The wet crystals were dried under reduced pressure at 100° C. to obtain 26.5 g (0.06 mol) of 4,4′-bicyclohexanone trimethylolpropane diacetal with a purity of 98.1% (GC area percentage). 4,4′-bicyclohexanone trimethylolpropane diacetal is hereinafter referred to as Compound 2. The obtained compound 2 was analyzed by IR spectrum and 1 The H-NMR spectrum was measured and the results are shown in FIG. 3 and FIG.

[0099] (Compound 2) IR(cm -1):906,932,1011,1037,1088,1104,1204,1370,2861,2942,3388

[0100] [Reference Example 1] (Production of Cyclic Diol Compound 3) 2,2-Bis(4-oxocyclohexyl)propane-bis(trimethylolethane acetal) (compound 3) was synthesized according to Example 1 of JP 2019-14711 A (Patent Document 5).

[0101] [Example 3] (Production of cyclic diol compound 4) A 1500ml stainless steel (SUS) reactor was charged with 1.8g of palladium catalyst "Pd / C (N.E. Chemcat Corporation)", 90.0g (0.30mol) of bisphenol AP (4,4'-(1-phenylethylidene)bisphenol), 0.2g of sodium carbonate, and 512g of xylene. Hydrogen gas was then filled into the reactor until the pressure reached 1.0MPa, and the temperature was raised to 170℃, which was the reaction temperature. The reaction was carried out for 7 hours at 170℃ while supplying hydrogen gas so that the reaction pressure reached 1.0MPa. After that, the reactor contents were cooled, recovered, and filtered to remove the catalyst. The amount of filtrate recovered was 596 g. Analysis of the filtrate by GC showed that the conversion rate of the raw material bisphenol AP was 100%, and the purity of the target diketone (4,4'-(1-phenylethane-1,1-diyl)bis(cyclohexan-1-one)) was 68.5% (GC area percentage). The contents were concentrated in a rotary evaporator at a water temperature of 70°C and a reduced pressure of 30 mmHg until the contents were 100 g. Since it was a viscous liquid, 100 g of toluene was added to it, and the next ketalization reaction was carried out. A 1000ML four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark with a cooling tube was charged with 50g of a mixture of viscous liquid and toluene, 1.4g of methanesulfonic acid, 47.5g (0.40mol) of trimethylolethane, and 450g of toluene, and then the mixture was heated and stirred for about 5 hours under reflux conditions while removing the generated water. The reaction mixture was cooled to 80°C, and an aqueous sodium carbonate solution (a mixture of 2.12g of sodium carbonate and 10g of distilled water) was added and neutralized. The mixture was then cooled to room temperature and concentrated in a rotary evaporator at a water temperature of 70°C and a reduced pressure of 30mmHg to obtain 80.5g of a viscous liquid. The viscous liquid was dried in a reduced pressure dryer to obtain 32.5g of the crude product 4,4'-(1-phenylethylidene)biscyclohexanone trimethylolethane diacetal. 30.0 g of the crude product was placed in a 100 ML four-neck flask equipped with an oil bath, stirrer, thermometer, and distillation device. The four-neck flask was immersed in an oil bath heated to 250°C, and the pressure was gradually reduced from normal pressure to vacuum, allowing compounds with low boiling points to be distilled out. The solid remaining in the flask was removed, and 18 g of 4,4'-(1-phenylethylidene)biscyclohexanone trimethylolethane diacetal (compound 4) with a purity of 97.5% (GC area percentage) was obtained as a solid. This compound will be referred to as compound 4 below.

[0102] (Compound 4) IR(cm -1 ):878,963,1005,1022,1050,1395,2873,2941,3307

[0103] <Resin production and physical property evaluation> [Production Example 1] (Production of Polycarbonate Resin 1) 5.6 g (0.01 mol) of the compound 1 obtained in Example 1, 24.6 g (0.06 mol) of bisphenoxyethanolfluorene, 15.9 g (0.07 mol) of diphenyl carbonate, and 2.5 × 10 -2 mol / L sodium bicarbonate solution 17.0μL (4.2×10 -7mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After dissolving the substrate, the temperature was raised stepwise to 240°C over 80 minutes, and the pressure was reduced stepwise to 150 mmHg. The pressure was further reduced stepwise to a vacuum over 40 minutes, and after holding for 20 minutes, 25 g of the produced polycarbonate resin (hereinafter referred to as "polycarbonate resin 1") was taken out. During the reaction, phenol, which was a by-product, was distilled off. The taken-out polycarbonate resin 1 was pulverized, and the glass transition temperature was measured, which was 142.7°C. The number average molecular weight Mn was 14,600, the weight average molecular weight Mw was 26,300, and the polydispersity Mw / Mn was 1.8. The refractive index was 1.611. The Abbe number was 26.0. The total light transmittance was 90%. The results are shown in Table 1.

