Copolymerized polycarbonate resin, heat storage material containing same, and heat storage molded body

Abstract

To provide a copolymerized polycarbonate resin that excels in heat storage, heat resistance, and shape retention, and a heat storage material and a heat storage molded body containing the same.SOLUTION: This copolymerized polycarbonate resin has at least a constitutional unit (A) and a constitutional unit (B). The constitutional unit (A) is derived from a dihydroxy compound. The carbonate constitutional unit (B) is derived from polyoxyalkylene glycol. The ratio of the weight of the constitutional unit (B) derived from polyoxyalkylene glycol to the weight of the copolymerized polycarbonate resin is preferably more than 20 wt.% to 99 wt.% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a copolymer polycarbonate resin having excellent heat storage capacity, heat resistance, and shape retention, a heat storage material and a heat storage molded article containing the same, and a phase change material having excellent heat storage capacity, heat resistance, and shape retention. [Background technology]

[0002] In recent years, latent heat storage materials that utilize latent heat due to phase transitions such as liquid-solid phase transitions, crystalline-amorphous phase transitions, and polymorphic phase transitions have been attracting attention. Known polymers that can be used in latent heat storage materials are acrylate polymers having a main chain and long side chains, which undergo a phase transition and release or absorb latent heat, thereby exhibiting heat storage performance (Patent Documents 1 to 3). Patent Document 4 also describes a crystalline higher α-olefin copolymer having two or more types of higher α-olefin units with 10 or more carbon atoms as a polymer having a main chain and long side chains. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-268358 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-27189 [Patent Document 3] Special Publication No. 2011-528396 [Patent Document 4] Japanese Patent Application Laid-Open No. 2005-75908 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, polycarbonate resins, which generally contain bisphenols as monomer components, are widely used as so-called engineering plastics in fields such as electrical and electronic components, automotive parts, optical recording media, and lenses, taking advantage of their advantages such as transparency, heat resistance, and mechanical strength. However, they have not been sufficiently studied as resins applicable to heat storage materials.

[0005] An object of the present disclosure is to provide a copolymer polycarbonate resin having excellent heat storage capacity, heat resistance, and shape retention, a heat storage material and a heat storage molded article containing the same, and a phase change material having excellent heat storage capacity, heat resistance, and shape retention. [Means for solving the problem]

[0006] A first aspect of the present disclosure is a copolymer polycarbonate resin having at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from a polyoxyalkylene glycol, the weight ratio of the structural unit (B) to the total weight of the copolymer polycarbonate resin is more than 20% by weight and 99% by weight or less; The copolymer polycarbonate resin is one in which the number of carbon atoms m1 of the alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol and the number average molecular weight of the polyoxyalkylene glycol satisfy any one of the following relationships (α1) to (α3): m1 is 2 or 3, and the number average molecular weight is 3,000 or more and 20,000 or less (α1) m1 is 4, 5, or 6, and the number average molecular weight is 1,500 or more and 20,000 or less (α2) m1 is an integer of 7 or more, and the number average molecular weight is 800 or more and 20,000 or less (α3) [ka] (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

[0007] A second aspect of the present disclosure is a copolymer polycarbonate resin having at least structural units (A) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and heteroalicyclic dihydroxy compounds, and structural units (B) derived from polyoxyalkylene glycol, The copolymer polycarbonate resin is characterized in that the alkylene group R in the repeating unit represented by the following formula (7), which constitutes the polyoxyalkylene glycol, has 7 or more carbon atoms, and the number average molecular weight of the polyoxyalkylene glycol is 800 or more and 20,000 or less. [ka] (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

[0008] of the present disclosure reference An embodiment is a copolymer polycarbonate resin having at least a structural unit (A) derived from a dihydroxy compound and a structural unit (B) derived from a polyoxyalkylene glycol, The alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol has 2 or more carbon atoms, The copolymeric polycarbonate resin has a weight ratio of the structural unit (B) of more than 50% by weight and not more than 99% by weight relative to the total weight of the copolymeric polycarbonate resin. [ka] (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

[0009] A fourth aspect of the present disclosure is a polymerizable composition comprising at least a structural unit (A) derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from polytetramethylene glycol having a number average molecular weight of 1,500 or more and 20,000 or less, The copolymer polycarbonate resin has a melting enthalpy ΔH(L) of 20 J / g or more as measured within a temperature range of -30°C to 80°C by differential scanning calorimetry.

