Thermoplastic resin with carbonate bonds

Abstract

To provide a new thermoplastic resin having a carbonate bond and a condensed ring.SOLUTION: A carbonate-based resin includes a structure represented by the following formula (A1). In the formula (A1), X represents formula (B1). Rings Y and Z forming a condensed ring with cyclobutane in the formula (B1) each independently represents an alicyclic carbon ring having 15 or less carbon atoms which may have a substituent. The alicyclic carbon ring may include a hetero atom and may have a condensed ring. L1 and L2 in the formula (B1) each independently represents a divalent hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to thermoplastic resins having carbonate linkages. [Background technology]

[0002] Resins having carbonate bonds, such as polycarbonate resins and polyester carbonate resins, are widely used as thermoplastic resins. For example, polycarbonate resins generally contain bisphenols as monomer components, and are widely used as so-called engineering plastics in the fields of electric and electronic parts, automobile parts, medical parts, building materials, films, sheets, bottles, optical recording media, lenses, etc., taking advantage of their advantages such as transparency, heat resistance, and mechanical strength. In addition, polycarbonate diols are used as raw materials for polyurethanes, etc., by reacting them with isocyanate compounds, for example.

[0003] In recent years, polycarbonate resins containing compounds other than bisphenol as monomer components have been developed. For example, Patent Documents 1 and 2 have developed polycarbonate resins containing an ether group-containing diol, such as isosorbide, as a monomer component. Patent Documents 3 to 5 propose polycarbonate resins containing a compound containing a fluorene ring as a monomer component. Patent Documents 6 and 7 propose polycarbonate resins containing a condensed ring compound containing a norbornane skeleton as a monomer component. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. WO2004 / 111106 [Patent Document 2] International Publication No. WO2007 / 063823 [Patent Document 3] Patent No. 5119250 [Patent Document 4] Patent No. 5204200 [Patent Document 5] JP 2015-25111 A [Patent Document 6] Japanese Patent Application Publication No. 6-43302 [Patent Document 7] JP 2002-322267 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, the applications of thermoplastic resins having carbonate bonds, such as polycarbonate resins, have been expanding, and the required performance in terms of mechanical properties, heat resistance, etc. has become more diverse. Therefore, the development of thermoplastic resins having novel structures is desired.

[0006] The present invention has been made in view of the above background, and aims to provide a novel thermoplastic resin having a carbonate bond and a condensed ring. [Means for solving the problem]

[0007] One aspect of the present invention is a thermoplastic resin containing a structure represented by the following formula (A1).

[0008] [ka]

[0009] [ka]

[0010] X in formula (A1) represents the above formula (B1). The rings Y and Z forming a condensed ring with the cyclobutane in formula (B1) each independently represent an alicyclic carbon ring having 15 or less carbon atoms which may have a substituent. The alicyclic carbon ring may contain a heteroatom. L in formula (B1) 1 and L 2 each independently represents a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. Effect of the Invention

[0011] According to the above embodiment, it is possible to provide a novel thermoplastic resin having a carbonate bond and a condensed ring. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a diagram showing the reaction for synthesizing dihydroxy compound P1 by process A. [Diagram 2] FIG. 2 is a diagram showing the reaction for synthesizing dihydroxy compound P1 by process B. [Diagram 3] FIG. 3 is a diagram showing the reaction for synthesizing dihydroxy compound P1 by process C. [Figure 4] FIG. 4 is a diagram showing the reaction for synthesizing dihydroxy compound P1 by process D. [Diagram 5] FIG. 5 is a diagram showing the reaction for synthesizing dihydroxy compound P1 by process E. [Figure 6] FIG. 6 is a diagram showing a reaction for synthesizing compound (P1) from compound (N1) and compound (N2). [Figure 7] FIG. 7 shows a first example group of combinations of starting materials and dihydroxy compounds obtained from the starting materials. [Figure 8] FIG. 8 shows a second example group of combinations of each starting material and a dihydroxy compound obtained from the starting material. [Figure 9] FIG. 9 is an NMR chart of the polycarbonate copolymer obtained in Example 1-1. [Figure 10] FIG. 10 is an NMR chart of the polycarbonate copolymer obtained in Example 1-2. [Figure 11] FIG. 11 is an NMR chart of the polycarbonate copolymer obtained in Example 1-3. [Figure 12] FIG. 12 is an NMR chart of the polycarbonate copolymer obtained in Example 1-4. [Figure 13]FIG. 13 is an NMR chart of the polycarbonate copolymer obtained in Example 1-5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The following describes the embodiments of the present invention in detail, but the following description of the configuration and the like is merely an example of an embodiment of the present invention, and the present invention is not limited to the following content as long as it does not exceed the gist of the present invention. In addition, when the expression "~" is used in this specification, it is used to mean that the numerical values ​​or physical values ​​written before and after it are included. In addition, the numerical values ​​or physical values ​​written as upper and lower limits are used to mean that the values ​​are included. In addition, "ppm" and "%" mean "ppm by weight" and "% by weight", respectively, unless otherwise specified. In addition, "parts by weight" and "parts by mass", "% by weight" and "% by mass" are essentially synonymous.

[0014] The thermoplastic resin having a carbonate bond has a structure represented by the following formula (A1). In this specification, the thermoplastic resin having a carbonate bond is appropriately referred to as a "carbonate-based resin". Examples of the carbonate-based resin include a polycarbonate resin having a carbonate bond and a polyester carbonate resin having a carbonate bond and an ester bond.

[0015] The carbonate-based resin is a concept that includes not only homopolymers having a repeating structure of formula (A1), but also copolymers having a repeating structure of formula (A1) and a structure other than formula (A1) (specifically, copolymeric polycarbonates and copolymeric polyester carbonates).

[0016] [ka]

[0017] The carbonate-based resin has a structure in which a plurality of divalent structural units (hereinafter also simply referred to as "structural units") are linked via a divalent linking group (hereinafter also simply referred to as "linking group"). The linking group may be bonded to a unit located at the terminal of the plurality of structural units, or a polymerization reactive group may be bonded to the unit.

[0018] At least a part of the linking groups of the carbonate resin is a carbonate bond (-OC(=O)-O-), and when a plurality of linking groups are present in the carbonate resin, the linking groups may be carbonate bonds and bonds other than carbonate bonds. Examples of the other bonds include ester bonds, amide bonds, phosphonate bonds, and sulfone bonds.

[0019] From the viewpoint of inexpensive and easy synthesis of the carbonate-based resin, it is preferable that all the linking groups in the carbonate-based resin are carbonate bonds, or carbonate bonds and ester bonds. Also, from the viewpoint of easy adjustment of the molar ratio of the monomers used during polymerization and easy polymerization, it is more preferable that all the linking groups in the thermoplastic resin are carbonate bonds. In other words, the carbonate-based resin is preferably a polycarbonate resin or a polyester carbonate resin, and more preferably a polycarbonate resin. When the linking group is asymmetric, such as an ester bond, the linking group may link two adjacent structural units in any direction.

[0020] The structure represented by formula (B1) is appropriately referred to as a “structural unit B1.” Formula (B1) represents X in formula (A1) and is a partial structural formula of formula (A1).

[0021] [ka]

[0022] The carbonate-based resin has a structural unit B1. As shown in formula (B1), ring Y and ring Z sandwich cyclobutane and each form a condensed ring with cyclobutane. In other words, ring Y and ring Z sandwich cyclobutane and are condensed to this cyclobutane. In formula (B1), ring Y and ring Z each independently represent an alicyclic carbon ring having 15 or less carbon atoms. The alicyclic carbon ring means a cyclic skeleton of an alicyclic compound, and is a concept including not only a ring composed of carbon but also a heterocycle. If the carbon number of the alicyclic carbon ring exceeds 15, there are many rigid bonds, there is no room for bond rotation, and the carbonate-based resin may become brittle. In addition, if the carbon number exceeds 15, it becomes difficult to synthesize at low cost, and the production cost increases. From the viewpoint of further suppressing the resin from becoming brittle and the production cost from increasing, the carbon number of the alicyclic carbon ring is preferably 12 or less, more preferably 10 or less. The lower limit of the number of carbon atoms in an alicyclic carbocycle is 3. The number of carbon atoms in an alicyclic carbocycle specifically refers to the number of atoms connected in a ring in the alicyclic carbocycle, and in the case of a heterocycle, it means the number including not only the number of carbon atoms but also atoms other than carbon (specifically, heteroatoms).

[0023] At least one of the alicyclic carbocycles of ring Y and ring Z may have one or more substituents. Examples of the substituent that at least one of the alicyclic carbocycles of ring Y and ring Z may have include a hydrocarbon group having 1 to 14 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 3 to 14 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, a silyl group, a sulfinyl group, a sulfo group, an alkylthio group, an arylthio group, an amino group, a halogen atom, a nitro group, a cyano group, and the like.

[0024] Specific examples of the hydrocarbon group having 1 to 14 carbon atoms include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and an aryl group having 3 to 14 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Examples of the alkynyl group having 2 to 10 carbon atoms include an acetylene group and a propynyl group. Examples of the aryl group having 3 to 14 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

[0025] An example of an acyl group having 1 to 10 carbon atoms is an acetyl group. An example of an alkoxy group having 1 to 12 carbon atoms is a methoxy group, an ethoxy group, or a propoxy group. An example of an aryloxy group having 3 to 14 carbon atoms is a phenoxy group. An example of an acyloxy group having 1 to 10 carbon atoms is a methoxyacetyl group or a phenoxyacetyl group. An example of a silyl group is a trimethylsilyl group. An example of a sulfo group is a sulfo group, a methylsulfonyl group, or an ethylsulfonyl group. An example of a sulfinyl group is a methylsulfinyl group or an ethylsulfinyl group. An example of an alkylthio group is a methylthio group or an ethylthio group. An example of an arylthio group is a phenylthio group. An example of an amino group is an amino group or a dimethylamino group.

[0026] The substituents which may be present on ring Y and ring Z, such as the above-mentioned hydrocarbon group having 1 to 14 carbon atoms, may further have one or more substituents, and examples of the substituents include an alkoxy group, a halogen atom, a nitro group, and a cyano group.

[0027] From the viewpoint of increasing the proportion of rigid skeletons among the structural units of the carbonate resin and obtaining a resin with excellent heat resistance, it is preferable that the alicyclic carbon ring has no substituent and a hydrogen atom is bonded to the carbon atom constituting the alicyclic carbon ring, or that the alicyclic carbon ring has a hydrocarbon group having 1 to 14 carbon atoms as a substituent. From the viewpoint of improving toughness and reducing the melt viscosity, for example, improving the fluidity of the resin during molding, it is preferable that the substituent is an alkyl group having 5 to 12 carbon atoms. From the viewpoint of improving the heat resistance of the resin, it is preferable that the substituent is an alkyl group having 1 to 4 carbon atoms. From the viewpoint of further improving the heat resistance of the resin and the ease of synthesis of the monomer, it is preferable that the substituent is an alkyl group having 1 to 2 carbon atoms, and more preferably an alkyl group having 1 carbon atom (specifically, a methyl group). From the viewpoint of further improving the heat resistance of the resin and making the raw materials available at low cost, it is preferable that the alicyclic carbon rings in rings Y and Z each have one methyl group as a substituent, and that the other carbon atoms constituting the alicyclic carbon ring (i.e., the carbon atoms other than the carbon atom to which the methyl group is bonded) have no substituents and are bonded to hydrogen atoms. From the viewpoint of enabling the resin to have both excellent heat resistance and toughness and making the raw materials available at low cost, it is preferable that the alicyclic carbon rings in rings Y and Z do not have any substituents. However, in the viewpoint of enabling the resin to have both excellent heat resistance and toughness and making the raw materials available at low cost, it is preferable that the alicyclic carbon rings in rings Y and Z each have one methyl group as a substituent. 1 and L 2 represents a linking group and is not included in the substituents.

[0028] From the viewpoint of toughness and heat resistance of the carbonate-based resin, the substituents of the alicyclic carbon rings of rings Y and Z are preferably alkoxy groups having 1 to 10 carbon atoms, more preferably alkoxy groups having 1 to 3 carbon atoms from the same viewpoint, and further preferably methoxy groups from the viewpoint of superior toughness and heat resistance.

[0029] If the hydrogen atom at the β-position carbon of the hydroxyl group is substituted with an alkyl group, the elimination of the hydroxyl group from the monomer during the production of the resin can be suppressed. This allows the polymerization temperature to be increased and a resin with a larger molecular weight can be obtained. 1 , L 2 When is a methylene group, L is a carbon atom of the alicyclic carbocyclic ring in ring Y and ring Z. 1 , L 2 It is preferred that a substituent is further bonded to the carbon atom to which is bonded.

[0030] In this specification, the term "alicyclic carbocycle" includes those having a fused ring. At least one of the alicyclic carbocycles, ring Y and ring Z, may have a fused ring. In this case, the number of carbon atoms in the alicyclic carbocycle containing the fused ring (specifically, ring Y and ring Z) is 15 or less as described above. When the alicyclic carbocycle contains a fused ring, the bond distance between the monomer units constituting the resin (specifically, the bond distance between the structural units B1) can be increased. This improves the mechanical properties such as the toughness of the resin.

[0031] At least one of the alicyclic carbon rings of ring Y and ring Z may contain a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom. From the viewpoint of imparting polarity to the structural unit B1 and improving the affinity between the thermoplastic resin having the structural unit B1 and a different polymer, and the compatibility when blended with a different polymer, the heteroatom is preferably an oxygen atom and / or a sulfur atom. The alicyclic carbon ring may contain a heteroatom, for example, as the functional group. In addition, the alicyclic carbon ring may contain a heteroatom as a crosslinked structure described later. From the viewpoint of facilitating the synthesis of the monomer, of being unlikely to inhibit the condensation polymerization reaction during the production of the carbonate-based resin, and of being able to reduce the polarity of the carbonate-based resin and suppress the water absorption rate, it is preferable that ring Y and ring Z do not contain a heteroatom.

[0032] At least one of the alicyclic carbon rings of ring Y and ring Z preferably has at least one carbon ring having 4 or more carbon atoms constituting the ring. In this case, the skeleton constituting the resin becomes rigid, and heat resistance is improved.

[0033] At least one of the alicyclic carbon rings of ring Y and ring Z preferably has a structure in which a hydrocarbon group having 5 or less carbon atoms bonded to a carbon atom constituting the alicyclic carbon ring is bonded to another carbon atom constituting the alicyclic carbon ring to form a ring, such as a norbornane skeleton. That is, it is preferable that the alicyclic carbon ring has a structure in which a hydrocarbon group having 5 or less carbon atoms is crosslinked. In this case, the skeleton constituting the resin becomes rigid, and the heat resistance and pencil hardness are improved. From the viewpoint of improving this effect, the carbon number of the hydrocarbon group of the crosslinked structure is more preferably 3 or less, and even more preferably 2 or less.

[0034] In addition, at least one of the alicyclic carbocycles of ring Y and ring Z preferably has a structure in which an oxygen atom bonded to a carbon atom constituting the alicyclic carbocycle is bonded to another carbon atom constituting the alicyclic carbocycle to form a ring, such as, for example, oxabicyclo[2.2.1]heptane. That is, it is preferable to have a structure in which an oxygen atom is bridged to the alicyclic carbocycle (i.e., a cyclic ether bond). In this case, the polarity of the heteroelement is high, so the compatibility between the carbonate resin and a different polymer is improved. In addition, at least one of the alicyclic carbocycles of ring Y and ring Z preferably has a structure in which a sulfur atom bonded to a carbon atom constituting the cyclic carbocycle is bonded to another carbon atom constituting the alicyclic carbocycle to form a ring, such as, for example, thiabicyclo[2.2.1]heptane. That is, it is preferable to have a structure in which a sulfur atom is bridged to the alicyclic carbocycle (i.e., a cyclic thioether bond). In this case, similarly, the polarity of the heteroelement is high, so the effect of improving the compatibility between the carbonate resin and a different polymer is obtained.

[0035] L 1 and L 2each independently represents a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group is, for example, an alkylene group, and may be linear or branched. From the viewpoint of further improving the toughness and moldability of the resin (specifically, the fluidity of the molten resin during molding), L 1 and L 2 The number of carbon atoms of the hydrocarbon group is preferably 3 to 5. On the other hand, from the viewpoint of improving the heat resistance by forming a rigid skeleton while ensuring the toughness of the resin, L 1 and L 2 The number of carbon atoms in the hydrocarbon group is preferably 1 to 2. Furthermore, from the viewpoint of reducing the cost of raw materials for synthesizing monomers during the production of carbonate-based resins, L 1 and L 2 is preferably a methylene group, which is also called a methanediyl group.

[0036] It is preferable that the alicyclic skeletons of ring Y and ring Z in formula (B1) are different from each other. That is, it is preferable that ring Y and ring Z are asymmetric with respect to the cyclobutane ring in formula (B1). In this case, the solubility can be improved, and the effect of being advantageous in the synthesis of monomers and the preparation of polymers can be obtained. In addition, the effect of being able to reduce the photoelastic coefficient of the carbonate resin having the structure of formula (B1) can be obtained.

[0037] Formula (B1) is preferably represented by the following formula (B1') or (B1''). In formula (B1'), there is one substituent bonded to ring Y and one substituent bonded to ring Z in formula (B1), and L 1 and L 2 is a methylene group, and in formula (B1″), there is one substituent bonded to each of ring Y and ring Z in formula (B1), and L 1 and L 2is a direct bond. In this case, it is possible to achieve a high level of compatibility between toughness and heat resistance of the resin. In formula (B1') and formula (B1''), rings Y and Z which form a condensed ring with cyclobutane each independently represent an alicyclic carbon ring having 4 to 15 carbon atoms constituting the ring. This alicyclic carbon ring may contain a heteroatom and may have a condensed ring, as in formula (B1). In addition, R 1 and R 2 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. The hydrocarbon group and alkoxy group are as described above.

[0038] [ka]

[0039] [ka]

[0040] In formula (B1'), R 1 ,R 2 are each preferably independently a hydrogen atom or a methyl group. 1 and R 2 is preferably a methyl group. This means that no substituent is bonded to the carbon atoms other than the carbon atom to which the methyl group is bonded, and instead hydrogen atoms are bonded. In this case, the raw materials can be obtained at low cost, and the skeleton constituting the carbonate resin becomes rigid, improving the heat resistance. From the same viewpoint, R in formula (B1'') is preferably a methyl group. 1 ,R 2 Each of R is preferably independently a methoxy group or an ethoxy group. 1 and R 2is more preferably a hydrogen atom. As a result, the alicyclic carbon ring in ring Y and ring Z does not have a substituent, and a hydrogen atom is bonded to the carbon atom constituting the alicyclic carbon ring. In this case, too, the raw material can be obtained at low cost, and the skeleton constituting the carbonate resin becomes rigid, improving heat resistance.

[0041] Rings Y and Z in formula (B1), formula (B1'), and formula (B1'') are each preferably independently any ring selected from the following formulae (C1) to (C11), and more preferably alicyclic carbon rings represented by formulae (C1) to (C7). In this case, it is possible to achieve both heat resistance and toughness. In addition, * in formulae (C1) to (C11) indicates the site of formation of the condensed ring, and the rings of formulae (C1) to (C11) form condensed rings with cyclobutane in formula (B1), formula (B1'), and formula (B1'') at the positions sandwiched by *. Formulae (C1) to (C11) are partial structural formulae representing rings Y and rings Z in formulae (B1), formula (B1'), and formula (B1'').