[0104] [Production Example 2] (Production of Polycarbonate Resin 2) 8.0 g (0.02 mol) of the compound 1 obtained in Example 1, 20.6 g (0.05 mol) of bisphenoxyethanolfluorene, 15.2 g (0.07 mol) of diphenyl carbonate, and 2.5 × 10 -2 mol / L sodium bicarbonate solution 16.3μL (4.1×10 -7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After dissolving the substrate, the temperature was raised stepwise to 240°C over 80 minutes, and the pressure was reduced stepwise to 150 mmHg. The pressure was further reduced stepwise to a vacuum over 40 minutes, and after holding for 20 minutes, 25 g of the produced polycarbonate resin (hereinafter referred to as "polycarbonate resin 2") was taken out. During the reaction, phenol, which was a by-product, was distilled off. The taken-out polycarbonate resin 2 was pulverized, and the glass transition temperature was measured, which was 142.2°C. The number average molecular weight Mn was 12700, the weight average molecular weight Mw was 25800, and the polydispersity Mw / Mn was 2.0. The refractive index was 1.597. The Abbe number was 30.2. The total light transmittance was 91%. The results are shown in Table 1.

[0105] [Production Example 3] (Production of Polycarbonate Resin 3) 6.5 g (0.02 mol) of the compound 3 obtained in Reference Example 1, 26.0 g (0.06 mol) of bisphenoxyethanolfluorene, 16.3 g (0.08 mol) of diphenyl carbonate, and 2.5 × 10 -2 mol / L sodium bicarbonate solution 30.0 μL (7.5 × 10 -7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After dissolving the substrate, the temperature was raised stepwise to 240°C over 80 minutes, and the pressure was reduced stepwise to 150 mmHg. The pressure was further reduced stepwise to a vacuum over 40 minutes, and after holding for 20 minutes, 27 g of the produced polycarbonate resin (hereinafter referred to as "polycarbonate resin 3") was taken out. During the reaction, phenol by-product was distilled off. The taken-out polycarbonate resin 3 was pulverized, and the glass transition temperature was measured, which was 148.8°C. The number average molecular weight Mn was 15,700, the weight average molecular weight Mw was 32,200, and the polydispersity Mw / Mn was 2.1. The refractive index was 1.610. The Abbe number was 26.2. The total light transmittance was 90%.

[0106] [Production Example 4] (Production of Polycarbonate Resin 4) 7.9 g (0.02 mol) of the compound 3 obtained in Reference Example 1, 18.4 g (0.04 mol) of bisphenoxyethanolfluorene, 13.2 g (0.06 mol) of diphenyl carbonate, and 2.5 × 10 -2 mol / L sodium bicarbonate solution 24.3μL (6.1×10 -7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After dissolving the substrate, the temperature was raised stepwise to 240°C over 80 minutes, and the pressure was reduced stepwise to 150 mmHg. The pressure was further reduced stepwise to a vacuum over 40 minutes, and after holding for 20 minutes, 29 g of the produced polycarbonate resin (hereinafter referred to as "polycarbonate resin 4") was taken out. During the reaction, phenol by-product was distilled off. The taken-out polycarbonate resin 4 was pulverized, and the glass transition temperature was measured, which was 149.0°C. The number average molecular weight Mn was 17,000, the weight average molecular weight Mw was 35,800, and the polydispersity Mw / Mn was 2.1. The refractive index was 1.594. The Abbe number was 28.5. The total light transmittance was 90%.

[0107] [Production Example 5] (Production of Polycarbonate Resin 5) 6.8 g (0.01 mol) of the compound 4 obtained in Example 3, 23.8 g (0.05 mol) of bisphenoxyethanolfluorene, 15.0 g (0.07 mol) of diphenyl carbonate, and 2.5 × 10 -2 mol / L sodium bicarbonate solution 24.8μL (6.9×10 -7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After dissolving the substrate, the temperature was raised stepwise to 240°C over 80 minutes, and the pressure was reduced stepwise to 150 mmHg. The pressure was further reduced stepwise to a vacuum over 40 minutes, and after holding for 20 minutes, 25 g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 5") was taken out. During the reaction, phenol, which was a by-product, was distilled off. The polycarbonate resin 5 taken out was pulverized, and the glass transition temperature was measured, which was 147.6°C. The number average molecular weight Mn was 13,400, the weight average molecular weight Mw was 28,100, and the polydispersity Mw / Mn was 2.1. The refractive index was 1.620. The Abbe number was 25.0. The total light transmittance was 90%. The results are shown in Table 1.

[0108] [Production Example 6] (Production of Polycarbonate Resin 5) 9.2 g (0.02 mol) of the compound 4 obtained in Example 3, 18.8 g (0.04 mol) of bisphenoxyethanolfluorene, 13.5 g (0.07 mol) of diphenyl carbonate, and 2.5 × 10 -2 mol / L sodium bicarbonate solution 24.7μL (6.2×10 -7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After dissolving the substrate, the temperature was raised stepwise to 240°C over 80 minutes, and the pressure was reduced stepwise to 150 mmHg. The pressure was further reduced stepwise to a vacuum over 40 minutes, and after holding for 20 minutes, 25 g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 5") was taken out. During the reaction, phenol, which was a by-product, was distilled off. The polycarbonate resin 5 taken out was pulverized, and the glass transition temperature was measured, which was 147.9°C. The number average molecular weight Mn was 14100, the weight average molecular weight Mw was 29600, and the polydispersity Mw / Mn was 2.1. The refractive index was 1.609. The Abbe number was 26.2. The total light transmittance was 90%. The results are shown in Table 1.