[0010] A fifth aspect of the present disclosure is a heat storage material containing the copolymeric polycarbonate resin.

[0011] A sixth aspect of the present disclosure is a heat storage molded body obtained by molding the heat storage material.

[0012] A seventh aspect of the present disclosure is a phase change material composed of a polymer having carbonate bonds in its molecular chain and having a melting enthalpy ΔH(L) of 20 J / g or more as measured within a temperature range of −30° C. to 80° C. by differential scanning calorimetry. [Effects of the Invention]

[0013] The copolymer polycarbonate resin has excellent heat storage capacity, heat resistance, and shape retention. By using such a copolymer polycarbonate resin, it is possible to obtain a high-performance heat storage material and a heat storage molded article. Furthermore, the phase transition material has excellent heat storage capacity, heat resistance, and shape retention. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is an NMR spectrum of the polycarbonate copolymer (that is, the copolymerized polycarbonate resin) obtained in Example 4. [Figure 2] FIG. 2 is an NMR spectrum of the polycarbonate copolymer (that is, the copolymerized polycarbonate resin) obtained in Example 6. [Figure 3] FIG. 3 is an NMR spectrum of the polycarbonate copolymer (i.e., copolymerized polycarbonate resin) obtained in Example 12. [Figure 4] FIG. 4 is an NMR spectrum of the polycarbonate copolymer (i.e., copolymerized polycarbonate resin) obtained in Example 13. [Figure 5] FIG. 5 is an NMR spectrum of the polycarbonate copolymer (i.e., copolymerized polycarbonate resin) obtained in Example 14. [Figure 6] FIG. 6 is an NMR spectrum of the polycarbonate copolymer (that is, the copolymerized polycarbonate resin) obtained in Example 7. [Figure 7] FIG. 7 is an NMR spectrum of the polycarbonate copolymer (that is, the copolymerized polycarbonate resin) obtained in Example 8. [Figure 8] FIG. 8 is an NMR spectrum of the polycarbonate copolymer (that is, the copolymerized polycarbonate resin) obtained in Example 9. [Figure 9] FIG. 9 is a DSC curve of the polycarbonate copolymer (i.e., copolymerized polycarbonate resin) obtained in Example 15. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in detail below, but the present invention is not limited to the following description and can be practiced with any modifications within the scope of the gist of the present invention.

[0016] In this specification, when "~" is used to express a numerical value or a physical property value, the values ​​before and after the "~" are included.

[0017] In this specification, the term "repeating structural unit" refers to a structural unit in which the same structure appears repeatedly in a resin and which constitutes the resin by linking together. For example, in the case of a polycarbonate resin, the repeating structural unit also includes the carbonyl group. Furthermore, the term "structural unit" refers to a partial structure that constitutes a resin, and a specific partial structure contained in the repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a partial structure sandwiched between a polymerizable reactive group present at the terminal portion of a polymer and a linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is the linking group, and a partial structure sandwiched between adjacent carbonyl groups is referred to as a structural unit. A structural unit containing a carbonyl group is appropriately referred to as a carbonate structural unit.

[0018] [I] Regarding the first aspect First, the copolymer polycarbonate resin according to the first aspect of the present disclosure will be described. The first aspect of the present disclosure is, as described above, a copolymer polycarbonate resin having at least structural units (A) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and heteroalicyclic dihydroxy compounds, and structural units (B) derived from polyoxyalkylene glycol, the weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is more than 20% by weight and 99% by weight or less; The copolymer polycarbonate resin is one in which the number of carbon atoms m1 of the alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol and the number average molecular weight of the polyoxyalkylene glycol satisfy any one of the following relationships (α1) to (α3):

[0019] m1 is 2 or 3, and the number average molecular weight is 3,000 or more and 20,000 or less (α1) m1 is 4, 5, or 6, and the number average molecular weight is 1,500 or more and 20,000 or less (α2) m1 is an integer of 7 or more, and the number average molecular weight is 800 or more and 20,000 or less (α3)

[0020] [ka] (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

[0021] The first aspect can be restated as, for example, the following aspects 1-1 to 1-3.