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048]

change

[0049]

change

[0050]

change

[0051]

change

[0052]

change

[0053] From the viewpoint of achieving both toughness and heat resistance of the carbonate-based resin, it is preferable that rings Y and Z in formulas (B1), (B1'), and (B1'') are each independently any one selected from the group consisting of formulas (C5), (C7), (C8), and (C11). Furthermore, from the viewpoint of improving the heat resistance of the carbonate-based resin and making the raw materials available at low cost, it is preferable that rings Y and Z in formulas (B1), (B1'), and (B1'') are each independently any one of formulas (C2) and (C6). In addition, since polarity is imparted to the structural unit B1, from the viewpoints of improving the affinity between the carbonate-based resin and a different polymer (specifically, a polar resin), improving the adhesion at the interface with the different polymer, improving the heat resistance, and making the raw materials available at low cost, it is preferable that the rings Y and Z in formulas (B1), (B1'), and (B1'') are each independently either one of formulas (C9) and (C10). In addition, from the viewpoints of improving the heat resistance and toughness of the carbonate-based resin and making the raw materials available at low cost, it is preferable that the rings Y and Z in formulas (B1), (B1'), and (B1'') are each independently either one selected from the group consisting of formulas (C1), (C3), (C4), and (C7). From the viewpoints of further improving the toughness of the carbonate-based resin and making the raw materials available at low cost, it is preferable that rings Y and Z in formula (B1), formula (B1'), and formula (B1'') are each independently any one selected from the group consisting of formula (C3), formula (C4), and formula (C7).

[0054] Specific examples of formula (B1') and formula (B'') include the following formulas (B2) to (B23).

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058]

change

[0059]

change

[0060]

change

[0061]

change

[0062]

change

[0063]

change

[0064]

change

[0065]

change

[0066]

change

[0067]

change

[0068] [ka]

[0069] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0070] R in formulas (B2) to (B26) 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. The hydrocarbon group having 1 to 14 carbon atoms and the alkoxy group having 1 to 12 carbon atoms are the same as those in the above formula (B1).

[0071] From the viewpoint of being able to obtain raw materials at low cost, R 1 and R 2are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group. The alkyl group having 1 to 12 carbon atoms is the same as that in the above formula (B1). From the viewpoint of being able to obtain raw materials at low cost, R 1 and R 2 are each independently preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.

[0072] From the viewpoint of further improving the heat resistance of the carbonate-based resin, the formula (B1′) is the formula (B4), the formula (B5), the formula (B7), or the formula (B11), and R 1 and R 2 are each preferably independently a hydrogen atom or a methyl group. From the viewpoint of imparting polarity to the structural unit B1, and thereby improving the affinity between the carbonate resin and a different polymer and the adhesiveness at the interface with the different polymer, it is preferable that Formula (B1') is Formula (B13) or Formula (B14), and R 1 and R 2 are preferably each independently a hydrogen atom or a methyl group. From the viewpoint of achieving high levels of both heat resistance and toughness of the carbonate-based resin, it is preferable that Formula (B1') is Formula (B2), Formula (B3) or Formula (B11), and R 1 and R 2 are preferably each independently a hydrogen atom or a methyl group. From the viewpoint of achieving high levels of heat resistance and toughness of the carbonate-based resin and inexpensive availability of the raw materials, it is preferable that formula (B1') is formula (B2) or formula (B3), and R 1 and R 2 are preferably each independently a hydrogen atom or a methyl group. From the viewpoints of achieving high levels of heat resistance and toughness of the carbonate-based resin, inexpensive availability of raw materials, and ease and cost of synthesis of the monomer, it is preferable that Formula (B1') is Formula (B2), and R 1 and R 2Preferably, each independently represents a hydrogen atom or a methyl group.

[0073] From the viewpoint of further improving the heat resistance of the carbonate-based resin, the formula (B1″) is the formula (B18), the formula (B19), the formula (B21), or the formula (B25), and R 1 and R 2 are each preferably independently a methoxy group or an ethoxy group. From the viewpoint of achieving high levels of both heat resistance and toughness of the carbonate-based resin, it is preferable that Formula (B1″) is Formula (B16), Formula (B17), or Formula (B25), and R 1 and R 2 are each preferably independently a methoxy group or an ethoxy group. From the viewpoint of achieving high levels of heat resistance and toughness of the carbonate-based resin and inexpensive availability of the raw materials, it is preferable that Formula (B1″) is Formula (B2) or Formula (B17), and R 1 and R 2 are each preferably independently a methoxy group or an ethoxy group. From the viewpoints of achieving high levels of heat resistance and toughness of the carbonate-based resin, inexpensive availability of raw materials, and ease and cost of synthesis of the monomer, it is preferable that Formula (B1″) is Formula (B16), and R 1 and R 2 is preferably each independently a methoxy group or an ethoxy group.

[0074] Next, the monomer for constituting the structural unit B1 will be described. The carbonate-based resin has a repeating structural unit of formula (B1). The repeating structural unit of formula (B1) is appropriately referred to as the "first structural unit B1". In the production of a carbonate-based resin having such a repeating structural unit, a dihydroxy compound represented by the following formula (P1) is used as a monomer raw material. That is, L, which is the linking group in formula (B1), 1 , L 2 A dihydroxy compound having a hydroxy group bonded to each of the terminals of L is used. 1 , L 2may each be a direct bond. The dihydroxy compound forms a polymer chain of the carbonate-based resin together with the oxygen atom of the hydroxy group. Therefore, in the carbonate-based resin, the structure of the above formula (B1) that does not contain an oxygen atom derived from the hydroxy group of the dihydroxy compound can be regarded as a structural unit. 1 , L 2 The structure in which -O- is bonded to the end of the formula (B1) can be regarded as a structural unit. 1 , L 2 The structural unit having -O- bonded to the end thereof is appropriately referred to as the "second structural unit B1".

[0075] [ka]

[0076] In formula (P1), ring Y, ring Z, substituents, heteroatoms, fused rings, L 1 , L 2 is the same as the above-mentioned formula (B1) except that it is a dihydroxy compound, and the preferred forms are also the same as the above-mentioned formulas (B1), (B1'), (B1''), etc. Preferred forms of formula (P1) are shown in formulas (P2) to (P15). R in formulas (P2) to (P15) 1 and R 2 are the same as those of formulae (B2) to (B15). Specifically, formulae (P2) to (P15) are preferred forms of monomers for constituting formula (B1'). Preferred forms of monomers for constituting formula (B'') include monomers in which the two hydroxymethyl groups shown in each of formulae (P2) to (P15) are replaced with hydroxy groups, and descriptions of their chemical formulas are omitted except for (P16).

[0077] [ka]

[0078] [ka]

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088]

change

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] When a polycarbonate resin is produced using a compound represented by the following formula (P24) as a monomer, a polycarbonate resin having a structural unit represented by the following formula (B24) is obtained. The brittle fracture stress of a homopolycarbonate of the compound represented by formula (P24) was estimated using the polymer property estimation software Polymer-Design Tools version 1.1 manufactured by DTW Associates, Inc. in the United States, and the estimated value by the Bicerano method was 153 MPa. This value exceeds the value of a homopolycarbonate of 2,3-di(hydroxymethyl)-perhydro-1,4:5,8-dimethanonaphthalene (DMNDM) represented by the following formula (Z1) estimated by the same method. When a resin is subjected to force, it is called brittle fracture when it breaks with almost no deformation, and the stress at which brittle fracture occurs is the brittle fracture stress. In general, the higher the brittle fracture stress, the more excellent the toughness of the resin, which can withstand a large stress. In other words, it is suggested that a polycarbonate resin having a structural unit represented by formula (B24) exhibits excellent toughness. Since it has a structure similar to that of formula (B24), it is believed that a polycarbonate resin having a structural unit of formula (B1) also exhibits excellent toughness.

[0093] In addition, when the glass transition temperature Tg of a polycarbonate resin produced using the compound represented by formula (P24) as a monomer was calculated using the Bicerano method of the above software, the Tg was 120°C (extrapolated value). This value exceeds that of the homopolycarbonate of tricyclodecane dimethanol described below. In other words, it is suggested that a polycarbonate resin having a structural unit of formula (B24) exhibits excellent heat resistance. Since it has a structure similar to formula (B24), a polycarbonate resin having a structural unit of formula (B1) is also considered to exhibit excellent heat resistance.

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] The method for producing the dihydroxy compound of formula (P1) is not particularly limited, but it can be produced, for example, by Production Methods A to C shown in Figures 1 to 3. It can also be produced by Production Methods D and E shown in Figures 4 and 5.

[0098] In Figures 1 to 3, ring Y1 and ring Z1 each independently represent an alicyclic carbocyclic ring having 15 or less carbon atoms and having two double bonds in the alicyclic carbocyclic ring. This alicyclic carbocyclic ring may have a substituent, may contain a heteroatom, or may have a condensed ring. The substituent, heteroatom, and condensed ring are the same as those in formula (B1) above.

[0099] In Figures 1 to 3, ring Y2 and ring Z2 each independently represent an alicyclic carbocyclic ring having 15 or less carbon atoms and having one double bond in the alicyclic carbocyclic ring. This alicyclic carbocyclic ring may have a substituent, may contain a heteroatom, or may have a condensed ring. The substituent, heteroatom, and condensed ring are the same as those in formula (B1) above.

[0100] In Figs. 1 to 3, M 1 and M 2 are each independently a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. The divalent hydrocarbon group may have a substituent having 1 to 5 carbon atoms. Specifically, the divalent hydrocarbon group is an alkylene group. 1 and L 2 is the same as in the above formula (B1), P is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0101] As shown in FIG. 1, compound (M3) is produced from compound (M1) and compound (M2). Specifically, two unsaturated molecules having 2m and 2n π electrons, such as compound (M1) and compound (M2), form two metal-carbon bonds and one carbon-carbon bond in the presence of a transition metal active species (specifically, a metal catalyst), and are cyclized to form a metallacycle (not shown). At this time, the oxidation state of the metal center formally increases by two valences. After that, a carbon-carbon bond is formed through reductive elimination, and the oxidation state of the transition metal center is reduced to regenerate the active species. This allows multiple reactions, such as the polymerization of unsaturated molecules, to proceed. At this time, when Pd or Ni is used, a four-membered ring is formed (see Kenji Ito, "Cycloaddition Reactions Using Organic Transition Metal Complexes," 2002, vol. 60, No. 1, pp. 28-41). In addition, when an Fe catalyst is used, a four-membered ring is formed from two unsaturated molecules (see Jordan M. Hoyt et al., “Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes,” Science, Vol. 349, Issue 6251, August 28, 2015, p. 960-p. 963).Also, in unsaturated structures with heteroatoms at bridgehead or other positions, such as 1,4-dihydro-epoxynaphthalene, Ni can be used to form four-membered rings (see Daw-Jen Huang et al., “[2+2]Dimerization of norbornadiene and its derivatives in the presence of nickel complexes and zinc metal”, Journal of Organometallic Chemistry, 490, 1995, C1-C7).

[0102] In the manufacturing method shown in Figures 1 to 3, a cyclic diene compound such as a cyclopentadiene skeleton, or a compound having a distorted unsaturated bond such as a norbornene skeleton can be used as compound (M1), compound (M2), compound (M5), and compound (M8). By using a compound having a cyclopentadiene skeleton and a compound having a norbornene skeleton as raw materials, the reactivity of the raw materials is increased, and a four-membered ring structure (specifically, cyclobutane) is easily formed.

[0103] In addition, compounds with distorted unsaturated bonds such as the norbornene skeleton can form four-membered rings by photocyclization. In fact, it is known that dicyclopentadiene dimerizes when irradiated with light in the presence of a metal catalyst (Robert G. Salomon et al., “Copper(I) catalysis in photocycloadditions. I. Norbornene” Journal of the American Chemical Society, 1974, 96, 4, p. 1137). Therefore, compounds with four-membered ring structures can also be produced by photocyclization. However, photoreactions generally have low yields and are not suitable for the synthesis of alicyclic compounds with asymmetric structures relative to the four-membered ring, such as those shown in Figures 1 to 3 and 6.

[0104] As shown in Figure 1, in Process A, a cyclization reaction occurs between compound (M1) and compound (M2) to obtain compound (M3). Then, an oxo reaction occurs to obtain compound (M4) in which an aldehyde is added to compound (M3). Then, a hydrogenation reaction (i.e., a reduction reaction) of compound (M4) produces compound P1.

[0105] In the manufacturing method A, in the cyclization reaction of the compound (M1) and the compound (M2), Pd(dba)2, Pd(acac)2, Pd(PPh3)4, PdCl2(PPh3)2, PdCl2(dppp), PdCl2(H2NCH2CH2NH2), NiCl2, NiBr2, NiCl2(PPh3)2, Ni(Cod)2, etc. are used as transition metal catalysts, and FeCl3 is used as an iron catalyst and TiCl4 is used as a titanium catalyst. As the ligand, P(p-tolyl)3, PPh3, P[(p-MeO)Ph]3, P(Cy)3, etc. are used, but the ligand may not be used. As the reducing agent, for example, zinc can be used. The reaction temperature is, for example, 60 to 200°C. As the solvent, acetonitrile, tetrahydrofuran (i.e., THF), toluene, xylene, trimethylbenzene, tetralin, decalin, etc. are used. When a low boiling point solvent is used, the reaction may be carried out under pressure, for example, at a pressure of 0.5 MPa to 10 MPa. For the purpose of adjusting the pH during the reaction, acetic acid, propionic acid, 4-methoxybenzoic acid, benzoic acid, formic acid, chloroacetic acid, trifluoroacetic acid, pyridinium p-toluenesulfonate (i.e., PPTS), tosylic acid, methanesulfonic acid, sulfuric acid, and the like are used.

[0106] For example, compound (M3) can be converted to M 1 and M 2 The compound (M4) in which Rh is a direct bond is obtained. The reaction temperature is, for example, 20 to 200°C. The rhodium compound used in this step may be a precursor, regardless of its form, as long as it forms a complex with an organic phosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. That is, Rh(acac)(CO)2, Rh2O3, Rh4(CO) 12 , Rh6(CO) 16Alternatively, a catalyst precursor such as Rh(NO3)3 may be introduced into the reaction mixture together with an organic phosphorus compound to form a catalytically active rhodium metal hydride carbonyl phosphorus complex in the reaction vessel, or a rhodium metal hydride carbonyl phosphorus complex catalyst may be prepared in advance and introduced into the reaction vessel. The preferred amount of the rhodium catalyst is as follows. The preferred amount of the rhodium catalyst is preferably 50 to 50,000 ppm, more preferably 50 to 2,000 ppm, in terms of the amount of rhodium metal relative to 100 parts by weight of the raw material compound (M3). The molar ratio of the ligand to the rhodium metal (wherein ligand / rhodium) is in the range of 1 to 50. As the organic phosphorus compound, P(-R 1 )(-R 2 )(-R 3 ), phosphine represented by P(-OR 1 )(-OR 2 )(-OR 3 ) in phosphines and phosphites. 1 , R 2 , R 3Specific examples of the phosphite include an alkyl group having 1 to 12 carbon atoms which may be substituted, an alicyclic alkyl group having 1 to 12 carbon atoms which may be substituted, and an aryl group having 1 to 12 carbon atoms which may be substituted. Specific examples of the phosphite suitable for use in this step include tris(2-t-butylphenyl)phosphite, tris(3-methyl-6-t-butylphenyl)phosphite, tris(3-methoxy-6-t-butylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, di(2-t-butylphenyl)t-butylphosphite, and the like. The phosphines and phosphites are not limited to these. In addition, the phosphines and phosphites may be used alone or in combination of two or more kinds. As the solvent, methylcyclohexane, cyclohexane, toluene, xylene, trimethylbenzene, aliphatic hydrocarbons having 5 or more carbon atoms, ethylbenzene, propanol, butanol, and the like are used. The pressure condition during the reaction is, for example, 1 MPa to 15 MPa. For example, a mixed gas of hydrogen / carbon monoxide is used for the reaction, and the molar ratio of hydrogen to carbon monoxide in this mixed gas is preferably in the range of 0.2 to 5.0. The molar ratio of this mixed gas is the composition ratio in the introduced gas. The synthesis method of the compound (M4) containing an aldehyde group is not limited to the oxo reaction, and may be other known reactions.

[0107] The compound (M4) can be converted to the compound (P1) by the reduction reaction. A hydrogenation catalyst (i.e., a reduction catalyst) can be used for the reduction reaction. A metal catalyst such as a transition metal catalyst can be used as the hydrogenation catalyst. As such a metal catalyst, a rhodium catalyst in the above-mentioned oxo reaction; a metal belonging to Group VIII of the periodic table such as nickel, cobalt, ruthenium, palladium, and platinum having a known hydrogen reduction ability; copper chromite; copper-zinc, and the like can be used. These metal catalysts may be used as a metal element or a metal oxide, or may be used in the form of a metal element or a metal oxide supported on an inorganic carrier such as silica, alumina, diatomaceous earth, or carbon, or may be used in the form of a metal complex or the like. From the viewpoint of the hydrogen reduction reaction rate and catalyst separation after the reaction, among the hydrogenation catalysts, Rh catalyst, Raney nickel, nickel / diatomaceous earth, copper chromite, ruthenium / carbon, and ruthenium / alumina catalysts are particularly preferably used. As the solvent in the reduction reaction, methylcyclohexane, cyclohexane, toluene, xylene, trimethylbenzene, aliphatic hydrocarbons having 5 or more carbon atoms, ethylbenzene, propanol, butanol, etc. are used. The pressure condition during the reaction is, for example, 1 MPa to 15 MPa. As the ligand, the ligand preferred in the oxo reaction may be used, or no ligand may be used. It is preferable that the molar ratio of hydrogen to carbon monoxide in the carbon monoxide mixed gas is in the range of 0.2 to 5.0 as the introduced gas composition (hydrogen / carbon monoxide), or that only hydrogen gas is used. It is also possible to carry out hydrogen reduction without quenching after the oxo reaction. In that case, the same catalyst as that in the oxo reaction step, or a separate preferred catalyst is added. The synthesis of (P1) from (M4) containing an aldehyde group is not limited to the above hydrogen reduction reaction, and may be carried out by other known reactions. For example, sodium borohydride is an example of another reducing agent. A reducing agent such as sodium borohydride is used together with the solvent used in the reduction step described above or an alcohol solvent such as methanol or ethanol.

[0108] The ligand abbreviations have the following meanings: dba: dibenzylideneacetone acac: acetylacetonate PPh: Phenylphosphine dppp: diphenylphosphinopropane tolyl: methylphenyl group Cy: Cyclohexyl group Me: Methyl group Ph: Phenyl group

[0109] As shown in FIG. 2, Process B uses Compound (M1) and Compound (M5) as starting materials for cyclization reaction. Unlike Compound (M2) in Process A, Compound (M5) in Process B has only one unsaturated bond, so excessive cyclization is suppressed in Process B. In this respect, Process B is preferable. Compound (M6) is obtained by cyclization reaction between Compound (M1) and Compound (M5). Compound (M7) is obtained by adding aldehyde to Compound (M6) by, for example, Oxo reaction. Compound (P1) is then obtained by hydrogenation reaction of Compound (M7). The reaction conditions for cyclization reaction, Oxo reaction, and hydrogenation reaction are the same as those in Process A.

[0110] As shown in FIG. 3, Process C uses compound (M1) and compound (M8) as starting materials for cyclization reaction. Unlike compound (M2) in Process A, compound (M8) in Process C has only one unsaturated bond, so excessive cyclization is suppressed in Process C. In this respect, Process C is preferable. Compound (M9) is obtained by cyclization reaction between compound (M1) and compound (M8). Then, compound (M10) is obtained by adding aldehyde to compound (M9) by, for example, oxo reaction. Then, compound (P1) is obtained by hydrogenation reaction of compound (M10). The reaction conditions for cyclization reaction, oxo reaction, and hydrogenation reaction are the same as those in Process A.