[0109] [Comparative Production Example 1] (Production of Polycarbonate Resin A) Bisphenoxyethanolfluorene (BPEF) 59.0 g (0.13 mol), diphenyl carbonate 30.0 g (0.14 mol), and 2.5 × 10 -2 mol / L sodium bicarbonate solution 55.0μL (137.5×10 -8 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After dissolving the substrate, the temperature was raised stepwise to 240°C over 80 minutes, and the pressure was reduced stepwise to 150 mmHg. The pressure was further reduced stepwise to a vacuum over 40 minutes, and after holding for 20 minutes, 55 g of the produced polycarbonate resin (hereinafter referred to as "polycarbonate resin A") was taken out. During the reaction, phenol by-product was distilled off. The taken-out polycarbonate resin A was pulverized, and the glass transition temperature was measured, which was 147°C. The number average molecular weight Mn was 21940, the weight average molecular weight Mw was 41680, and the polydispersity Mw / Mn was 1.90. The refractive index was 1.638. The birefringence was -0.023×10 at a wavelength of 588.8 nm. -2 The Abbe number was 23.5. The total light transmittance was 90%. [Table 1]

[0110] From the results in Table 1, it was found that the polycarbonate resins obtained using compounds 1 and 3 each have a lower refractive index and a higher Abbe number than the polycarbonate resin made of BPEF in Comparative Production Example 1. In addition, when Production Examples 1 and 2, Production Examples 3 and 4, and Production Examples 5 and 6 are compared, it was found that a polycarbonate resin having a lower refractive index and a higher Abbe number can be obtained by increasing the copolymerization ratio of the monomer (resin modifier) ​​represented by formula (1). In other words, it was found that the refractive index and Abbe number of the polycarbonate resin can be adjusted to the desired range by using the resin modifier.

[0111] From the results in Table 1, it was found that a polycarbonate resin having a relatively high Abbe number was obtained by increasing the compounding ratio of Compound 1. It was also found that the increase in the Abbe number was large when the compounding ratio was increased. It was found that the decrease in the refractive index of the polycarbonate resin was small even when the compounding ratio of Compound 4 was increased. By increasing the compounding ratio of Compound 4, a polycarbonate resin having a higher glass transition temperature and a higher Abbe number than the polycarbonate resin made of BPEF in Comparative Production Example 1 was obtained. By increasing the compounding ratio of compound 3, the refractive index decreases and the glass transition temperature increases, so that a resin can be obtained that has both good optical properties such as refractive index, birefringence, and Abbe number, and good heat resistance represented by the glass transition temperature. In addition, it is useful because the raw materials are easily available industrially. [Industrial Applicability]

[0112] The resin modifier of the present invention is useful as a resin modifier for polycarbonate resin or polycarbonate resin. By using the resin modifier, the physical properties such as glass transition temperature, refractive index, birefringence, Abbe number, etc. of the resin can be widely adjusted. Therefore, it is suitable for use in optical members such as optical lenses, optical films, and optical sheets.

Claims

1. A resin modifier for polycarbonate resin or polyester polycarbonate resin, comprising a compound represented by formula (1): 【Chemistry 1】 [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.

2. R １ and are the same or different and are a C1-4 alkyl group.

3. 3. The resin modifier according to claim 1, which is a resin modifier for a polycarbonate resin or a polyester polycarbonate resin used for optical members.

4. A compound represented by formula (1B): 【Chemistry 2】 [In the formula, R １１ are the same or different and each is a hydrogen atom, a methyl group, or an ethyl group.

5. A resin modifier comprising the compound according to claim 4.

6. The resin modifier according to claim 5 , wherein the resin modifier is a polyester resin, a polycarbonate resin, or a polyester polycarbonate resin.

7. The resin modifier according to claim 5 , which is a resin modifier for a resin used in an optical member.

8. A method for producing a compound represented by formula (1B), comprising a step of reacting a compound represented by formula (3B) with a compound represented by formula (4A). 【Chemistry 3】 [In the formula, R １１ are the same or different and each is a hydrogen atom, a methyl group, or an ethyl group.

9. A method for modifying a polycarbonate resin or a polyester polycarbonate resin using the resin modifier according to claim 1.

10. The method according to claim 9, wherein the modification method is a method for adjusting at least one property selected from the group consisting of glass transition temperature, refractive index, and Abbe number of a polycarbonate resin or a polyester polycarbonate resin obtained after copolymerization by adjusting the content of the resin modifier according to claim 1 in the total polyol raw material.

11. A resin containing a structural unit represented by formula (2), the resin being a polycarbonate resin or a polyester carbonate resin. 【Chemistry 4】 [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.

12. An optical member comprising the resin according to claim 11.

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