[0022] Aspect 1-1 is a copolymer polycarbonate resin having at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from a polyoxyalkylene glycol, the weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is more than 20% by weight and 99% by weight or less; The copolymer polycarbonate resin is characterized in that the alkylene group R in the repeating unit represented by the formula (7) constituting the polyoxyalkylene glycol has 2 or 3 carbon atoms, and the number average molecular weight of the polyoxyalkylene glycol is 3,000 or more and 20,000 or less. Aspect 1-1 satisfies the relationship of formula (α1) in the first aspect.

[0023] Aspect 1-2 is a copolymer polycarbonate resin having at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from a polyoxyalkylene glycol, the weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is more than 20% by weight and 99% by weight or less; The copolymer polycarbonate resin is characterized in that the alkylene group R in the repeating unit represented by the formula (7) constituting the polyoxyalkylene glycol has 4 to 6 carbon atoms, and the number average molecular weight of the polyoxyalkylene glycol is 1500 or more and 20000 or less. Aspect 1-1 satisfies the relationship of formula (α2) in the first aspect.

[0024] A first to third aspect is a copolymer polycarbonate resin having at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from a polyoxyalkylene glycol, the weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is more than 20% by weight and 99% by weight or less; The present invention relates to a copolymer polycarbonate resin in which the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 7 or more carbon atoms, and the molecular weight of the polyoxyalkylene glycol is 800 or more and 20,000 or less. Aspect 1-3 satisfies the relationship of formula (α3) in the first aspect. From the viewpoint of ease of availability, the number of carbon atoms in the alkylene group R is preferably 30 or less (i.e., m1 is an integer of 30 or less), more preferably 25 or less (i.e., m1 is an integer of 25 or less), and even more preferably 20 or less (i.e., m1 is an integer of 20 or less).

[0025] Structural unit (A) The copolymeric polycarbonate resin has structural units (A) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and heteroalicyclic dihydroxy compounds. That is, the copolymeric polycarbonate resin has at least one of structural units derived from an aliphatic dihydroxy compound, structural units derived from an alicyclic dihydroxy compound, and structural units derived from a heteroalicyclic dihydroxy compound. The copolymeric polycarbonate resin may also have, for example, structural units derived from an aliphatic dihydroxy compound, structural units derived from an alicyclic dihydroxy compound, and structural units derived from a heteroalicyclic dihydroxy compound. In such cases, these structural units are collectively referred to as structural units (A).

[0026] The dihydroxy compound forming the structural unit (A) is one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and heteroalicyclic dihydroxy compounds.

[0027] In this specification, an aliphatic dihydroxy compound is defined as a dihydroxy compound that is not aromatic and does not have a carbocyclic structure. An alicyclic dihydroxy compound is defined as a carbocyclic dihydroxy compound that is not aromatic. In this specification, a heteroalicyclic dihydroxy compound is defined as a cyclic dihydroxy compound that contains one or more heteroatoms as ring-constituting atoms. In this specification, a heteroalicyclic dihydroxy compound is a concept that does not include the above-mentioned alicyclic dihydroxy compounds.

[0028] The structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and heteroalicyclic dihydroxy compounds is a segment that contributes to the heat resistance and shape retention of the copolymeric polycarbonate resin. By containing the structural unit (A), the copolymeric polycarbonate resin has excellent heat resistance and shape retention.

[0029] The aliphatic dihydroxy compound is not particularly limited, but examples thereof include straight-chain aliphatic dihydroxy compounds and branched-chain aliphatic dihydroxy compounds. Examples of the linear aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, and 1,18-octadecanediol. Examples of the branched chain aliphatic dihydroxy compound include 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol. The number of carbon atoms in the aliphatic dihydroxy compound is not particularly limited, but preferably has 1 to 30 carbon atoms, more preferably has 2 to 25 carbon atoms, further preferably has 5 to 22 carbon atoms, and particularly preferably has 10 to 20 carbon atoms. In this case, crystals are more likely to be formed, the enthalpy of fusion is increased, and the heat storage performance is improved. From the viewpoint of availability of raw materials, linear aliphatic dihydroxy compounds having 1 to 30 carbon atoms are preferred, linear aliphatic dihydroxy compounds having 2 to 25 carbon atoms are more preferred, linear dihydroxy compounds having 5 to 22 carbon atoms are even more preferred, and linear dihydroxy compounds having 10 to 20 carbon atoms are particularly preferred. Of these, 1,10-decanediol, 1,12-dodecanediol, and 1,18-octadecanediol are particularly preferred.