[0111] As shown in FIG. 4, in the process D, the compound (M5') synthesized in the same manner as the compound (M5) and the compound (M5) are used as starting materials for the cyclization reaction. Unlike the compounds (M1) and (M2) in the process A, the compounds (M5) and (M5') in the process D have only one unsaturated bond. Therefore, excessive cyclization is suppressed in the process D. From this viewpoint, it is preferable to carry out the process D. The compound (P1-1) is obtained by the cyclization reaction between the compound (M5) and the compound (M5'). The compound (M5) and the compound (M5') may be the same. The reaction conditions for the cyclization reaction are the same as those in the process A.

[0112] As shown in FIG. 5, the process E uses the compound (M8') synthesized in the same manner as the compound (M8) and the compound (M8) as starting materials for the cyclization reaction. Unlike the compounds (M1) and (M2) in the process A, the compounds (M8) and (8') in the process E have only one unsaturated bond. Therefore, excessive cyclization is suppressed in the process E. From this viewpoint, the process E is preferably carried out. The compound (M11) is obtained by the cyclization reaction between the compound (M8) and the compound (M8'). Then, the compound (P1) is obtained by the hydrogenation reaction of the compound (M11). The compound (M8) and the compound (M8') may be the same. The reaction conditions for the cyclization reaction and the hydrogenation reaction are the same as those in the process A.

[0113] Although the substituents are omitted in FIGS. 1 to 5, compound P1 having a substituent bonded to an alicyclic carbon ring can be produced by using compounds having a substituent, for example, compound (M1), compound (M2), compound (M5), compound (M5'), compound (M8), and compound (M8').

[0114] As shown in Fig. 6, compound (P2) can be obtained, for example, by process A. Compound (N3) and compound (N4) can be obtained by cyclizing compound (N1) and compound (N2). Even if only (N1) is used as the starting material in this process without using (N2), cracking progresses during the reaction to produce (N2), and as a result, compound (N3) and compound (N4) can be obtained by the cyclization reaction between compound (N1) and compound (N2). Even if only (N2) is used in this process without using (N1), the dimerization of (N2) proceeds during the reaction to produce (N1), and as a result, (N3) and (N4) can be obtained by the cyclization reaction between compound (N1) and compound (N2) (see Kyung-sun Son, “Selective synthesis of tricyclopentadiene from dicyclopentadiene with homogeneous Pd catalysts,” Applied Organometallic Chemistry, 2014, Vol. 28, p. 151-155). Next, compound (N5) is obtained from compound (N3) and compound (N4) by an oxo reaction, and compound (N5) is reduced to obtain compound (P2). Although the description of the substituents is omitted in Figure 6, as described above, for example, compounds having substituents as compound (N1) and compound (N2) can be used to obtain compound P2 having a substituent.

[0115] As examples of compound (P1), the raw materials used for the synthesis of the above-mentioned compounds (P2), (P8), (P9), (P11), (P13), and (P14) are shown in FIG. 7. In FIG. 7, B 1 , B 2 represents a hydroxymethyl group.

[0116] Compound (P2) shown in FIG. 7 is produced by Process A using only compound (Q1), only compound (Q2), or compound (Q1) and compound (Q2) as starting materials. Compound (P8) is produced by Process B or Process C using compound (Q1) and compound (Q3) as starting materials. Compound (P9) is produced by Process B or Process C using compound (Q1) and compound (Q4) as starting materials. Compound (P11) is produced by Process B or Process C using compound (Q1) and compound (Q5) as starting materials. Compound (P13) is produced by Process B or Process C using compound (Q1) and compound (Q6) as starting materials. Compound (P14) is produced by Process B or Process C using compound (Q1) and compound (Q7) as starting materials. Other compounds represented by formula (P1) can also be produced, for example, by Production Methods A to C, by appropriately selecting starting materials.

[0117] As examples of compound (P1), the starting materials used in the synthesis of the above-mentioned compounds (P4), (P5), (P6), (P12), and (P15) are shown in FIG. 8. In FIG. 8, B 1 , B 2 represents a hydroxymethyl group. 1 , D 2 represents a hydroxymethyl group, a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, or a phenoxycarbonyl group. Compounds (P4), (P5), (P6), (P12), and (P15) can be produced by the above-mentioned Production Method D and Production Method E.

[0118] In addition, compound (M3) can be epoxidized and ring-opened with a solvent such as alcohol to obtain L 1 ,L 2 Compounds (W2) and (W3) containing a hydroxyl group directly bonded to the epoxidation are obtained. Preferred oxidizing agents for the epoxidation include metachlorobenzoic acid (i.e., mCPBA), hydrogen peroxide, and peracetic acid, and alcohols for the ring opening include methanol, ethanol, and propanol.

[0119] [ka]

[0120] In formula (Z-3), the two epoxy groups of compound (W1) are contained on ring Y and ring Z, respectively. In addition, the carbon atom to which the hydroxy group of compound (W2) is bonded and the carbon atom to which the methoxy group is bonded are adjacent carbon atoms constituting the same alicyclic carbocyclic skeleton. In other words, in formula (Z-3), the hydroxy group and the methoxy group of compound (W2) are each bonded to any two adjacent carbon atoms constituting the alicyclic carbocyclic skeleton.

[0121] The carbonate-based resin is preferably composed of a copolymer polycarbonate further containing a structural unit derived from a dihydroxy compound other than the structural unit B1. Specifically, the carbonate-based resin preferably contains, together with the structural unit B1, one or more structural units derived from a dihydroxy compound other than the compound represented by formula (P1). In this case, the desired properties can be imparted to the carbonate-based resin by introducing the structural unit derived from the other dihydroxy compound.

[0122] From the viewpoint of improving the surface hardness of the carbonate-based resin or from the viewpoint of reducing the photoelastic coefficient, the content ratio of the structural unit B1 in the carbonate-based resin is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 15 mol% or more, even more preferably 25 mol% or more, and particularly preferably 37.5 mol% or more, based on the amount of substance. The content ratio of the structural unit B1 is preferably 50 mol% or less. From the same viewpoint, the content ratio of the structural unit B1 in the carbonate-based resin is preferably 1 mass% or more, more preferably 10 mass% or more, even more preferably 40 mass% or more, even more preferably 55 mass% or more, and particularly preferably 75 mass% or more, based on the mass. The content ratio of the structural unit B1 is that of the above-mentioned second structural unit. That is, in this specification, the content ratio of the structural unit derived from a dihydroxy compound in the carbonate-based resin (for example, the structural unit B1, the structural unit D4 described later, etc.) is that of a structural unit containing oxygen atoms derived from a hydroxy group at both ends. As with the oxygen atoms of dihydroxy compounds, the content of structural units derived from dicarboxylic acids in carbonate resins refers to structural units containing carbonyl groups derived from carboxylic acids at both ends.

[0123] On the other hand, from the viewpoint of achieving both the wet heat resistance and the film strength of the carbonate-based resin, the content ratio of the structural unit B1 in the carbonate-based resin is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, even more preferably 4 mol% or more, and particularly preferably 5 mol% or more, based on the amount of substance. Also, it is preferably 50 mol% or less, more preferably 37.5 mol% or less, even more preferably 25 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. From the same viewpoint, the content ratio of the structural unit B1 in the carbonate-based resin is preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 5 mass% or more, even more preferably 7 mass% or more, and particularly preferably 10 mass% or more, based on the mass. Also, it is preferably 95 mass% or less, more preferably 80 mass% or less, even more preferably 60 mass% or less, even more preferably 50 mass% or less, and particularly preferably 40 mass% or less.

[0124] From the viewpoint of enabling improvements in optical properties such as transparency, weather resistance, moldability, heat resistance, and other properties, it is preferable that the carbonate-based resin further contains a structural unit derived from at least one compound selected from the group consisting of isosorbide, isomannide, and isoided. Hereinafter, the structural unit derived from at least one compound selected from the group consisting of isosorbide, isomannide, and isoided will be referred to as "structural unit D1" as appropriate. The structural unit D1 is represented by the following formula (D1).

[0125] [ka]

[0126] When the carbonate-based resin has the structural unit D1, the carbonate-based resin becomes a copolymer polycarbonate having at least the structural unit B1 and the structural unit D1. In addition, from the viewpoint of being obtained by dehydration condensation of sorbitol produced from various starches, which are abundant and easily available as a plant-derived resource, and from the viewpoint of being carbon neutral, it is more preferable that the carbonate-based resin has a structural unit derived from isosorbide.

[0127] From the viewpoint of improving heat resistance, the content of the structural unit D1 in the carbonate-based resin is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, particularly preferably 40 mol% or more, and also preferably 49 mol% or less, based on the total molar amount of all dihydroxy compounds, all dicarboxylic compounds, and all carbonates in the carbonate-based resin. From the same viewpoint, the content of the structural unit D1 in the carbonate-based resin is preferably 5 mass% or more, more preferably 20 mass% or more, even more preferably 40 mass% or more, even more preferably 60 mass% or more, particularly preferably 80 mass% or more, and preferably 99 mass% or less, based on the total mass of all dihydroxy compounds, all dicarboxylic compounds, and all carbonates in the carbonate-based resin. From the viewpoint of suppressing water absorption rate and balancing with mechanical strength and optical properties, the content of the structural unit D1 in the carbonate-based resin is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, particularly preferably 30 mol% or more, preferably 49 mol% or less, more preferably 47 mol% or less, more preferably 45 mol% or less, even more preferably 42 mol% or less, and particularly preferably 40 mol% or less. From the same viewpoint, the content of the structural unit D1 in the carbonate-based resin is preferably 5 mass% or more, more preferably 20 mass% or more, more preferably 30 mass% or more, even more preferably 37.5 mass% or more, and particularly preferably 42.5 mass% or more, based on the total mass of all dihydroxy compounds, all dicarboxylic compounds, and all carbonates in the carbonate-based resin. Furthermore, it is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less.

[0128] From the viewpoint of improving optical properties such as transparency, mechanical strength, and properties such as fluidity during melting, the carbonate-based resin preferably contains a structural unit derived from an aliphatic dihydroxy compound other than the structural unit B1 and the structural unit D1. The structural unit derived from an aliphatic dihydroxy compound other than the structural unit B1 and the structural unit D1 is hereinafter referred to as "structural unit D2" as appropriate, and the structural unit derived from an alicyclic dihydroxy compound is hereinafter referred to as "structural unit D2'". Note that the structural units D2 and D2' are concepts that do not include not only the structural unit B1 and the structural unit D1, but also the structural units D3 to D7 described below. When the carbonate-based resin has the structural unit D2 and / or D2', the carbonate-based resin becomes a copolymer polycarbonate having at least the structural unit B1 and the structural unit D2 and / or the structural unit D2'. Examples of the aliphatic dihydroxy compound include a linear aliphatic dihydroxy compound and a branched aliphatic dihydroxy compound, and do not include an alicyclic dihydroxy compound.

[0129] Examples of linear aliphatic dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-pentanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polydecamethylene glycol.

[0130] Examples of the branched aliphatic hydrocarbon dihydroxy compound include neopentyl glycol and hexylene glycol.

[0131] From the viewpoint of imparting flexibility to the carbonate-based resin and improving the toughness of the resin, the dihydroxy compound constituting the structural unit D2 is particularly preferably a linear aliphatic dihydroxy compound having a primary hydroxyl group. Examples of linear aliphatic dihydroxy compounds having a primary hydroxyl group include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol.

[0132] From the viewpoint of improving properties such as toughness, the content of the structural unit D2 in the carbonate-based resin is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, particularly preferably 40 mol% or more, and preferably 49 mol% or less, based on the total molar amount of all structural units based on all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates in the carbonate-based resin. From the same viewpoint, the content of the structural unit D2 in the carbonate-based resin is preferably 5% by mass or more, more preferably 15% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more, based on the total mass of all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates in the carbonate-based resin. Also, it is preferably 99% by mass or less. From the viewpoint of achieving both heat resistance and mechanical strength, the content of the structural unit D2 in the carbonate-based resin is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, even more preferably 4 mol% or more, and particularly preferably 15 mol% or more, based on the total molar amount of all structural units based on all dihydroxy compounds, all dicarboxylic compounds, and all carbonates in the carbonate-based resin. Also, it is preferably 49 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. From a similar viewpoint, the content of structural unit D2 in the carbonate-based resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 4% by mass or more, and particularly preferably 5% by mass or more, preferably 99% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less, relative to the total mass of the carbonate-based resin based on all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates in the carbonate-based resin.

[0133] Examples of the alicyclic dihydroxy compound include 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and dihydroxy compounds derived from terpene compounds such as limonene.

[0134] From the viewpoint of imparting flexibility to the carbonate-based resin and improving the toughness of the resin, the dihydroxy compound constituting the structural unit D2' is preferably 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, or the like.

[0135] From the viewpoint of improving properties such as toughness, the content of the structural unit D2' in the carbonate-based resin is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, particularly preferably 40 mol% or more, and preferably 49 mol% or less, relative to the total molar amount of all structural units based on all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates in the carbonate-based resin. From a similar viewpoint, the content is preferably 5 mass% or more, more preferably 15 mass% or more, even more preferably 30 mass% or more, even more preferably 50 mass% or more, particularly preferably 70 mass% or more, and preferably 99 mass% or less, based on the total mass of all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonate-based carbonate resins in the carbonate-based resin. From the viewpoint of achieving both heat resistance and mechanical strength, the content of the structural unit D2' in the carbonate-based resin is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, even more preferably 4 mol% or more, particularly preferably 5 mol% or more, preferably 49 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less, relative to the total molar amount of all structural units based on all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates in the carbonate-based resin. From a similar viewpoint, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 4% by mass or more, and particularly preferably 5% by mass or more, and is preferably 99% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less, relative to the total mass of all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates in the carbonate-based resin.

[0136] The carbonate-based resin may further contain a structural unit derived from a dihydroxy compound represented by the following formula (D3). In this case, the glass transition temperature of the carbonate-based resin may be controlled within a suitable range, which may facilitate melt molding and film formation of the resin. In addition, in this case, optical properties (specifically, low photoelastic coefficient) may be imparted to the resin. The carbonate-based resin may contain one or more structural units represented by formula (D3). The structural unit represented by formula (D3) is appropriately referred to as "structural unit D3".

[0137] [ka]

[0138] In formula (D3), R 21 ~R 24 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

[0139] Examples of the dihydroxy compound represented by formula (D3) include the dihydroxy compounds described in paragraph

[0024] of International Publication No. 2017 / 159525.

[0140] From the viewpoint of obtaining a carbonate-based resin having a reduced photoelastic coefficient and a high surface hardness, the content of the structural unit D3 in the carbonate-based resin is preferably 5 mol% or more, more preferably 15 mol% or more, even more preferably 22.5 mol% or more, even more preferably 32.5 mol% or more, particularly preferably 40 mol% or more, and preferably 49 mol% or less, based on the total molar amount of all dihydroxy compounds, all dicarboxylic compounds, and all carbonates in the carbonate-based resin. From the same viewpoint, the content of the structural unit D3 in the carbonate-based resin is preferably 10 mass% or more, more preferably 30 mass% or more, even more preferably 45 mass% or more, even more preferably 65 mass% or more, particularly preferably 80 mass% or more, and preferably 99 mass% or less, based on the total mass of all dihydroxy compounds, all dicarboxylic compounds, and all carbonates in the carbonate-based resin.

[0141] On the other hand, in order to improve the melt moldability and film formability of the carbonate-based resin, from the viewpoint of adjusting the glass transition temperature and mechanical strength to a suitable range, the content of the structural unit A5 is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 17.5 mol% or more, particularly preferably 20 mol% or more, preferably 45 mol% or less, more preferably 40 mol% or less, even more preferably 35 mol% or less, particularly preferably 30 mol% or less, and most preferably 27.5 mol% or less. From the same viewpoint, it is preferably 10 mass% or more, more preferably 20 mass% or more, more preferably 30 mass% or more, even more preferably 35 mass% or more, and particularly preferably 40 mass% or more, based on the total mass of all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates in the carbonate-based resin. Furthermore, it is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less.

[0142] The carbonate-based resin may further contain a structural unit represented by the following formula (D4) and / or the following formula (D5). In this case, the carbonate-based resin can obtain reverse wavelength dispersion, and is suitable for optical films such as retardation films. The structural unit represented by formula (D4) is appropriately referred to as "structural unit D4", and the structural unit represented by formula (D5) is appropriately referred to as "structural unit D5". When the carbonate-based resin has the structural unit D5, the carbonate-based resin is a carbonate-based resin having a carbonate bond and an ester bond, that is, a polyester carbonate.

[0143] [ka]

[0144] [ka]

[0145] The structural unit represented by formula (D4) is appropriately referred to as the "first structural unit D4". When the carbonate-based resin has a structural unit represented by formula (D4), similarly to the above-mentioned structural unit (B1), the carbonate-based resin has R 22 , R 24 This structural unit is appropriately referred to as the "second structural unit D4".

[0146] In formula (D4) and formula (D5), A 1 ~A 8 R each independently represents =CH- or =N-. 22 , R 23 , and R 24 each independently represents a group in which two or more groups selected from the group consisting of a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, an optionally substituted aralkylene group having 6 to 12 carbon atoms, an optionally substituted alkylene group having 1 to 10 carbon atoms, and an optionally substituted arylene group having 4 to 10 carbon atoms are linked via an oxygen atom, an optionally substituted nitrogen atom, or a carbonyl group.

[0147] In formula (D4) and formula (D5), R 25 ~R 32 R each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 3 to 14 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 3 to 14 carbon atoms, an optionally substituted acyloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, an optionally substituted alkenyl group having 2 to 10 carbon atoms, an optionally substituted alkynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a halogen atom, a nitro group, or a cyano group.25 ~R 32 At least two adjacent groups among these may be bonded to each other to form a ring. v represents an integer value of 0 to 5.

[0148] If the content ratio of the structural unit (D4) and the structural unit (D5) in the carbonate-based resin is excessively high, the photoelastic coefficient and reliability may deteriorate, and high birefringence may not be obtained even if a film composed of the carbonate-based resin is stretched. In addition, if the proportion of the oligofluorene structural unit in the carbonate-based resin is excessively high, the range of molecular design is narrowed, making it difficult to modify the resin as needed. On the other hand, even if the desired reverse wavelength dispersion is obtained with a very small amount of the oligofluorene structural unit, in this case, the optical properties change sensitively according to a slight variation in the content of the oligofluorene. Therefore, it becomes difficult to manufacture a carbonate-based resin so that the various properties fall within a certain range.

[0149] R in formula (D4) and formula (D5) 22 , R 23 , and R 24 With regard to the above, specific examples of the "arylene group having 4 to 10 carbon atoms" in the "arylene group having 4 to 10 carbon atoms which may be substituted" include, but are not limited to, phenylene groups such as a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group; naphthylene groups such as a 1,5-naphthylene group and a 2,6-naphthylene group; and heteroarylene groups such as a 2,5-pyridylene group and a 2,4-furylene group.

[0150] R in formula (D4) and formula (D5) 22 , R 23 , and R 24Regarding the above, examples of the "aralkylene group having 6 to 10 carbon atoms" in the "aralkylene group having 6 to 12 carbon atoms which may be substituted" include groups consisting of an aromatic ring structure and two linear or branched alkylene groups each bonded to any two positions of the aromatic ring structure. The aromatic ring structure may be a hydrocarbon ring structure such as a benzene ring or a naphthalene ring, or a heterocyclic structure such as a furan ring or a pyridine ring. Specific examples of the aralkylene group having 6 to 10 carbon atoms include, but are not limited to, those shown in the following group [G].

[0151] [ka]

[0152] From the viewpoints of ease of synthesis and inexpensive procurement of raw materials, it is preferred that the structural unit D4 be represented by the following formula (D4-1), and the structural unit D5 be represented by the following formula (D5-1).

[0153] [ka]

[0154] [ka]

[0155] In formula (D4-1) and formula (D5-1), A 4 and A 5 R in formula (D4-1) and formula (D5-1) each independently represents =CH- or =N-. 22 , R 23 , R 24 are R in formulas (D4) and (D5), respectively. 22 , R 23 , R 24 The same applies to R in formula (D4-1) and formula (D5-1). 25 ~R 32 are R in formula (D4) and formula (D5), respectively. 25 ~R 32 v is an integer of 0 to 2.

[0156] In formula (D4-1) and formula (D5-1), R 22 , R 23 , and R 24 are each independently preferably an optionally substituted alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.

[0157] From the viewpoints of ease of synthesis and inexpensive procurement of raw materials, it is preferred that the structural unit D4 is represented by the following formula (D4-2), and the structural unit D5 is represented by the following formula (D5-2).

[0158] [ka]

[0159] [ka]

[0160] In formula (D4-2) and formula (D5-2), A 5 R in formula (D4-2) and formula (D5-2) represents =CH- or =N-. 22 , R 23 , R 24 are R in formulas (D4) and (D5), respectively. 22 , R 23 , R 24 The same applies to R in formula (D4-1) and formula (D5-1). 25 ~R 32 are R in formula (D4) and formula (D5), respectively. 25 ~R 32 v is an integer of 0 to 2.

[0161] From the viewpoints of ease of synthesis and inexpensive procurement of raw materials, the structural unit D4 and the structural unit D5 are preferably represented by the following formula (D4-3) and the following formula (D5-3), respectively.

[0162] [ka]

[0163] [ka] In formula (D4-3) and formula (D5-3), R 22 , R 23 , R 24 each independently represents a direct bond, a methylene group, or an ethylene group.

[0164] From the viewpoint of facilitating synthesis and improving reverse wavelength dispersion, it is more preferable that the structural unit D4 is represented by the following formula (D4-4), and the structural unit D5 is represented by the following formula (D5-4).

[0165] [ka]

[0166] [ka]

[0167] In formula (D4-4) and formula (D5-4), R 22 , R 23 , R 24 each independently represents a direct bond, a methylene group, or an ethylene group.

[0168] From the viewpoint of improving the reverse wavelength dispersion, it is more preferable that the structural unit D4 is represented by the following formula (D4-5), and the structural unit D5 is represented by the following formula (D5-5).

[0169] [ka]

[0170] [ka]

[0171] In formula (D4-5) and formula (D5-5), R22 , R 23 , R 24 each independently represents a direct bond, a methylene group, or an ethylene group.

[0172] From the viewpoint of inexpensive procurement of raw materials, specifically, the structural unit D4 and the structural unit D5 are preferably at least one selected from the structural group shown below.

[0173] [ka]

[0174] [ka]

[0175] In addition, the structural group shown below has aromatic rings densely introduced and has a rigid skeleton, and therefore shows a low photoelastic coefficient. Carbonate-based resins containing structural units with low photoelastic coefficients have little change in retardation due to stress, and are preferable from the viewpoints of moldability and reliability. In other words, from the viewpoints of moldability and reliability of retardation change, it is preferable that the structural unit D4 and the structural unit D5 are at least one selected from the structural group shown below.

[0176] [ka]

[0177] [ka]

[0178] From the viewpoints of achieving both low-cost synthesis and low water absorption, and further enabling adjustment to a preferable wavelength dispersion, it is particularly preferable that the structural unit D5 has a structure represented by the following formula (D5-5).

[0179] [ka]

[0180] The carbonate-based resin having the structural unit D4 and the structural unit D5 can be produced, for example, by a method such as polymerization of a monomer represented by the following formula (j).

[0181] [ka]

[0182] A in formula (j) 1 ~A 8 , R 22 ~R 32 , v are each A in the above formula (D4). 1 ~A 8 , R 22 ~R 32 , and v. J 1 and J 2 Each of J independently represents a polymerization reactive group. 1 and J 2 is, for example, a hydroxyl-containing group such as a hydroxyl group or a hydroxyalkyl group. 1 and J 2 may be the same or different. Since the preparation of the monomer represented by formula (j) tends to be carried out in a short process, J 1 and J 2 are preferably identical.

[0183] The monomer represented by formula (j) can be used as a raw material for a polymer having a divalent oligofluorene as a repeating unit. The polymerization reactive group is J 1 and J 2 It is preferable that the substituents acting as polymerization reactive groups under the polymerization conditions of polycarbonate are only R 25 ~R 32 It is preferable that it is not included in.

[0184] J in formula (j) 1 and J 2 is preferably a hydroxy group. A monomer in which J1 and J2 are hydroxy groups can be used to produce a polycarbonate resin having good optical properties.1 and J 2 A monomer in which is a hydroxy group is represented by the following formula (j1).

[0185] [ka]

[0186] In addition, J in formula (j) 1 and J 2 is preferably an ester group. 1 and J 2 Monomers in which the ester group is used can be used to produce polyester carbonates with good optical performance. The ester group is preferably a 2-(methoxycarbonyl)ethyl group, a 2-(ethoxycarbonyl)ethyl group, or a 2-(methoxycarbonyl)propyl group, in that it can be easily introduced using industrially available methyl acrylate, ethyl acrylate, or methyl methacrylate.

[0187] The ester group is preferably a phenoxycarbonylalkyl group, since the activity of the ester group is improved and the transesterification reaction proceeds easily, and polyester carbonate can be synthesized in one step by reacting a diester compound, a dihydroxy compound, and a carbonic acid diester under the same conditions. In particular, 2-(phenoxycarbonyl)methyl, 2-(phenoxycarbonyl)ethyl, and 2-(phenoxycarbonyl)propyl groups are particularly preferred, since they can be introduced by a method using 2-bromophenyl acetate, phenyl acrylate, and phenyl methacrylate, or by a method of transesterification from 2-bromoacetate, 2-chloroacetate, 2-iodoacetate, acrylic acid esters, and methacrylic acid esters. 1 and J 2 The monomer in which is an ester group is represented, for example, by the following formula (j2).

[0188] [ka]

[0189] In formula (j2), J 3 and J 4 each independently represents an organic substituent having 1 to 10 carbon atoms or a halogen atom.

[0190] J 3 and J 4 In the above, specific examples of the organic substituent having 1 to 10 carbon atoms include, but are not limited to, linear alkyloxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, and an n-decyloxy group; branched alkyloxy groups such as an isopropyloxy group, a 2-methylpropyloxy group, a 2,2-dimethylpropyloxy group, and a 2-ethylhexyloxy group; cyclic alkyloxy groups such as a cyclopropyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cyclooctyloxy group; aryloxy groups such as a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group; heteroaryl groups including a 1-imidazoyl group, heteroaryloxy groups such as a 2-pyridyloxy group and a 2-furyloxy group; and aralkyloxy groups such as a benzyloxy group, a 2-phenylethoxy group, and a p-methoxybenzyloxy group. Specific examples of the halogen atom include, but are not limited to, a chlorine atom and a bromine atom.

[0191] The method is advantageous in that it can efficiently synthesize polyester carbonates by removing the low-boiling alcohols produced by transesterification with dihydroxy compounds. 3 and J 4 is preferably a methyl group or an ethyl group. Since the ester exchange reaction proceeds easily, the diester compound, the dihydroxy compound, and the carbonic acid diester are all added to the reactor at once, and the polyester carbonate, which is a preferred polymer, can be synthesized in one step. 3 and J 4 is preferably an aryl group. In particular, a phenyl group is particularly preferred because it has a small molecular weight and can be distilled off as phenol after the synthesis of polyester carbonate. 3and J 4 When a compound in which J is an aryl group is used, it is preferable to use diaryl carbonates described later as the carbonic acid diester from the viewpoint of reactivity during polymerization, and from the viewpoint of easy removal of by-products, it is preferable to use diaryl carbonates described later as the carbonic acid diester. 3 and J 4 It is more preferable that the aryl group in the diaryl carbonate is the same as the aryl group in the diaryl carbonate. From the viewpoint of good polymerization reactivity and ability to obtain a carbonate-based resin using relatively simple equipment such as solution polymerization or interfacial polymerization, 3 and J 4 is preferably an acid chloride-containing group, and acid chloride and acid bromide are more preferred since they can be produced industrially at low cost.

[0192] Specific examples of the monomer represented by formula (j) include the following compounds.

[0193] [ka]

[0194] [ka] TIFF0007673462000088.tif134170

[0195] [ka] TIFF0007673462000090.tif229170

[0196] When the carbonate-based resin contains the structural unit D4 (specifically, the second structural unit D4) and / or the structural unit D5, from the viewpoints of improving the optical properties, making the wavelength dispersion properties of the optical film composed of the carbonate-based resin favorable, and adjusting the birefringence within a favorable range, the content ratio of the structural units D4 and the content ratio of the structural units D5 in the carbonate-based resin are, on a substance amount basis, preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 3 mol% or more, even more preferably 4 mol% or more, particularly preferably 5 mol% or more, preferably 45 mol% or less, more preferably 35 mol% or less, even more preferably 25 mol% or less, even more preferably 17.5 mol% or less, and particularly preferably 12.5 mol% or less. From a similar viewpoint, the content ratio of structural units D4 and the content ratio of D5 in the carbonate-based resin are, on a mass basis, preferably 2 mass% or more, more preferably 5 mass% or more, even more preferably 7.5 mass% or more, even more preferably 10 mass% or more, and particularly preferably 15 mass% or more, preferably 90 mass% or less, more preferably 70 mass% or less, even more preferably 50 mass% or less, even more preferably 35 mass% or less, and particularly preferably 25 mass% or less.

[0197] The carbonate-based resin may further contain a structural unit represented by the following formula (D6). In this case, the carbonate-based resin exhibits excellent optical properties. The carbonate-based resin may contain one or more structural units represented by formula (D6). The structural unit represented by formula (D6) is appropriately referred to as "structural unit D6".

[0198] [ka]

[0199] In formula (D6), V represents an arylene group which may be substituted, the substituent of V is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted, an aryl group having 3 to 14 carbon atoms which may be substituted, an acyl group having 1 to 10 carbon atoms which may be substituted, an alkoxy group having 1 to 10 carbon atoms which may be substituted, an aryloxy group having 3 to 14 carbon atoms which may be substituted, an acyloxy group having 1 to 10 carbon atoms which may be substituted, an amino group which may be substituted, an alkenyl group having 2 to 10 carbon atoms which may be substituted, an alkynyl group having 2 to 10 carbon atoms which may be substituted, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group; L7 and L8 each independently represent an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, or an aralkylene group having 6 to 12 carbon atoms which may be substituted; s represents an integer of 0 to 4, and t represents an integer of 0 to 4.

[0200] In formula (D6), s and t each independently represent an integer of 0 to 4, and from the viewpoint of heat resistance, an integer of 0 to 3 is preferable, and an integer of 0 to 2 is more preferable. Moreover, from the viewpoint of adjusting the glass transition temperature to a value that provides good molding processability and from the viewpoint of inexpensive synthesis of the monomer raw material, it is particularly preferable that s and t each independently represent 0 or 1.

[0201] From the viewpoint of ease of synthesis of the monomer raw material, the structural unit D6 is preferably represented by the following formula (D6-1).

[0202] [ka]

[0203] In formula (D6-1), V is a phenylene group or naphthylene group which may be substituted, the substituent of V is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted, s is 0 or 1, and t is 0 or 1.

[0204] From the viewpoint of ease of synthesis of the monomer raw materials and of adjusting the optical properties (specifically, preferable wavelength dispersion properties), the structural unit D6 is preferably represented by the following formula (D6-2).

[0205] [ka]

[0206] In formula (D6-2), R 33 represents a hydrogen atom, a methyl group, or a phenyl group; s represents 0 or 1; and t represents 0 or 1.

[0207] Specific examples of the structural unit D6 include the following structural units.

[0208] [ka]

[0209] The carbonate-based resin having the structural unit D6 can be produced, for example, by a method such as polymerization of a monomer represented by the following formula (i).

[0210] [ka]

[0211] In the formula (i), V and L 7 , L 8 , s, and t are V and L in the above formula (D6), respectively. 7 , L 8 , s, and t are the same as above. Specific examples of the monomer represented by formula (i) include the following.

[0212] [ka]

[0213] When the carbonate-based resin contains a structural unit derived from the above structural unit D6, from the viewpoint of obtaining favorable wavelength dispersion characteristics when the carbonate-based resin is used as an optical film, the content thereof is preferably 40 mass% or more relative to the total mass of all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonate-based carbonate-based resins in the carbonate-based resin, more preferably 45 mass% or more, even more preferably 50 mass% or more, even more preferably 55 mass% or more, and particularly preferably 60 mass% or more.

[0214] If the content ratio of the structural unit is too low, the wavelength dispersion characteristics of the carbonate-based resin when used as an optical film may not be favorable. If the content ratio of the structural unit is too high, the ratio of the retardation measured at a wavelength of 450 nm to the retardation measured at a wavelength of 550 nm when used as an optical film may become too large, resulting in unfavorable optical characteristics. Therefore, the total mass of all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonate-based carbonate-based resins in the carbonate-based resin is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less. The retardation ratio of the optical film refers to the ratio λ(450) / λ(550) of the retardation λ(450) of the optical film measured at a wavelength of 450 nm to the retardation λ(550) of the optical film measured at a wavelength of 550 nm.

[0215] The carbonate-based resin may further contain a structural unit represented by the following formula (D7). In this case, the toughness and heat resistance of the carbonate-based resin can be improved and the water absorption can be reduced. In addition, the raw material of the structural unit represented by formula (D7) is inexpensively available. The structural unit represented by formula (D7) is appropriately referred to as "structural unit D7".

[0216] [ka]

[0217] In formula (D7), R 1 R represents a direct bond, an oxygen atom, or an alkylene group having 1 to 40 carbon atoms which may have a substituent. 2 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 3 to 14 carbon atoms which may have a substituent, an acyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 3 to 14 carbon atoms which may have a substituent, an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituted alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a silicon atom which has a substituent, a halogen atom which has a substituent, a nitro group which has a substituent, or a cyano group which has a substituent. 3 and L 4 each independently represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, an arylene group having 4 to 10 carbon atoms which may have a substituent, or an aralkylene group having 6 to 12 carbon atoms which may have a substituent. o represents an integer of 0 to 4, and p represents an integer of 0 to 4.

[0218] From the viewpoint of heat resistance and ease of synthesis, L in formula (D7) 3 and L 4 are each independently preferably an alkylene group having 1 to 4 carbon atoms which may have a substituent, and more preferably an ethylene group. From the viewpoints of heat resistance and ease of synthesis, o and p in formula (D7) are each independently preferably 0 or 1.

[0219] From the viewpoint of ease of synthesis, the structural unit D7 is preferably represented by the following formula (D7-1).

[0220] [ka]

[0221] In formula (D7-1), R 1R represents a direct bond, an oxygen atom, or an alkylene group having 1 to 40 carbon atoms which may have a substituent. 3 , R 4 , R 7 , and R 8 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 3 to 14 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 3 to 14 carbon atoms, an optionally substituted acyloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, an optionally substituted alkenyl group having 2 to 10 carbon atoms, an optionally substituted alkynyl group having 2 to 10 carbon atoms, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group; L3 and L4 each independently represent an optionally substituted alkylene group having 1 to 10 carbon atoms; o represents 0 or 1; and p represents 0 or 1.

[0222] From the viewpoint of ease of synthesis due to the symmetric structure, the structural unit D7 is preferably represented by the following formula (D7-2).

[0223] [ka]

[0224] In formula (D7-2), R 1 R represents a direct bond, an oxygen atom, or an alkylene group having 1 to 40 carbon atoms which may have a substituent. 4 and R 7each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 3 to 14 carbon atoms which may have a substituent, an acyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, an aryloxy group having 3 to 14 carbon atoms which may have a substituent, an acyloxy group having 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a silicon atom which has a substituent, a halogen atom which has a substituent, a nitro group which has a substituent, or a cyano group which has a substituent. 3 and L 4 each independently represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. o represents 0 or 1, and p represents 0 or 1.

[0225] From the viewpoints of inexpensive procurement of raw materials and improved heat resistance, the structural unit D7 is preferably represented by the following formula (D7-3).

[0226] [ka]

[0227] In formula (D7-3), R 1 R represents a direct bond, an oxygen atom, or an optionally substituted alkylene group having 1 to 40 carbon atoms. 4 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms; L 3 and L 4 each independently represents an optionally substituted alkylene group having 1 to 10 carbon atoms; o represents 0 or 1; and p represents 0 or 1.

[0228] L in the above formula (D7-3) 3 Or L 4 When the alkylene group is longer, the heat resistance tends to decrease. Therefore, о and p are 0, or о or p is 1, and L 3 Or L 4is preferably an alkylene group having 1 to 2 carbon atoms. From the viewpoint of ease of synthesis, the alkylene group more preferably has 2 carbon atoms.

[0229] From the viewpoint of high heat resistance, R in the above formula (D7-3) 1 is preferably a direct bond or an oxygen atom. From the viewpoint of adjusting the ease of synthesis and high toughness, R in the above formula (D7-3) is 1 is preferably a methylene group, an alkylmethylene group having 2 to 40 carbon atoms, or a dialkylmethylene group having 3 to 40 carbon atoms, and more preferably an alkylmethylene group having 2 to 40 carbon atoms.

[0230] From the viewpoint of heat resistance, R in the above formula (D7-3) 1 It is more preferable that R in the above formula (D7-3) has a methylene group. From the viewpoint of ease of synthesis and improvement of toughness, 1 is more preferably an alkylmethylene group having 2 to 40 carbon atoms. From the viewpoint of procuring raw materials more inexpensively, the alkylmethylene group preferably has 2 to 4 carbon atoms. From the viewpoint of further improving toughness, the alkylmethylene group preferably has 3 or more carbon atoms, more preferably 10 or more, and even more preferably 12 or more carbon atoms. From the viewpoint of further improving heat resistance, the alkylmethylene group preferably has 40 or less carbon atoms, more preferably 30 or less, and even more preferably 20 or less carbon atoms. From the viewpoint of a balance between improving toughness and heat resistance, the alkylmethylene group preferably has 7 to 15 carbon atoms.

[0231] From the viewpoint of thermal stability, R in formula (D7-3) 1 is preferably a dialkylmethylene group having 3 to 40 carbon atoms. From the viewpoint of toughness, the dialkylmethylene group preferably has 5 or more carbon atoms, more preferably 10 or more, and even more preferably 20 or more. From the viewpoint of heat resistance, the dialkylmethylene group preferably has 40 or less carbon atoms, more preferably 30 or less, and even more preferably 20 or less. From the viewpoint of ease of synthesis, the dialkylmethylene group preferably has 3 to 10 carbon atoms.

[0232] From the viewpoint of heat resistance, R in formula (D7-3) 4 is preferably a hydrogen atom. From the viewpoint of inexpensive procurement of raw materials and toughness, R in formula (D7-3) is preferably 4 is preferably a methyl group.

[0233] From the viewpoint of high heat resistance, o and p in formula (D7-3) are preferably 0. Also, from the viewpoint of toughness, o and p in formula (D7-3) are preferably 1.

[0234] Specific examples of the structural unit D7 include any of the structures in the following structural group.

[0235] [ka]

[0236] The carbonate-based resin having the structural unit D7 is produced, for example, by polymerization of a monomer represented by the following formula (g).

[0237] [ka]

[0238] R in formula (g) 1 ~R 9 , L 3 , L 4 , o and p are each R in the above formula (D7). 1 ~R 9 , L 3 , L 4 , o and p are the same as above. Specific examples of the monomer represented by formula (g) include the following.

[0239] [ka]

[0240] From the viewpoint of improving the wet heat resistance and toughness of the carbonate-based resin, the content ratio of the structural unit D7 in the carbonate-based resin is, on a mass basis, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 25% by mass or more, and particularly preferably 35% by mass or more. Also, from the viewpoint of improving weather resistance, the content ratio of the structural unit D7 in the carbonate-based resin is preferably 95% by mass or less, more preferably 80% by mass or less, even more preferably 65% ​​by mass or less, even more preferably 55% by mass or less, and particularly preferably 45% by mass or less, based on the total mass of all dihydroxy compounds, all dicarboxylic acid compounds, and all carbonates constituting the carbonate-based resin.

[0241] [Method for producing carbonate-based resin having carbonate bond] When the carbonate-based resin is a polycarbonate resin, the polycarbonate resin is produced by a commonly used polymerization method. Specifically, there are a solution polymerization method using phosgene and a melt polymerization method in which a monomer raw material is reacted with a carbonic acid diester. Any of these methods may be used, but a melt polymerization method in which a raw material monomer (specifically, a dihydroxy compound) is reacted with a carbonic acid diester that is less toxic to the environment in the presence of a polymerization catalyst is preferred. In addition, in the polymerization method in which the carbonate-based resin is a polyester carbonate resin, the same ester exchange catalyst, polymerization conditions, additives in the polymerization process, etc. can be used as in the polymerization method for polycarbonate resin described below.

[0242] As the carbonic acid diester, one represented by the following formula (o) can be used.

[0243] [ka]

[0244] In formula (o), E 5 and E 6 are each independently an optionally substituted aliphatic group having 1 to 18 carbon atoms, or an optionally substituted aromatic group having 6 to 12 carbon atoms.

[0245] Examples of the carbonic acid diester represented by formula (o) include diphenyl carbonate and substituted diphenyl carbonates such as ditolyl carbonate. Examples of the carbonic acid diester represented by formula (o) include dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, etc. Preferred are diphenyl carbonate and substituted diphenyl carbonate. As the carbonic acid diester, one type of compound may be used, or two or more types of compounds may be used.

[0246] The carbonic acid diester may be substituted with a dicarboxylic acid or a dicarboxylic acid ester. The amount of the substituted carbonic acid diester in the total amount of the carbonic acid diester is preferably 50 mol% or less, more preferably 30 mol% or less. Examples of the dicarboxylic acid and the dicarboxylic acid ester include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. Also, the raw material dicarboxylic acid compound for introducing the structures (D4) and (D5) can be used. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate resin is obtained.

[0247] The amount of the carbonic acid diester used relative to the total dihydroxy compounds used in the reaction is preferably 0.90 to 1.10, more preferably 0.96 to 1.04, in molar ratio. If the amount of the carbonic acid diester used is less than 0.90, the terminal OH group of the polycarbonate resin increases, which may deteriorate the thermal stability of the polymer or make it difficult to obtain a desired high molecular weight product. On the other hand, if the amount of the carbonic acid diester used exceeds 1.10, not only may the rate of the transesterification reaction decrease under the same polymerization conditions or it become difficult to produce a polycarbonate resin with a desired molecular weight, but also the amount of the carbonic acid diester remaining in the polycarbonate resin may increase. The remaining carbonic acid diester may cause odor during molding or in the molded product.

[0248] As the raw material dihydroxy compound, a dihydroxy compound for introducing the structural unit B1 and a dihydroxy compound for introducing other structural units to be added as necessary are used. The mixing ratio of these dihydroxy compounds can be appropriately adjusted so as to obtain the desired physical properties and characteristics, as described above.

[0249] In addition, an alkali metal compound and / or an alkaline earth metal compound is used as a polymerization catalyst (ester exchange catalyst) in melt polymerization. It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with the alkali metal compound and / or the alkaline earth metal compound as an auxiliary. It is preferable to use only the alkali metal compound and / or the alkaline earth metal compound.

[0250] Examples of the alkali metal compound used as a polymerization catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborate, potassium phenylborate, lithium phenylborate, cesium phenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, and the like. Further examples include alcoholates of sodium, potassium, lithium, or cesium; disodium, dipotassium, dilithium, and dicesium salts of phenolates; and disodium, dipotassium, dilithium, and dicesium salts of bisphenol A.

[0251] Examples of alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

[0252] As the alkali metal compound and alkaline earth metal compound, one or more compounds can be used.

[0253] Specific examples of basic boron compounds include metal salts of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, butyltriphenyl boron, etc. Examples of metal salts include sodium salt, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt, strontium salt, etc.

[0254] Examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0255] Examples of basic ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0256] Examples of amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

[0257] As the above-mentioned basic compound, one or more compounds can be used.

[0258] When an alkali metal compound or an alkaline earth metal compound is used as the polymerization catalyst, the amount of the polymerization catalyst used per mol of all dihydroxy compounds used in the reaction is usually 0.1 to 500 μmol, preferably 0.5 to 300 μmol, and more preferably 1 to 250 μmol, calculated as the metal amount. If the amount of the polymerization catalyst used is too small, the polymerization activity required to produce a polycarbonate resin with a desired molecular weight may not be obtained. On the other hand, if the amount of the polymerization catalyst used is too large, the color of the polycarbonate resin may deteriorate, by-products may be generated, the flowability may decrease, or gel may be generated frequently. As a result, it becomes difficult to produce a polycarbonate resin with the desired quality.

[0259] In the production of polycarbonate resins, various dihydroxy compounds as raw materials may be supplied as solids, or may be supplied in a molten state by heating, or may be supplied as an aqueous solution if they are soluble in water. Supplying the dihydroxy compounds as raw materials in a molten state or an aqueous solution has the advantage that it is easy to measure and transport them in industrial production.

[0260] The method of reacting a raw material dihydroxy compound with a carbonic acid diester in the presence of a polymerization catalyst is usually carried out in a multi-stage process of two or more stages. Specifically, the first stage reaction is carried out at a temperature of 140 to 220°C, preferably 150 to 200°C, for 0.1 to 10 hours, preferably 0.5 to 3 hours. The second and subsequent stages of the reaction are carried out by gradually lowering the pressure from the first stage while increasing the reaction temperature, and removing the generated phenol from the reaction system. Finally, the polycondensation reaction is carried out at a reaction system pressure of 200 Pa or less and a temperature range of 210 to 280°C.

[0261] In reducing the pressure in the polycondensation reaction, it is preferable to control the balance between the temperature and the pressure in the reaction system. In particular, if either the temperature or the pressure is changed too quickly, unreacted monomers may be distilled off, the molar ratio of the dihydroxy compound to the carbonic acid diester may become inappropriate, and the degree of polymerization may decrease.

[0262] Specifically, in the case where a dihydroxy compound is used, for example, in addition to a dihydroxy compound represented by formula (P1), such as a compound represented by formula (24), isosorbide, or 1,4-cyclohexanedimethanol, and the ratio of 1,4-cyclohexanedimethanol used to the total dihydroxy compounds is 50 mol% or more in molar ratio, 1,4-cyclohexanedimethanol is likely to be distilled as a monomer. Therefore, it is preferable to carry out a polycondensation reaction while reducing pressure and raising the temperature at a rate of 40°C / h or less until the pressure in the reaction system reaches about 13 kPa, and then further raising the temperature at a rate of 40°C / h or less under a pressure of about 6.67 kPa, and finally carrying out a polycondensation reaction at a pressure of 200 Pa or less and a temperature of 200 to 250°C. In this case, a polycarbonate resin with a sufficiently high degree of polymerization is obtained.

[0263] In addition, when the molar ratio of 1,4-cyclohexanedimethanol to the total dihydroxy compounds is less than 50 mol%, a sudden increase in viscosity is likely to occur, and even more so when it is 30 mol% or less. Therefore, it is preferable to carry out the polycondensation reaction while increasing the temperature at a rate of 40°C / h or less under reduced pressure until the pressure in the reaction system reaches about 13 kPa, and then to carry out the reaction while increasing the temperature at a rate of 40°C / h or more under a pressure of about 6.67 kPa, and finally to carry out the polycondensation reaction at a temperature of 220°C to 290°C under a reduced pressure of 200 Pa or less. In this case, a polycarbonate resin with a sufficiently high degree of polymerization is obtained. It is more preferable to carry out the temperature increase at a rate of 50°C / h under the above-mentioned pressure of about 6.67 kPa.

[0264] The reaction can be carried out in a batch manner or a continuous manner, or in a combination of a batch manner and a continuous manner.

[0265] When producing a polycarbonate resin by melt polymerization, a phosphoric acid compound, a phosphorous acid compound, a metal salt of phosphoric acid, or a metal salt of phosphorous acid may be added during polymerization for the purpose of preventing coloration.

[0266] As the phosphoric acid compound, trialkyl phosphate such as trimethyl phosphate and triethyl phosphate is suitable. As the phosphoric acid compound, one kind of compound or two or more kinds of compounds can be used. The amount of the phosphoric acid compound added is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total dihydroxy compounds used in the reaction. If the amount of the phosphorus compound added is less than the lower limit, the coloring prevention effect is reduced. If the amount is more than the upper limit, it may cause an increase in haze, or the addition of the phosphorus compound may promote coloring or reduce heat resistance.

[0267] As the phosphorous acid compound, the following compounds used as heat stabilizers can be used. Specific examples include trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, etc. As the phosphorous acid compound, one or more compounds are used.

[0268] The amount of the phosphorous acid compound added is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total dihydroxy compounds used in the reaction. If the amount of the phosphorous acid compound added is less than the lower limit, the coloring prevention effect is reduced. If the amount is more than the upper limit, the haze may increase, or the addition of the phosphorous acid compound may promote coloring or reduce heat resistance.

[0269] A phosphoric acid compound and its metal salt, or a phosphorous acid compound and its metal salt can be used in combination. In this case, the total amount of these compounds and metal salts added is preferably 0.0001 mol% or more and 0.005 mol% or less, and more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total dihydroxy compounds. If the amount added is less than the lower limit, the coloring prevention effect is reduced. If the amount added is more than the upper limit, it may cause an increase in haze, or the addition may promote coloring or reduce heat resistance.

[0270] As the metal salt of a phosphate compound or a metal salt of a phosphite compound, an alkali metal salt or a zinc salt is preferred, and a zinc salt is more preferred. Among these zinc phosphate salts, a long-chain alkyl zinc phosphate salt is preferred.

[0271] Further, a heat stabilizer can be blended into the polycarbonate resin in order to prevent a decrease in molecular weight and a deterioration in color during molding or the like.

[0272] Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, and the like. phosphate, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like.

[0273] Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and dimethyl benzenephosphonate are preferably used.

[0274] As the heat stabilizer, one type of compound may be used, or two or more types of compounds may be used.

[0275] The heat stabilizer may be added during the melt polymerization and then added additionally. That is, after a suitable amount of a phosphorous acid compound or a phosphoric acid compound is blended to obtain a polycarbonate resin, a heat stabilizer such as a phosphorous acid compound may be further blended in. In this case, deterioration of the color of the polycarbonate resin can be further prevented.

[0276] The blending amount of the heat stabilizer is preferably from 0.0001 to 1 part by mass, more preferably from 0.0005 to 0.5 parts by mass, and further preferably from 0.001 to 0.2 parts by mass, based on 100 parts by mass of the polycarbonate resin.

[0277] The polycarbonate resin and the polycarbonate resin composition containing the polycarbonate resin and additives may be molded as they are, or may be molded after being pelletized in a melt extruder. Molding is carried out by a commonly known method such as injection molding, extrusion molding, compression molding, etc.

[0278] In order to improve the compatibility of the polycarbonate resin and obtain stable releasability and other physical properties, it is preferable to use a single screw extruder or a twin screw extruder for melt extrusion. In this case, the use of solvents and the like can be avoided, which reduces the burden on the environment and also improves productivity.

[0279] The melt-kneading temperature depends on the glass transition temperature of the polycarbonate resin. For example, when the glass transition temperature of the polycarbonate resin is lower than 90°C, the melt-kneading temperature of the extruder is usually 130°C to 250°C, preferably 150°C to 240°C. When the melt-kneading temperature is lower than 130°C, the melt viscosity of the polycarbonate resin increases, the load on the extruder increases, and the productivity may decrease. On the other hand, when the temperature is higher than 250°C, the melt viscosity of the polycarbonate resin decreases, making it difficult to obtain pellets. As a result, the productivity may decrease.

[0280] In addition, when the glass transition temperature of the polycarbonate resin is 90°C or higher, the melt kneading temperature is usually 200°C to 300°C, and preferably 220°C to 260°C. When the melt kneading temperature is lower than 200°C, the melt viscosity of the polycarbonate resin increases, which may increase the load on the extruder and reduce the productivity. On the other hand, when the temperature is higher than 300°C, the polycarbonate resin may be easily deteriorated. Specifically, the color of the polycarbonate resin may turn yellow, or the molecular weight may decrease, resulting in a decrease in strength.

[0281] When using an extruder, it is preferable to install a filter to prevent the polycarbonate resin from burning and the inclusion of foreign matter during extrusion. The opening of the filter (specifically, the size of the foreign matter to be removed) depends on the application, physical properties, and characteristics of the polycarbonate resin, but is preferably 100 μm or less. When it is particularly necessary to avoid the inclusion of foreign matter, the opening of the filter is more preferably 40 μm or less, and even more preferably 10 μm or less.

[0282] The extrusion of the polycarbonate resin is preferably carried out in a clean room, in which case it is possible to prevent foreign matter from being mixed into the extruded polycarbonate resin.

[0283] In addition, when the extruded polycarbonate resin is cooled to form chips, it is preferable to cool it by air cooling, water cooling, or the like. In the case of air cooling, it is preferable to use air from which foreign matter has been removed in advance using a HEPA filter or the like. In this case, it is possible to prevent foreign matter in the air from reattaching. In the case of water cooling, it is preferable to use water from which metal components have been removed using an ion exchange resin or the like and from which foreign matter has been removed using a filter. The mesh size of the filter can be appropriately selected, but is preferably 0.45 to 10 μm.

[0284] [Physical properties of carbonate-based resins with carbonate bonds] The physical properties and characteristics of the carbonate-based resin can be adjusted depending on the desired application.

[0285] <Glass transition temperature> From the viewpoint of increasing heat resistance, the glass transition temperature of the carbonate-based resin is preferably 100°C or higher, more preferably 105°C or higher, even more preferably 110°C or higher, even more preferably 115°C or higher, and particularly preferably 125°C or higher. From the viewpoint of increasing the glass transition temperature and improving heat resistance, a carbonate-based resin having at least one terminal that is not a hydroxyl group is preferred. On the other hand, if the glass transition temperature is too high, the carbonate-based resin may be deteriorated due to shear heat generated during extrusion. In this case, the melt viscosity may become too high during filtration through a filter, which may lead to deterioration of the carbonate-based resin. Therefore, the glass transition onset temperature Tg is preferably 260°C or lower, more preferably 230°C or lower, even more preferably 200°C or lower, and particularly preferably 180°C or lower. The glass transition temperature of the carbonate-based resin is adjusted to the above range by adjusting the type and mixing ratio of the monomers used during production, adjusting the polymerization temperature, or adjusting the amount of additives added.

[0286] The glass transition temperature is measured as the glass transition onset temperature of the carbonate-based resin. Specifically, the glass transition temperature of the carbonate-based resin is measured, for example, by the method described in the Examples.

[0287] <Saturated water absorption rate> If the saturated water absorption rate of the carbonate-based resin is high, the physical properties of the resin change under high humidity, which may reduce the reliability of the molded product. Therefore, the saturated water absorption rate of the carbonate-based resin is preferably 4 wt% or less, more preferably 3.5 wt% or less, even more preferably 3 wt% or less, even more preferably 2.8 wt% or less, and particularly preferably 2.5 wt% or less. The saturated water absorption rate of the carbonate-based resin is measured, for example, by the method described in the Examples. The saturated water absorption rate of the carbonate-based resin is adjusted to the above range by adjusting the type and mixing ratio of the monomers used during production, adjusting the polymerization temperature, and adjusting the amount of additives added.

[0288] <Boiling water test> The wet heat resistance of a carbonate-based resin can be evaluated based on the presence or absence of deformation caused by a boiling water test. From the viewpoint of excellent wet heat resistance stability, it is preferable that the carbonate-based resin does not deform in the boiling water test.

[0289] <Reduced viscosity> The degree of polymerization (specifically, molecular weight) of carbonate-based resins can be expressed by reduced viscosity if it is higher than a certain level. With the exception of polycarbonate diols and the like, which are used with a relatively low degree of polymerization (molecular weight), the degree of polymerization (specifically, molecular weight) of carbonate-based resins is measured by reduced viscosity. The reduced viscosity is measured as follows. First, a sample is prepared in which the carbonate-based resin concentration is precisely adjusted to 1.00 g / dl using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a weight ratio of 1:1. Next, the reduced viscosity of the sample is measured at a temperature of 30.0°C ± 0.1°C.

[0290] If the reduced viscosity of the carbonate-based resin is too low, the properties of the molded product obtained after molding, such as heat resistance, chemical resistance, abrasion resistance, and mechanical strength, may be reduced. Therefore, the reduced viscosity of the carbonate-based resin is preferably 0.20 dL / g or more, and more preferably 0.30 dL / g or more. On the other hand, if the reduced viscosity is too high, the fluidity of the resin during molding may decrease, the productivity and moldability may decrease, and the distortion of the molded product may become large. Therefore, the reduced viscosity is preferably 1.50 dL / g or less, more preferably 1.20 dL / g or less, even more preferably 1.00 dL / g or less, and even more preferably 0.90 dL / g or less. The reduced viscosity of the carbonate-based resin is measured, for example, by the method described in the Examples. The reduced viscosity of the carbonate-based resin is adjusted to the above range by adjusting the type and blending ratio of the monomers used during production, adjusting the polymerization temperature, and adjusting the amount of additives added.

[0291] <Bending test> The toughness of a carbonate-based resin is evaluated, for example, by a bending test. If the resin breaks during this test, the molded article may be brittle. More specifically, the bending test is performed according to the method described in the examples.

[0292] <Charpy impact test> The toughness of carbonate-based resins is evaluated, for example, by a Charpy impact test. If the Charpy impact strength is low, the molded product may become brittle. Therefore, a test piece with a notch tip radius of 0.25R was used, and measurements were performed at room temperature (23°C) in accordance with ISO179 (2000), with a Charpy impact test value of 1 kJ / m 2 It is preferable that the concentration is 2 kJ / m or more. 2 More preferably, it is 3 kJ / m or more. 2 It is more preferable that the Charpy impact test value is 1 kJ / m or more when measured at a low temperature (-20°C). 2 It is preferable that the concentration is 2 kJ / m or more. 2 More preferably, it is 3 kJ / m or more. 2 It is more preferable that the Charpy impact test value measured at room temperature (23°C) and low temperature (-20°C) is 3 kJ / m or more. 2 More specifically, the Charpy impact test is carried out by the method described in the Examples. The Charpy impact strength of the carbonate-based resin is adjusted to the above range by adjusting the type and mixing ratio of the monomers used in the production, the polymerization temperature, or the amount of additives added.

[0293] <Pencil hardness> If the hardness of the carbonate-based resin is low, the molded product is easily scratched. The pencil hardness of the carbonate-based resin is preferably B or more, more preferably F or more. From the viewpoint of further improving the scratch resistance of the molded product, the pencil hardness of the carbonate-based resin is more preferably H or more. The pencil hardness is measured by a pencil hardness test. More specifically, the pencil hardness is measured by the method described in the examples. The pencil hardness of the carbonate-based resin is adjusted to the above range by adjusting the type and mixing ratio of the monomers used during production, adjusting the polymerization temperature, or adjusting the amount of additives added.

[0294] <Photoelastic coefficient> If the photoelastic coefficient of carbonate-based resin is high, a phase difference occurs due to stress, resulting in low optical reliability. The photoelastic coefficient of carbonate-based resin is 18×10 -12 Pa -1 Less than or equal to 15×10 is preferred -12 Pa -1 Less than or equal to 12×10 is preferable. -12 Pa -1 The following is even better: 9×10 -12 Pa -1 The following is even more preferable: 4×10 -12 Pa -1 The following is particularly preferred. In addition, it is preferable that the resin having a negative photoelastic coefficient has a negative photoelastic coefficient from the viewpoint of reducing the photoelastic coefficient of other resins by blending. The photoelastic coefficient is specifically measured by the method described in the Examples.

[0295] <5% thermogravimetric reduction temperature (Td5)> If the 5% thermal weight loss temperature of the carbonate-based resin is high, it is difficult for the resin to undergo thermal decomposition. The 5% thermal weight loss temperature of the carbonate-based resin is preferably 200° C. or higher, more preferably 250° C. or higher, and particularly preferably 300° C. or higher. The 5% thermal weight loss temperature is specifically measured by the method described in the Examples.

[0296] [Resin composition] Various additives can be added to the carbonate-based resin to obtain a resin composition.

[0297] An antioxidant can be added to the carbonate-based resin, which can prevent the carbonate-based resin from being oxidized.

[0298] Examples of the antioxidant include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Examples of the antioxidant include methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, etc. One or more compounds can be used as the antioxidant.

[0299] The blending amount of the antioxidant is preferably 0.0001 to 0.5 parts by mass with respect to 100 parts by mass of the carbonate-based resin.

[0300] A mold release agent can be added to the carbonate resin, which improves the releasability from the mold during melt molding.

[0301] Examples of the release agent include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, and organopolysiloxanes.

[0302] The higher fatty acid ester is preferably a partial or full ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of such partial or full esters of a monohydric or polyhydric alcohol and a saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, stearyl stearate, behenic acid monoglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, and 2-ethylhexyl stearate.

[0303] Among these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

[0304] The higher fatty acid is preferably a saturated fatty acid having a carbon number of 10 to 30. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

[0305] These release agents may be used either as a single compound or as a combination of two or more compounds.

[0306] The amount of the release agent to be added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carbonate-based resin.

[0307] The carbonate resin may also contain a light stabilizer.

[0308] Examples of light stabilizers include 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), and 2,2'-p-phenylenebis(1,3-benzoxazin-4-one).

[0309] As the light stabilizer, one type of compound may be used, or two or more types of compounds may be used.

[0310] The amount of the light stabilizer to be added is preferably 0.01 to 2 parts by mass based on 100 parts by mass of the carbonate-based resin.

[0311] In addition, a bluing agent can be blended with the carbonate-based resin to eliminate the yellow color. As the bluing agent, any agent that is used for carbonate-based resins can be used without any problems. From the viewpoint of easy availability, anthraquinone-based dyes are preferred.

[0312] Specific examples of bluing agents include those having the general name Solvent Violet 13 [CA.No (Color Index No) 60725], those having the general name Solvent Violet 31 [CA.No 68210, those having the general name Solvent Violet 33 [CA.No 60725], those having the general name Solvent Blue 94 [CA.No 61500], those having the general name Solvent Violet 36 [CA.No 68210], those having the general name Solvent Blue 97 [Bayer's "Macrolex Violet RR"], and those having the general name Solvent Blue 45 [CA.No 61110].

[0313] The bluing agent may be used alone or in combination of two or more kinds.

[0314] The blending amount of the bluing agent is usually 0.1×10 −4 to 2×10 −4 parts by mass with respect to 100 parts by mass of the carbonate-based resin.

[0315] Examples of the method for mixing the carbonate-based resin with the various additives as described above include a method using a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder, etc. Another mixing method is a solution blending method in which each component is mixed in a state dissolved in a common good solvent such as methylene chloride. The mixing method is not particularly limited, and any method may be used as long as it is a commonly used polymer blending method.

[0316] The carbonate-based resin may be blended with other thermoplastic resins. From the viewpoint of good optical performance and tendency to be injection moldable, it is preferable to blend the carbonate-based resin with other thermoplastic resins. Specific examples of other thermoplastic resins that are blended together with the carbonate-based resin include polycondensation polymers, olefin polymers, and addition polymerization polymers, and polycondensation polymers are preferred.

[0317] More specifically, examples of the olefin polymer include polyethylene and polypropylene, and examples of the polymerization polymer include polyester, polyamide, polyester carbonate, polyamide, polyimide, and the like.

[0318] It is preferable that the carbonate-based resin and the other thermoplastic resin have compatibility. In this case, when the resin composition and the molded article thereof exhibit excellent transparency, the decrease in the transparency can be prevented.

[0319] The resin composition obtained by the above blending is a polymer coexistence product in which a polymer having at least the structural unit B1 (i.e., a carbonate-based resin) and another polymer different from this polymer (i.e., the above-mentioned other thermoplastic resin) coexist. In this case, the resin composition can contain the structural unit B1, for example, at any molar fraction. From the viewpoint of improving the surface hardness or reducing the photoelastic coefficient, the content ratio of the structural unit B1 of the carbonate-based resin in the total amount of thermoplastic resin contained in the resin composition (specifically, the total amount of the carbonate-based resin having the structural unit B1 and the other thermoplastic resin) is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 15 mol% or more, even more preferably 25 mol% or more, and particularly preferably 37.5 mol% or more, based on the amount of substance. From a similar viewpoint, the content ratio of the structural unit B1 of the carbonate-based resin in the total amount of the thermoplastic resin contained in the resin composition is, on a mass basis, preferably 1 mass% or more, more preferably 10 mass% or more, even more preferably 40 mass% or more, even more preferably 60 mass% or more, and particularly preferably 75 mass% or more.

[0320] On the other hand, from the viewpoint of achieving both moist heat resistance and film strength, the content ratio of the structural unit B1 of the carbonate-based resin in the total amount of the thermoplastic resin contained in the resin composition is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, even more preferably 4 mol% or more, and particularly preferably 5 mol% or more, based on the amount of substance. Also, it is preferably 50 mol% or less, more preferably 37.5 mol% or less, even more preferably 25 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. From the same viewpoint, the content ratio of the structural unit B1 of the carbonate-based resin in the total amount of the thermoplastic resin contained in the resin composition is preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 5 mass% or more, even more preferably 7 mass% or more, and particularly preferably 10 mass% or more, based on the mass. Furthermore, it is preferably 95% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0321] In addition, a resin composition such as a polymer alloy can be obtained by kneading a carbonate-based resin with a synthetic resin, a biodegradable resin, a rubber, or the like. As the synthetic resin, the biodegradable resin, or the rubber, one or more kinds of resins or rubbers can be used. As the synthetic resin, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, acrylonitrile-butadiene-styrene copolymer (i.e., ABS), acrylonitrile-styrene copolymer (i.e., AS, SAN), or the like can be used. As the biodegradable resin, polylactic acid, polybutylene succinate, or the like can be used.

[0322] A resin composition can be prepared by adding additives such as a nucleating agent, a flame retardant, a flame retardant assistant, an inorganic filler, an impact modifier, a hydrolysis inhibitor, a foaming agent, a dye, a pigment, etc. to the carbonate-based resin together with the other resins described above. As such additives, those generally used in thermoplastic resin compositions are used.

[0323] [Method of molding thermoplastic resin having carbonate bonds] Carbonate-based resins and resin compositions containing the same are molded by commonly known methods such as injection molding, extrusion molding, and compression molding. Molded articles are obtained by molding. In this manner, it is possible to obtain molded articles having excellent properties such as heat resistance, transparency, light resistance, weather resistance, and mechanical strength.

[0324] [Uses of thermoplastic resins with carbonate bonds] Carbonate-based resins are suitable for applications such as films, sheets, bottles, various structural materials, and optical components. In addition, carbonate-based resins containing at least the structural unit B1 are excellent in mechanical strength and wet heat resistance, and therefore are suitable for applications such as films, sheets, bottles, containers, various structural materials, automotive parts, glass substitute materials, and injection molding materials, which require flexibility, surface hardness, and wet heat resistance. In addition, carbonate-based resins containing at least the structural unit B1 are considered to have excellent optical reliability because of their low photoelastic coefficient. Therefore, such carbonate-based resins are also suitable for applications such as retardation films, diffusion sheets, and optical films used in polarizing films, optical disks, binders for fixing dyes and charge transfer agents, and lenses used in cameras, finders, CCDs, CMOS, and the like.

[0325] [Why it's effective] The reason why the present invention is effective is not yet clear, but is presumed to be as follows. The carbonate-based resin containing the structural unit B1 has a specific fused ring skeleton as described above and is novel. Such a carbonate-based resin has a cyclobutane skeleton with a non-planar structure and has two carbon ring structures sandwiching the cyclobutane skeleton.

[0326] The condensed ring structure containing a cyclobutane structure has a large distortion and a very rigid skeleton compared to the condensed ring structures containing a cyclopentane structure and a cyclohexane structure, so the resulting resin exhibits high heat resistance and surface hardness, and almost no local structural changes occur even when stress is applied, so it exhibits the excellent effect of a low photoelastic coefficient, which is one of the important optical properties. On the other hand, a rigid structure that exhibits high heat resistance generally has a high yield stress and tends to be a brittle material. However, surprisingly, despite the rigid skeleton of the condensed ring structure containing the cyclobutane structure, the resulting carbonate-based resin had good toughness.

[0327] It is generally known that the more entanglements per unit volume of the main chain in a resin, the less likely it is to undergo brittle fracture. Polymers with bulky substituents in the side chain, such as polystyrene, have a shorter main chain length per molecular weight, which reduces the number of entanglements per unit volume of the main chain and makes them more likely to undergo brittle fracture. For the same reason, the inventors of the present application have found that carbonate-based resins using the above-mentioned DMNDM, which has bulky substituents in the side chain, have high heat resistance but are very brittle. On the other hand, the cyclobutane structure occupies a small volume three-dimensionally in the resin and does not impair the number of entanglements in the main chain, so carbonate-based resins with this condensed ring exhibit high heat resistance and surface hardness while maintaining their toughness. EXAMPLES

[0328] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, "%" indicates "% by mass".

[0329] [Evaluation method] The physical properties and characteristics of the thermoplastic resin compositions and molded articles were evaluated by the following methods.

[0330] (1) Press film production Polycarbonate resin pellets were vacuum dried at 90°C for 5 hours or more. A spacer was prepared by hollowing out a metal plate (SUS) with an outer width of 10 cm length, 10 cm width, and 0.5 mm thickness, leaving a width of 1 cm, and an inner width of 8 cm length and 8 cm width. This spacer was sandwiched between two mirror-finished SUS plates with a length of 10 cm length, width of 10 cm width, and thickness of 1.5 mm, and about 4 g of pellets were placed inside the spacer frame and heat pressed. The heat press temperature was 200 to 230°C, the preheating time was 5 to 7 minutes, and the pressure during molding was 40 MPa. The pressure time during molding was 1 minute. After the heat press, the sheet-like sample was taken out together with the mirror plate and spacer, and was pressurized and cooled for 3 minutes at a pressure of 20 MPa using a water tube cooling press. A film with a thickness of 400 to 500 μm was produced.

[0331] (2) Glass transition temperature Tg The glass transition temperature was measured using a differential scanning calorimeter "EXSTAR 6220" manufactured by SII Nano Technology Co., Ltd. The measurement was performed in accordance with JIS K7121:1987. Specifically, about 10 mg of the measurement sample was heated at a heating rate of 10 ° C / min, and the sample heated to 250 ° C was quenched with liquid nitrogen and heated again to 250 ° C at a heating rate of 10 ° C / min. From the DSC data obtained in the second heating, the midpoint glass transition onset temperature is calculated from the temperature at which a straight line equidistant in the vertical direction from a straight line extending the low-temperature side baseline and the high-temperature side baseline intersects with the curve of the step-like change part of the glass transition. This midpoint glass transition onset temperature is treated as the glass transition temperature Tg.

[0332] (3) Reduced viscosity A polycarbonate resin was dissolved using a solvent to prepare a polycarbonate solution with a concentration of 1.00 g / dl. A mixed solvent of phenol and 1,1,2,2-tetrachloroethane was used as the solvent. The mixing ratio of phenol to 1,1,2,2-tetrachloroethane was 1:1 by mass. Dissolution in the mixed solvent was carried out for 30 minutes while stirring at 110°C, and the polycarbonate solution after cooling was used to measure the reduced viscosity. The reduced viscosity was measured at a temperature of 30.0°C ± 0.1°C using a Ubbelohde viscometer "DT-504 automatic viscometer" manufactured by Chuo Rika Co., Ltd. The relative viscosity η was calculated from the passage time t0 of the solvent and the passage time t of the solution using the following formula (α): rel Calculate the relative viscosity η rel From the following formula (β), the specific viscosity η sp (Unit: g cm -1 ·sec -1 In the formula (β), η0 is the viscosity of the solvent. And the specific viscosity η sp Divide by the concentration c (g / dL) of the polycarbonate solution to obtain the reduced viscosity η (η = η sp / c) was calculated. A higher value indicates a higher molecular weight. η rel =t / t0 (α) η sp =(η-η0) / η0=η rel -1 (β)

[0333] (4) Saturated water absorption rate The film prepared by method (1) was cut into a shape of approximately 40 mm in length and 40 mm in width to prepare a measurement sample. The measurement test piece (film) was dried in a vacuum dryer at 90°C under vacuum for 5 hours or more, and then cooled to room temperature while maintaining the vacuum. Dry air was introduced to return the pressure to normal pressure, and the dry weight W0 of the measurement test piece (film) was quickly measured. The test piece (film) was immersed in 500cc of pure water at room temperature (23°C) and left for 144 hours. After 144 hours, the test piece (film) was taken out, the water on the surface of the test piece (film) was wiped off with a cloth, and the weight W1 after water absorption was quickly measured. The saturated water absorption rate was calculated using the following formula. Saturated water absorption rate (%)=((W1-W0) / W0)×100

[0334] (5) Boiling water test (evaluation of moist heat resistance) The film prepared by method (1) was cut into a shape measuring approximately 40 mm in length and 40 mm in width to prepare a measurement sample. The test piece (film) was placed in a mesh basket and immersed in a water tank heated to 100°C and left for 3 hours. After 3 hours, the mesh basket was removed and the test piece was cooled, after which the appearance of the test piece was observed. Test pieces (films) that were not deformed were rated as pass (○), and those that were deformed were rated as fail (×).

[0335] (6) Charpy impact test The polycarbonate resin pellets were vacuum dried at 90°C for 5 hours or more. Then, using a Micro15cc Twin Screw Compounder manufactured by Leo Labs, the pellets were melted at 240°C for 3 minutes (180 seconds) under a nitrogen atmosphere, and then injection molded at a mold temperature of 70°C and a cylinder temperature of 240°C to obtain ISO test pieces for mechanical property testing. The obtained test pieces were subjected to a notched Charpy impact test in accordance with ISO179 (2000) to obtain the notched Charpy impact strength. In this test, measurements were made using test pieces with a notch tip radius of 0.25R. The Charpy impact test was performed at room temperature (23°C) and at a low temperature (-20°C).

[0336] (7) Bending test A test piece 5 mm wide and 20 mm long was cut out from the film prepared by method (1). When both ends of the test piece were bent, those that were bent were marked with an ◯, and those that broke were marked with an ×.

[0337] (8)Pencil hardness The pencil hardness of the film prepared by method (1) was measured in accordance with JIS K5600-5-4:1999 using a pencil hardness tester (No. 601-B, manufactured by Mize Testing Instruments Co., Ltd.) under conditions of a load of 750 g and a measurement speed of 60 mm / min.

[0338] (9) Photoelastic coefficient <Sample Preparation> A sample with a width of 5 mm and a length of 20 mm was cut out from the film prepared by method (1). <Measurement> The measurements were performed using a combination of a birefringence measuring device consisting of a He-Ne laser, a polarizer, a compensator, an analyzer, and a photodetector, and a vibration type viscoelasticity measuring device (UBM Co., Ltd.) (for details, see Journal of the Society of Rheology, Japan, Vol. 19, p. 93-97 (1991)). The cut sample was fixed to the viscoelasticity measuring device, and the storage modulus E' was measured at a frequency of 96 Hz at room temperature of 25 ° C. At the same time, the emitted laser light was passed through the polarizer, sample, compensator, and analyzer in that order, and picked up by a photodetector (photodiode), and the amplitude and phase difference with respect to strain were obtained for the waveform of angular frequency ω or 2ω through a lock-in amplifier, and the strain optical coefficient O' was obtained. At this time, the directions of the polarizer and the analyzer were adjusted to be perpendicular to each other and to form an angle of π / 4 with respect to the extension direction of the sample. The photoelastic coefficient C was calculated from the storage modulus E' and the strain optical coefficient O' using the following formula. C=O' / E' (10) 5% thermogravimetric reduction temperature (Td5) Using a TG / DTA7200 manufactured by SII Nano Technology, approximately 10 mg of the sample was placed in a container and measured from 40°C to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere (nitrogen flow rate 50 ml / min), and the temperature at which the weight decreased by 5% (Td5) was calculated. The higher this temperature, the less likely the sample is to undergo thermal decomposition. (11)NMR (nuclear magnetic resonance) NMR of the resins of Examples 1-1 to 1-5 was measured as follows. Approximately 30 mg of a sample was placed in an NMR sample tube with an outer diameter of 5 mm and dissolved in 0.7 ml of deuterated chloroform (containing 0.03 v / v % tetramethylsilane). The NMR was measured using a Bruker "AVANCE III 950" at a resonance frequency of 950.3 MHz, a flip angle of 30°, and a measurement temperature of 25° C. 1 H-NMR was measured. The NMR of the compounds in the production examples was measured in the same manner as for the resins in the above examples, except that the device was changed to a JEOL "ECZ400S" and the frequency was changed to 400 MHz.

[0339] <Production Example 1> (1) Synthesis of Pentacyclopentadeca-3(5),4(6)-diene (N3,N4) Under a nitrogen atmosphere, cyclopentadiene (200 g, 3.03 mol), tris-p-tolylphosphine (41 g, 136 mmol), acetic acid (550 mL), acetonitrile (250 mL), and Pd(dba)2 (26 g, 45.4 mmol) were added to an autoclave, and the inside of the autoclave was stirred at 100°C for 3 hours. Water (2000 mL) was added to the reaction liquid in the autoclave, and petroleum ether (1500 mL) was added, and extraction was repeated three times. The organic layer was then concentrated and purified by column chromatography. As a result, 110 g of pentacyclopentadeca-3(5),4(6)-diene was obtained. 1 The H NMR analysis confirmed that pentacyclopentadeca-3(5),4(6)-diene was obtained. The analytical results are as follows:

[0340] [ka]

[0341] 1 H NMR(400MHz, CDCl3):δ= 5.70-5.75(m, 2H), 5.63-5.70(m, 2H), 5.54(dd, J= 5.6, 2.0 Hz, 2H), 5.37-5.45(m, 2H), 2.97(dqt, J=10.4, 5.2, 5.2, 5.2, 2.4, 2.4 Hz, 2H), 2.74(br, J=3.2 Hz, 1H), 2.63-2.69(m, 1H), 2.53-2.63(m, 2H), 2.46-2.53(m, 2H), 2.14-2.28(m, 6H), 2.12(td, J= 4.8, 2.4 Hz, 6H), 1.99-2.06(m, 2H), 1.94(br, J= 6.4 Hz, 1H), 1.78-1.88(m, 2H), 1.67-1.73(m, 1H), 1.46(tt, J= 2.4, 1.2 Hz, 1H) 1.44(dt, J= 3.6, 1.2Hz, 1H)

[0342] (2) Synthesis of compound (N5) A stainless steel autoclave (i.e., reactor) with an internal volume of 300 mL was charged with 45.7 g (230 mmol) of pentacyclopentadeca-3(5),4(6)-diene, 20.12 g (0.47 mmol) of Rh(acac)(CO), 1.37 g (2.1 mmol) of tris(2,4-di-t-butylphenyl)phosphite, and 145 mL of methylcyclohexane, and the reactor was sealed. The inside of the reactor was replaced with nitrogen, and then replaced with water gas (specifically, a mixed gas with a molar ratio of CO / H2=1 / 1), and water gas was further charged until the internal pressure of the reactor reached 1 MPa. The contents of the reactor were heated and stirred to bring the internal temperature to 70°C, and water gas was injected until the internal pressure reached 5 MPa. The water gas consumed in the reaction was continuously supplied from the accumulator via a pressure regulator, and the reaction was carried out at 70° C. for 6 hours while maintaining the internal pressure at 5 MPa.

[0343] The recovered reaction solution was extracted four times with 100 mL of a mixture of methanol and water. The volume ratio of the mixture was methanol / water = 4 / 1. Methanol was distilled off from the recovered aqueous solution containing methanol under reduced pressure to obtain an aqueous phase. The aqueous phase was extracted three times with 100 mL of toluene. The toluene solution was dehydrated over anhydrous Na2SO4, the drying agent was filtered off, and the filtrate was concentrated to obtain a pale yellow oil. 1 It was confirmed by H NMR that this oily substance was compound (N5). The yield of compound (N5) was 58.0 g (224 mmol), and the yield was 97.6%. 1 The H NMR analysis confirmed that compound (N5) was obtained, with the following analytical results:

[0344] 1 H NMR(400MHz, CDCl3):δ= 9.9-9.4(m, 2H), 3.2-3.0(m, 0.5H), 2.7-2.35(m, 4H), 2.3-1.9(m, 3.5H), 1.9-1.3(m, 10H)

[0345] [ka]

[0346] (3) Synthesis of compound (P2) Compound (P2) was produced from compound (N5) by hydrogenation reaction. Specifically, 70.6g (274mmol) of compound (N5), 2.6g of Ru / C (0.13g as Ru, 1.2mmol), and 100mL of methanol were charged into a stainless steel autoclave with an internal volume of 300mL, and the reactor was sealed. The inside of the reactor was replaced with nitrogen, then replaced with hydrogen, and hydrogen was further filled into the reactor until the internal pressure reached 1MPa. The contents of the reactor were heated and stirred to bring the internal temperature to 90°C, and hydrogen was injected until the internal pressure reached 8MPa. The hydrogen consumed in the reaction was continuously supplied from the pressure accumulator via a pressure regulator, and the reaction was carried out at 100°C for 12 hours while maintaining the internal pressure at 8MPa. The reaction liquid was filtered through Celite to remove the catalyst, and the filtrate was concentrated with an evaporator. The residue was purified by column chromatography (packing material: silica gel, solvent: hexane / ethyl acetate=1 / 1 (volume ratio)) to obtain a pale yellow oil. 1 From the results of analysis by H NMR and GC-MS, it was confirmed that the oily substance was an isomer mixture of compound (P2). The yield of compound (P2) was 19.0 g (72 mmol), and the yield was 26.3%. Compound (P2) is referred to as "DA13" as appropriate. 1 H NMR(400MHz,CDCl3): δ=3.8-3.2(m, 4H), 2.7-2.2(m, 2H), 2.1-1.0(m, 20H) GC-MS(CI+,NH3) [M+NH4] + m / z: 280, M + =262 C 17 H 26 O2 molecular weight 262.4

[0347] The GC-MS (gas chromatography mass spectrometry) measurement was carried out as follows. Ionization was carried out by the CI method, and ammonia was used as the reagent gas. The injection temperature was 250°C, and the analysis temperature was raised from 50°C at 10°C / min, held at 220°C for 10 minutes, and then raised to 300°C at 15°C / min. The GC used was an Agilent Technology 7890, and the column was an Agilent Technology DB-1 (0.25mmφ×30m, film thickness 0.25μm).

[0348] [ka]

[0349] In the examples, DA13 prepared by the above-mentioned hydrogenation reaction was used, but DA13 can also be produced from compound (N5) by the following NaBH3 reaction. First, a dropping funnel was attached to a 500 mL three-neck flask containing a rotor. 31.1 g (120 mmol) of compound (N5) and 150 mL of methanol were added to the flask and stirred, and then the flask was cooled in an ice bath so that the internal temperature of the flask was 0°C. 3.6 g (90 mmol) of sodium borohydride (purity 95%) was dissolved in 20 mL of 1% NaOH aqueous solution from the dropping funnel, and the aqueous solution was dropped into the flask over 40 minutes, and then the flask was stirred at room temperature for another hour. The reaction solution in the flask was cooled in an ice bath, and 30 mL of 15% sulfuric acid was added to the reaction solution to decompose the sodium borohydride remaining in the reaction solution. The reaction solution was concentrated under reduced pressure to obtain a residue. The residue was separated into two phases by adding 300 mL of ethyl acetate and 100 mL of water to obtain an aqueous phase. This aqueous phase was extracted twice with 100 mL of ethyl acetate. Anhydrous Na2SO4 (i.e., a drying agent) was added to the oil phase to dehydrate it, and the drying agent was removed by filtration. The oil phase was then concentrated in an evaporator to obtain a concentrate. Inorganic matter was removed from the concentrate by chromatography using SiO2 as a packing material and acetone as a solvent, and the concentrate was further concentrated in an evaporator to obtain a pale yellow oil. 1The results of H NMR analysis confirmed that this oily substance was DA13. The yield of DA13 was 30.2 g (115 mmol), and the yield was 96.0%.

[0350] Regarding the above-mentioned oil 1 The results of the H NMR analysis are as follows: 1 H NMR(400MHz,CDCl3): δ=3.8-3.2(m, 4H), 2.7-2.2(m, 2H), 2.1-1.0 (m, 20H)

[0351] <Production Example 2> Synthesis of NCDDM Add norbornadiene (10 g, 108.53 mmol, 11.04 mL) and Ru(CO) to the autoclave. 12 (1.39 g, 2.17 mmol), DMAc (i.e., dimethylacetamide) (2.15 g, 21.71 mmol, 2.24 mL), and NMP (6 mL) were added to the reactor, which was then sealed and replaced with nitrogen, and the mixture was stirred at 80°C for 10 hours. The progress of the reaction was confirmed by TLC (petroleum ether: ethyl acetate = 10:1, Rf = 0.9). The reaction was stopped by adding water, and the mixture was extracted with 30 mL x 3 dichloromethane and washed with saturated saline (20 mL x 2) and pure water. After dehydration using sodium sulfate, the mixture was dried and purified using a silica gel column (solvent: hexane) to obtain NCD as pale yellow crystals in a yield of 1.88 g and 15.6%. 1 The results of 1 H NMR analysis confirmed that this oily substance was NCD.

[0352] 1 H NMR(400MHz,CDCl3): δ=6.03(d,4H), 2.65(d,4H), 1.71 (d,2H), 1.36 (s,4H),1.25 (d,2H)

[0353] [ka]

[0354] In a 300mL stainless steel autoclave, 25.0g (136mmol) of NCD, 20.09g (0.35mmol) of Rh(acac)(CO), 0.88g (1.4mmol) of tris(2,4-di-t-butylphenyl)phosphite, and 120mL of methylcyclohexane were charged and the reactor was sealed. The inside of the reactor was replaced with nitrogen, then replaced with water gas (CO / H2=1 / 1), and water gas was further filled up to 1MPa. The reactor was heated and stirred, and water gas was injected at an internal temperature of 80°C until the reactor pressure reached 7MPa. The water gas consumed in the reaction was continuously supplied from the accumulator via a pressure regulator, and the reaction was carried out at an internal pressure of 6.5MPa and 100°C for 1 hour. THF was added to the gel-like reaction mixture, which was then recovered as a homogeneous solution, and the solvent was distilled off under reduced pressure to obtain a brown viscous liquid. 1 H NMR analysis confirmed that this recovered product was the NCD diformyl compound, which was used in the next reaction without further purification.

[0355] 1 H NMR(400MHz,CDCl3) δ9.7-9.4 (m, 2H), 2.5-2.3 (m, 2H), 2.3-2.0 (m, 4H), 2.0-1.6 (m, 6H), 1.4-1.1 (m, 3H), 1.0-0.8 (m, 3H)

[0356] [ka]

[0357] In a 1000mL three-neck flask, NCD diformyl body (total amount of oxo reaction concentrate, theoretical amount 33.2g, 136mmol), 300mL THF, and 80mL ethanol were added and stirred in an ice bath to obtain a homogeneous solution. 5.60g (133mmol) of sodium borohydride (weight purity 90%) was dissolved in 150mL of 1mol / L NaOH aqueous solution, and added in 10 portions so that the internal temperature of the reaction solution did not exceed 10℃. After the entire amount was added, the temperature was raised to room temperature and the reaction was carried out for 1 hour. The mixture was cooled in an ice bath, and 40mL of 3mol / L HCl aqueous solution was added while maintaining the internal temperature below 10℃ to decompose the unreacted NaBH4. After removing the solvent with an evaporator, the aqueous phase was extracted with chloroform. The recovered oil phase was washed with desalted water, dehydrated with anhydrous MgSO4, the drying agent was filtered off, and the filtrate was concentrated to obtain a crude product. This crude product was washed with acetonitrile and acetone to isolate a white powdery solid of NCDDM in a yield of 15.5 g (62 mmol) and 45.9%.

[0358] 1 H NMR(400MHz, CDCl3) δ3.5-3.2 (m, 6H), 2.0-1.8 (m, 8H), 1.5-1.3 (m, 2H), 1.3-1.1 (m, 6H), 1.0-0.8 (m, 2H)

[0359] [ka]

[0360] <Production Example 3> Synthesis of TPSA 20g, 50.43mmol of pentacyclopenta-3(5),4(6)-diene (N3,N4) and 102.96g, 1.01mol of Ac2O were dissolved in 800mL of toluene, and 16.95g, 690.86mmol of Na2CO3·3H2O2 were added in 4 portions at 30 minute intervals, and the mixture was heated and stirred at 60°C for 5 hours. After quenching with a saturated aqueous solution of Na2S2O4, water was added and the mixture was extracted with ethyl acetate. The product was dehydrated using sodium sulfate and dried, and purified using silica gel chromatography (petroleum ether / ethyl acetate = 8 / 1) to obtain 12g of 5,16-dioxaheptacycloheptadecane as a yellow solid containing a mixture of isomers in a yield of 67%.

[0361] 1H NMR (400 MHz, CDCl3) δ3.6 (s, 1H), 3.6 (s, 2H), 3.5 (m, 1H), 3.4 (m, 3H), 3.3 (m, 2H), 3.3 (m, 2H), 2.4-2.3 (m, 19H), 2.2 (m, 6H) , 2.0 (m, 7H) , 1.7 (m, 3H) , 1.4 (m, 3H)

[0362] [ka]

[0363] Sulfuric acid was added to anhydrous methanol solution (600mL) of 5,16-dioxaheptacycloheptadecane containing isomers (30g, 130.26mmol) and stirred at room temperature for 4 hours. The reaction was stopped by adding 300mL of saturated aqueous sodium bicarbonate solution, and the methanol was distilled off under reduced pressure, followed by addition of water and extraction with ethyl acetate (200mLx5). The residue was washed with saturated aqueous sodium chloride solution and dehydrated with sodium sulfate. The solvent was distilled off and purified by column chromatography (heptane:ethyl acetate=1:3). 51g of TPSA was obtained as a white solid by recrystallization using ethyl acetate / heptane solvent.

[0364] 1 H NMR(400MHz,CDCl3) δ4.1(d, 2H), 3.7 (br, 2H), 3.5 (m, 3H), 3.5 (d, 5H), 3.4 (d, 2H), 3.3 (s, 1H), 2.2(br, 1H), 2.2-1.9 (m, 27H), 1.4 (t, 2H), 1.1 (m, 2H) Td5: 223℃

[0365] [ka]

[0366] <Production Example 4> Synthesis of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane (FN2) FN2 was synthesized by the method described in JP 2015-25111 A.

[0367] [ka]

[0368] [Raw materials used] The abbreviations and manufacturers of the compounds used in the Production Examples and Examples are as follows: <Dihydroxy compounds> ISB: Isosorbide [Rocket Fleuret] CHDM: 1,4-cyclohexanedimethanol (cis, trans mixture), [SK Chemicals] TCDDM: Tricyclodecane dimethanol [Oxea] DA13: Dihydroxy compound synthesized in Production Example 1 (pentacyclo[7.5.1.02,8.03,7.010,14]pentadecanedimethanol) NBD: Norbornadiene synthesized in Production Example 2 NCD: norbornadiene dimer synthesized in Example 2 NCDDM: Dihydroxy compound of norbornadiene dimer synthesized in Production Example 2 ·TPSA: Dihydroxy compound synthesized in Production Example 3 <Carbonate diester> DPC: Diphenyl carbonate [Mitsubishi Chemical Corporation] <Diester component> FN2: Diester (bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane) synthesized in Production Example 4 <Polymerization catalyst> Calcium acetate monohydrate (Ca(CH3COO)2·H2O) [Kishida Chemical Co., Ltd.]

[0369] (Example 1-1) In this example, a polycarbonate resin was produced using DA13 and ISB as dihydroxy compounds. Specifically, 5.70 g (0.0022 mol) of DA13, 7.41 g (0.051 mol) of isosorbide (hereinafter abbreviated as "ISB"), 15.83 g (0.0739 mol) of diphenyl carbonate (hereinafter abbreviated as "DPC"), and 1.27 × 10 calcium acetate monohydrate as a polymerization catalyst. -4 g(7.25×10 -6mol) was charged into a reaction vessel as a 0.2% aqueous solution, and the heating vessel was heated to 150°C under a nitrogen atmosphere. Stirring was performed as necessary, and the temperature was raised to 220°C in 60 minutes at normal pressure to dissolve the raw materials. In the first step of the reaction, the temperature was kept at 220°C for 30 minutes, and then the pressure was reduced from normal pressure to 13.3 kPa in 40 minutes, and then the pressure was kept at 13.3 kPa for 60 minutes, and the generated phenol was extracted outside the reaction vessel. In the second step, the temperature of the heating tank was raised to 240°C in 20 minutes, and the generated phenol was extracted outside the reaction vessel while controlling the pressure to be 0.200 kPa or less in 30 minutes. After reaching a predetermined stirring torque, the reaction was terminated, and the reaction product was removed from the reaction vessel to obtain a polycarbonate copolymer (specifically, a polycarbonate copolymer having a molar ratio of structural units derived from DPC / structural units derived from DA13 / structural units derived from ISB=100 / 30 / 70). The reduced viscosity of the obtained polycarbonate copolymer was 0.502 dl / g, and the glass transition temperature Tg was 143°C. The saturated water absorption at room temperature was 1.9 wt%. There was no deformation in the boiling water test. The 5% thermal weight loss temperature (Td5) was 345°C under a nitrogen atmosphere. The NMR chart of this polycarbonate copolymer is shown in Figure 9.

[0370] (Example 1-2) In this example, polycarbonate resin was produced using DA13 and ISB as dihydroxy compounds. The materials used were 4.03 g (0.0154 mol) of DA13, 8.98 g (0.0614 mol) of ISB, 16.77 g (0.0783 mol) of DPC, and 1.35 × 10 calcium acetate monohydrate as a catalyst. -4 g (7.68×10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of structural units derived from DPC / structural units derived from DA13 / structural units derived from ISB=100 / 20 / 80) was prepared in the same manner as in Example 1-1, except that a polycarbonate copolymer having a molar ratio of structural units derived from DPC / structural units derived from DA13 / structural units derived from ISB=100 / 20 / 80 was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.638 dl / g, and the glass transition temperature Tg was 152°C. The saturated water absorption at room temperature was 2.7 wt%. No deformation was observed in the boiling water test. The 5% thermal weight loss temperature (Td5) was 341°C in a nitrogen atmosphere. The NMR chart of this polycarbonate copolymer is shown in FIG.

[0371] (Examples 1-3) A polycarbonate resin was prepared using DA13, ISB, and TCDDM as dihydroxy compounds. The materials used were 13.00 g (0.0495 mol) of DA13, 19.45 g (0.0991 mol) of TCDDM, 50.68 g (0.3468 mol) of ISB, 108.24 g (0.5053 mol) of DPC, and 8.73 × 10 calcium acetate monohydrate as a catalyst. -3 g(4.95×10 -5 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units / TCDDM-derived structural units=100 / 10 / 70 / 20) was prepared in the same manner as in Example 1-1, except that a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units / TCDDM-derived structural units=100 / 10 / 70 / 20 was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.669 dl / g, and the glass transition temperature Tg was 134°C. The saturated water absorption at room temperature was 1.9 wt%. No deformation was observed in the boiling water test. The 5% thermal weight loss temperature (Td5) was 346°C in a nitrogen atmosphere. The NMR chart of this polycarbonate copolymer is shown in FIG.

[0372] (Examples 1 to 4) In this example, polycarbonate resin was produced using DA13, ISB, and CHDM as dihydroxy compounds. The materials used were 21.46 g (0.0818 mol) of DA13, 23.59 g (0.1636 mol) of CHDM, 83.68 g (0.5726 mol) of ISB, 178.73 g (0.8344 mol) of DPC, and 1.44 × 10 calcium acetate monohydrate as a catalyst. -2 g (8.18 × 10-5 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units / CHDM-derived structural units=100 / 10 / 70 / 20) was prepared in the same manner as in Example 1-1, except that a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units / CHDM-derived structural units=100 / 10 / 70 / 20 was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.689 dl / g, and the glass transition temperature Tg was 130°C. The saturated water absorption rate at room temperature was 2.1 wt%. No deformation was observed in the boiling water test. The 5% thermal weight loss temperature (Td5) was 343°C in a nitrogen atmosphere. The NMR chart of this polycarbonate copolymer is shown in FIG.

[0373] (Examples 1 to 5) In this example, polycarbonate resin was produced using DA13, ISB, and CHDM as dihydroxy compounds. The materials used were 4.03 g (0.0154 mol) of DA13, 1.11 g (0.0077 mol) of CHDM, 7.86 g (0.0538 mol) of ISB, 16.79 g (0.0784 mol) of DPC, and 3.38 × 10 calcium acetate monohydrate as a catalyst. -4 g (1.92 × 10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units / CHDM-derived structural units=100 / 20 / 70 / 10) was prepared in the same manner as in Example 1-1, except that a 0.2% aqueous solution (mol) of 1,2-dichlorophenyl ether was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.923 dl / g, and the glass transition temperature Tg was 140°C. The saturated water absorption rate at room temperature was 1.9 wt%. No deformation was observed in the boiling water test. The 5% thermal weight loss temperature (Td5) was 348°C in a nitrogen atmosphere. The NMR chart of this polycarbonate copolymer is shown in FIG.

[0374] (Comparative Example 1-1) In this example, polycarbonate resin was produced using ISB and CHDM as dihydroxy compounds. The materials used were 37.83 g (0.2623 mol) of CHDM, 89.44 g (0.6120 mol) of ISB, 191.05 g (0.8918 mol) of DPC, and 3.85 × 10 calcium acetate monohydrate as a catalyst. -3 g (2.19 × 10 -5 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / ISB-derived structural units / CHDM-derived structural units=100 / 70 / 30) was prepared in the same manner as in Example 1-1, except that the molar ratio of the structural units derived from DPC / ISB / CHDM was changed to 100 / 70 / 30. The reduced viscosity of the obtained polycarbonate copolymer was 0.615 dl / g, and the glass transition temperature Tg was 122° C. The saturated water absorption at room temperature was 2.0 wt%. In a boiling water test, the film was deformed.

[0375] (Comparative Example 1-2) In this example, polycarbonate resin was produced using ISB and TCDDM as dihydroxy compounds. The materials used were 47.19 g (0.2404 mol) of TCDDM, 81.98 g (0.5610 mol) of ISB, 175.1 g (0.8174 mol) of DPC, and 3.53 × 10 calcium acetate monohydrate as a catalyst. -3 g(2.00×10 -5 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / ISB-derived structural units / TCDDM-derived structural units=100 / 70 / 30) was prepared in the same manner as in Example 1-1, except that the molar ratio of the structural units derived from DPC / ISB / TCDDM was changed to 100 / 70 / 30. The reduced viscosity of the obtained polycarbonate copolymer was 0.602 dl / g, and the glass transition temperature Tg was 131° C. The saturated water absorption at room temperature was 1.8 wt%. The film was deformed in a boiling water test.

[0376] The glass transition temperatures, bending test results, boiling water test results, saturated water absorption, pencil hardness, and photoelastic coefficients of the polycarbonate resins of Examples 1-1 to 1-4 and Comparative Examples 1 to 1-2 are shown in Table 1. The glass transition temperature and photoelastic coefficient of the polycarbonate resin of Example 1-5 are also shown in Table 1.

[0377] [Table 1]

[0378] As can be seen from Table 1, the thermoplastic resins (specifically, polycarbonate resins) of Examples 1-1 to 1-5 containing specific structural units have sufficiently high glass transition temperatures. Moreover, Examples 1-1 to 1-4 maintained sufficiently high glass transition temperatures while exhibiting good results in the boiling water test and excellent moist heat resistance. In contrast, Comparative Examples 1-1 and 1-2 not containing specific structural units had low glass transition temperatures, failed the boiling water test, and were poor in moist heat resistance.

[0379] As can be seen from Table 1, the thermoplastic resins (specifically, polycarbonate resins) of Examples 1-1 to 1-4 containing specific structural units maintained sufficiently high glass transition temperatures while showing good results in bending tests and boiling water tests, and exhibited excellent toughness and moist heat resistance. In contrast, Comparative Examples 1-1 to 1-2 not containing specific structural units had low glass transition temperatures, insufficient toughness, and insufficient moist heat resistance.

[0380] As can be seen from Table 1, the thermoplastic resins of Examples 1-1 to 1-5 containing specific structural units have good results in the photoelastic coefficient while maintaining a sufficiently high glass transition temperature, and are excellent in optical reliability and heat resistance. In contrast, Comparative Examples 1-1 and 1-2, which do not contain specific structural units, have low glass transition temperatures or insufficient photoelastic coefficients. In particular, the results of Example 1-1 show that the thermoplastic resins containing specific structural units have a very low photoelastic coefficient and are excellent in optical reliability. Furthermore, Examples 1-1 to 1-4 have good results in pencil hardness and are excellent in mechanical strength.

[0381] Although not shown in Table 1, a comparison of the results of the Charpy impact test (specifically, the Charpy impact strength at room temperature and low temperature) between Examples 1-3 and Comparative Examples 1-2 showed that the Charpy impact strength at room temperature of Example 3 was 3 kJ / m 2 The Charpy impact strength at low temperatures is 3 kJ / m 2 On the other hand, the Charpy impact strength at room temperature of Comparative Example 1-2 was 3 kJ / m 2 The Charpy impact strength at low temperatures is 2 kJ / m 2 That is, Example 1-3 had impact resistance performance equal to or greater than that of Comparative Example 1-2. That is, it can be said that Example 1-3 has good toughness.

[0382] (Example 2-1) In this example, a polycarbonate resin was produced using DA13 and ISB as dihydroxy compounds. Compared to Example 1, 10.87 g (0.0414 mol) of DA13, 2.59 g (0.0178 mol) of ISB, 12.93 g (0.0604 mol) of DPC as materials, and 3.13 × 10 calcium acetate monohydrate as a catalyst were used. -3 g (1.78 × 10 -5 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units=100 / 70 / 30) was prepared in the same manner as in Example 1, except that a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units=100 / 70 / 30 was used. The resulting polycarbonate copolymer had a reduced viscosity of 0.621 dl / g and a glass transition temperature Tg of 125° C. The saturated water absorption at room temperature was 0.7 wt %. No deformation occurred in a boiling water test. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 2.

[0383] (Example 2-2) In this example, a polycarbonate resin was produced using DA13 and TCDDM as dihydroxy compounds. Compared to Example 1, 10.86 g (0.0414 mol) of DA13, 2.71 g (0.0138 mol) of TCDDM, 12.06 g (0.0563 mol) of DPC as materials, and 2.92 × 10 calcium acetate monohydrate as a catalyst were used. -3 g (1.66×10 -5 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / TCDDM-derived structural units=100 / 75 / 25) was prepared in the same manner as in Example 1, except that a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / TCDDM-derived structural units=100 / 75 / 25 was used. The reduced viscosity of the obtained polycarbonate copolymer was 1.256 dl / g, and the glass transition temperature Tg was 107°C. The saturated water absorption rate at room temperature was 0.3 wt%. Deformation occurred in the boiling water test. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 2.

[0384] (Example 2-3) In this example, polyester carbonate resin was produced using DA13 and ISB as dihydroxy compounds and FN2 as a diester component. The materials used were 40.31 parts by weight (0.154 mol) of DA13, 31.35 parts by weight (0.215 mol) of ISB, 28.19 parts by weight (0.044 mol) of FN2, 69.44 parts by weight (0.324 mol) of DPC, and 1.30×10 calcium acetate monohydrate as a catalyst. -3 Weight part (7.36×10 -6mol) was put into the reaction vessel, and the inside of the reaction vessel was replaced with reduced pressure and nitrogen. The raw materials were dissolved under stirring at 150°C for about 10 minutes under a nitrogen atmosphere. In the first reaction step, the pressure was adjusted to 53.3kPa, and the temperature was raised to 220°C over 30 minutes. 30 minutes after reaching 220°C, the pressure was reduced to 13.3kPa over 60 minutes. The generated phenol was extracted from the reaction system. Next, in the second reaction step, the heat medium temperature was raised to 245°C over 15 minutes while maintaining the pressure at 13.3kPa, and then the pressure was reduced to 0.10kPa or less over 30 minutes. After reaching a predetermined stirring torque, the pressure was returned to normal pressure with nitrogen to stop the reaction, and the generated polyester carbonate was extruded into water, and the strands were cut to obtain pellets. In this way, a polyester carbonate resin (specifically, a polyester carbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units / ISB-derived structural units / FN2-derived structural units=100 / 40 / 40 / 20) was prepared. The structural units derived from FN2 are shown below. The physical properties and evaluation results of the obtained polyester carbonate resin are shown in Table 2.

[0385] [ka]

[0386] [Table 2]

[0387] As can be seen from Table 2, for example, Example 2-1 has a sufficiently high glass transition temperature, good results in the bending test and boiling water test, and excellent toughness and moist heat resistance. It also has a low saturated water absorption. Example 2-2 has a practical glass transition temperature, good results in the bending test, and excellent toughness. It also has a very low saturated water absorption. In contrast, Comparative Example 4-2, which does not contain a specific structure, has a low glass transition temperature, fails the boiling water test, and is poor in moist heat resistance. The polyester carbonate of Example 2-3 has a sufficiently high glass transition temperature, good results in the boiling water test, and excellent moist heat resistance. It also has a sufficiently low photoelastic coefficient, making it suitable for optical applications.

[0388] (Example 3-1) In this example, polycarbonate resin was prepared using NCDDM and ISB as dihydroxy compounds. A polycarbonate resin (specifically, a polycarbonate copolymer with a molar ratio of DPC-derived structural unit / NCDDM-derived structural unit / ISB-derived structural unit=100 / 30 / 70) was prepared in the same manner as in Example 1, except that 5.51 g (0.0222 mol) of NCDDM, 7.58 g (0.0518 mol) of ISB, 16.16 g (0.0754 mol) of DPC were used as materials, and 1.30×10-3 g (7.40×10-4 mol, 2% aqueous solution) of calcium acetate monohydrate was used as a catalyst. The resulting polycarbonate copolymer had a reduced viscosity of 0.282 dl / g and a glass transition temperature Tg of 145°C. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 3.

[0389] (Example 3-2) In this example, polycarbonate resin was produced using NCDDM, ISB, and CHDM as dihydroxy compounds. Compared to Example 1, 2.05 g (0.0082 mol) of NCDDM, 2.38 g (0.0165 mol) of CHDM, 8.43 g (0.0577 mol) of ISB, 18.01 g (0.0841 mol) of DPC, and 1.45 × 10 calcium acetate monohydrate as a catalyst were used.-3 g(8.24×10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / NCDDM-derived structural units / ISB-derived structural units / CHDM-derived structural units=100 / 10 / 70 / 20) was prepared in the same manner as in Example 1, except that a 0.2% aqueous solution (mol) of DPC-derived structural units was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.804 dl / g, and the glass transition temperature Tg was 139° C. The saturated water absorption rate at room temperature was 2.2 wt %. No deformation occurred in the boiling water test. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 3.

[0390] (Example 3-3) In this example, a polycarbonate resin was produced using TPSA, ISB, and TCDDM as dihydroxy compounds. Compared to Example 1, 2.24 g (0.0076 mol) of TPSA, 2.99 g (0.0152 mol) of TCDDM, 7.79 g (0.0533 mol) of ISB, 16.64 g (0.0777 mol) of DPC, and 1.34 × 10 calcium acetate monohydrate as a catalyst were used. -3 g (7.62 × 10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / TPSA-derived structural units / ISB-derived structural units / TCDDM-derived structural units=100 / 10 / 70 / 20) was prepared in the same manner as in Example 1, except that a 0.2% aqueous solution of 1,000 mol of DPC-derived structural units was used. The resulting polycarbonate copolymer had a reduced viscosity of 0.795 dl / g and a glass transition temperature Tg of 146° C. The saturated water absorption at room temperature was 2.7 wt %. No deformation occurred in a boiling water test. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 3.

[0391] (Examples 3-4) In this example, a polycarbonate resin was produced using TPSA, ISB, and TCDDM as dihydroxy compounds. Compared to Example 1, 4.17 g (0.0142 mol) of TPSA, 2.78 g (0.0142 mol) of TCDDM, 6.21 g (0.0425 mol) of ISB, 15.47 g (0.0722 mol) of DPC, and 1.25 × 10 calcium acetate monohydrate as a catalyst were used. -3 g (7.08 × 10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / TPSA-derived structural units / ISB-derived structural units / TCDDM-derived structural units=100 / 20 / 60 / 20) was prepared in the same manner as in Example 1, except that a 0.2% aqueous solution (mol) of 1,2-dichlorophenyl ether was used instead. The resulting polycarbonate copolymer had a reduced viscosity of 0.640 dl / g and a glass transition temperature Tg of 148° C. The saturated water absorption at room temperature was 2.4 wt %. No deformation occurred in a boiling water test. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 3.

[0392] (Examples 3-5) In this example, a polycarbonate resin was produced using TPSA, ISB, and CHDM as dihydroxy compounds. Compared to Example 1, 2.37 g (0.0080 mol) of TPSA, 2.32 g (0.0161 mol) of CHDM, 8.22 g (0.0563 mol) of ISB, 17.57 g (0.0820 mol) of DPC, and 1.42 × 10 calcium acetate monohydrate as a catalyst were used. -3 g(804×10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / TPSA-derived structural units / ISB-derived structural units / CHDM-derived structural units=100 / 10 / 70 / 20) was prepared in the same manner as in Example 1, except that a 0.2% aqueous solution of 1,000 mol of DPC-derived structural units was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.876 dl / g, and the glass transition temperature Tg was 141° C. The saturated water absorption rate at room temperature was 2.9 wt%. No deformation occurred in the boiling water test. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 3.

[0393] (Examples 3 to 6) In this example, a polycarbonate resin was produced using TPSA, ISB, and CHDM as dihydroxy compounds. Compared to Example 1, 4.38 g (0.0149 mol) of TPSA, 1.07 g (0.0074 mol) of CHDM, 7.61 g (0.0521 mol) of ISB, 16.26 g (0.0759 mol) of DPC, and 1.31 × 10 calcium acetate monohydrate as a catalyst were used. -3 g (7.44 × 10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / TPSA-derived structural units / ISB-derived structural units / CHDM-derived structural units=100 / 20 / 70 / 10) was prepared in the same manner as in Example 1, except that a 0.2% aqueous solution of 1,000 mol of DPC-derived structural units was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.600 dl / g, and the glass transition temperature Tg was 158°C. The saturated water absorption at room temperature was 3.5 wt%. No deformation occurred in the boiling water test. The physical properties and evaluation results of the obtained polycarbonate copolymer are shown in Table 3.

[0394] [Table 3]

[0395] As can be seen from Table 3, for example, Example 3-1 has a high glass transition temperature and is excellent in heat resistance. Example 3-2 has a sufficiently high glass transition temperature, exhibits good results in bending tests and boiling water tests, and is excellent in toughness and moist heat resistance. Examples 3-3 to 3-6 contain carbonate resins with large molecular weights and structures having alkoxy groups, and are excellent in heat resistance and moist heat resistance.

[0396] (Example 4-1) In this example, a polycarbonate resin was produced using DA13 as a dihydroxy compound. Compared to Example 1, 13.65 g (0.0520 mol) of DA13 and 11.37 g (0.0531 mol) of DPC were used as materials, and 2.75 × 10 calcium acetate monohydrate was used as a catalyst. -3 g (1.56 × 10 -6 A polycarbonate resin (specifically, a polycarbonate copolymer in which, in terms of molar ratio, the structural units derived from DPC / the structural units derived from DA13=100 / 100) was prepared in the same manner as in Example 1, except that a polycarbonate copolymer having a molar ratio of DPC-derived structural units / DA13-derived structural units=100 / 100 was used. The resulting polycarbonate copolymer had a reduced viscosity of 0.639 dl / g and a glass transition temperature Tg of 116° C. The saturated water absorption at room temperature was 0.31 wt %. No deformation occurred in a boiling water test. The physical properties and evaluation results of the obtained polycarbonate homopolymer are shown in Table 4.

[0397] (Comparative Example 4-1) In this example, polycarbonate resin was produced using CHDM as the dihydroxy compound. In comparison with Example 1, 12.71 g (0.0881 mol) of CHDM, 19.26 g (0.0899 mol) of DPC, and 4.66 × 10 calcium acetate monohydrate were used as the catalyst. -3 g (2.64 × 10 -5 A polycarbonate resin (specifically, a polycarbonate copolymer having a molar ratio of DPC-derived structural units / CHDM-derived structural units=100 / 100) was produced in the same manner as in Example 1, except that a polymerization initiator (polymerization initiator; DPC; 2% aqueous solution) was used in the second step, and the temperature of the heating bath was not increased to 240° C. in 20 minutes, but was continued at 220° C. in the second step. The reduced viscosity of the obtained polycarbonate copolymer was 1.051 dl / g, and the glass transition temperature Tg was 40° C. The saturated water absorption at room temperature was 0.41 wt%. It deformed in a boiling water test. The physical properties and evaluation results of the obtained polycarbonate homopolymer are shown in Table 4.

[0398] (Comparative Example 4-2) In this example, polycarbonate resin was produced using TCDDM as the dihydroxy compound. In comparison with Example 1, 13.25 g (0.0675 mol) of TCDDM and 14.46 g (0.0675 mol) of DPC were used as materials, and 3.57 × 10 calcium acetate monohydrate was used as a catalyst. -3 g (2.02 × 10 -5 A polycarbonate resin (specifically, a polycarbonate copolymer in which, in terms of molar ratio, the structural units derived from DPC / the structural units derived from TCDDM=100 / 100) was prepared in the same manner as in Example 1, except that a polycarbonate copolymer having a molar ratio of DPC-derived structural units / TCDDM-derived structural units=100 / 100 was used. The reduced viscosity of the obtained polycarbonate copolymer was 0.836 dl / g, and the glass transition temperature Tg was 77° C. The saturated water absorption at room temperature was 0.36 wt %. It was deformed in the boiling water test. The physical properties and evaluation results of the obtained polycarbonate homopolymer are shown in Table 4.

[0399] [Table 4]

[0400] As can be seen from Table 4, the thermoplastic resin (homopolymer) composed of an alicyclic monomer and DPC shown in Example 4-1 has a high glass transition temperature and excellent reliability in humidity and heat resistance. Also, the photoelastic coefficient is very low. On the other hand, in Comparative Examples 4-1 and 4-2, the glass transition temperature is 100°C or less, and the reliability in humidity and heat resistance is significantly impaired.

[0401] (Experimental Example) In this example, the thermal decomposition resistance of DA13, ISB, TCDDM, and SPG was evaluated. Specifically, the 5% weight loss temperature (i.e., Td5) of each monomer was measured. SPG is spiro glycol. The measurement method is as described above. The results are shown in Table 5.

[0402] [Table 5]

[0403] As can be seen from Table 5, DA13 has a higher Td5 than other monomers. Therefore, it has excellent thermal decomposition resistance and is suitable for the synthesis of thermoplastic resins such as carbonate-based resins. In other words, when used as a monomer for a thermoplastic resin, the decomposition of the monomer due to heat during polymerization is suppressed, and the difference between the composition of the monomer charged in the polymerization process and the composition of the thermoplastic resin obtained in the polymerization process can be reduced. This makes it possible to stably produce a thermoplastic resin with certain physical properties.

Claims

1. A thermoplastic resin having a structure represented by the following formula (A1): 【Chemistry 1】 【Chemistry 2】 (X in formula (A1) represents formula (B1) above, and rings Y and Z forming a condensed ring with cyclobutane in formula (B1) above are each independently any alicyclic carbon ring selected from the following formulas (C1) to (C11) which may have a substituent, * in formulas (C1) to (C11) below represents a site where the condensed ring is formed, L in formula (B1) above represents 1 and L 2 each independently represents a direct bond or a divalent hydrocarbon group having 1 to 5 carbon atoms. 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】

2. The thermoplastic resin according to claim 1, wherein the substituent is a hydrocarbon group having 1 to 14 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 3 to 14 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, a silyl group, a sulfinyl group, a sulfo group, an alkylthio group, an arylthio group, an amino group, a halogen atom, a nitro group, or a cyano group.

3. The thermoplastic resin according to claim 1 or 2, wherein the rings Y and Z in the formula (B1) are each independently an alicyclic carbon ring selected from the formulas (C1) to (C7).

4. The thermoplastic resin according to any one of claims 1 to 3, wherein the formula (B1) is any one selected from the following formulas (B2) to (B12) and the following formulas (B16) to (B26): 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 【Chemistry 18】 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemical 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemical 27】 【Chemistry 28】 【Chemical Formula 29】 【Chemistry 30】 【Chemistry 31】 【Chemistry 32】 【Chemical 33】 【Chemical 34】 【Chemistry 35】 (R in formulas (B2) to (B12) and (B16) to (B26) 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 14 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

5. R in the above formulas (B2) to (B12) and (B16) to (B26) 1 and R 2 The thermoplastic resin according to claim 4 , wherein each independently represents a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group.

6. The thermoplastic resin according to any one of claims 1 to 5, wherein the alicyclic skeletons of ring Y and ring Z in formula (B1) are different from each other.

7. The thermoplastic resin according to any one of claims 1 to 6, having a glass transition temperature of 100°C or higher.

8. The thermoplastic resin according to any one of claims 1 to 7, having a reduced viscosity of 0.2 dl / g or more and 1.50 dl / g or less.

9. The thermoplastic resin according to any one of claims 1 to 8, further comprising a structural unit derived from at least one compound selected from the group consisting of isosorbide, isomannide, and isoided.

10. The thermoplastic resin according to any one of claims 1 to 9, which is a polycarbonate resin or a polyester carbonate resin.

11. A molded article made of the thermoplastic resin according to any one of claims 1 to 10.

Images