[0030] The alicyclic dihydroxy compound is not particularly limited, but examples thereof include dihydroxy compounds containing one or more four-membered ring structures as part of their structure, and dihydroxy compounds containing one or more five- or six-membered ring structures as part of their structure. The six-membered ring structure may be fixed in a chair or boat shape by a covalent bond. When the alicyclic dihydroxy compound contains at least one five- or six-membered ring structure in its structure, the heat resistance of the copolymer polycarbonate resin may be improved. Therefore, the alicyclic dihydroxy compound is preferably a compound containing one or more five- or six-membered ring structures as part of its structure. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. If the number of carbon atoms is too large, the heat resistance of the copolymer polycarbonate resin will be high, but the synthesis and purification of the alicyclic dihydroxy compound will be difficult, and the production cost of the alicyclic dihydroxy compound will tend to be high. The smaller the carbon number, the easier it is to purify the alicyclic dihydroxy compound, and the easier it tends to be to obtain the alicyclic dihydroxy compound. From the viewpoint of further improving heat resistance, the hydroxy compound containing one or more 5-membered or 6-membered ring structures as part of its structure is preferably an alicyclic dihydroxy compound containing one or more 5-membered or 6-membered ring structures as part of its structure and / or a dihydroxy compound having a cyclic ether structure.

[0031] Specific examples of alicyclic dihydroxy compounds containing one or more 5-membered ring structures or 6-membered ring structures as part of their structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II): HOCH2-R 5 -CH2OH (I) HO-R 6 -OH (II) However, in formula (I) and formula (II), R 5 and R 6 each independently represents a substituted or unsubstituted divalent group containing a cycloalkyl structure having 4 to 30 carbon atoms.

[0032] The cyclohexanedimethanol (hereinafter, sometimes referred to as "CHDM"), which is an alicyclic dihydroxy compound represented by the general formula (I), is a compound represented by the general formula (I) in which R 5 is represented by the following general formula (Ia) (wherein R 7 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples of such isomers include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.

[0033] [ka]

[0034] Tricyclodecane dimethanol (hereinafter, sometimes referred to as "TCDDM") and pentacyclopentadecanedimethanol, which are alicyclic dihydroxy compounds represented by the general formula (I), can be prepared by the following general formula (I): 5 is represented by the following general formula (Ib) (wherein n represents 0 or 1).

[0035] [ka]

[0036] The alicyclic dihydroxy compound represented by the general formula (I), decalin dimethanol or tricyclotetradecane dimethanol, is a compound represented by the general formula (I), 5 is represented by the following general formula (Ic) (wherein m represents 0 or 1). Specific examples of such isomers include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, etc.

[0037] [ka]

[0038] Furthermore, the norbornane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (I), is a compound represented by the general formula (I) in which R 5 is represented by the following general formula (Id) (wherein p represents 1 or 2). Specific examples of such isomers include, when p=1, bicyclo[2.2.1]heptane-2,3-dimethanol (2,3-norbornane dimethanol), bicyclo[2.2.1]heptane-2,5-dimethanol, etc.

[0039] [ka]

[0040] When p=2, the alicyclic dihydroxy compound bicyclooctanedimethanol is a compound represented by the general formula (I): 5 These include various isomers represented by the following general formula (Id): Specific examples of such isomers include bicyclo[2,2,2]octane-1,4-dimethanol (hereinafter sometimes referred to as "BODM") represented by the following formula (Id-1):

[0041] [ka]

[0042] Adamantane dimethanol (hereinafter, sometimes referred to as "ADDM"), which is an alicyclic dihydroxy compound represented by general formula (I), is a compound represented by general formula (I) in which R 5 is represented by the following general formula (Ie): 3,7 ]-1,3-dimethanol, tricyclo[3,3,1,1 3,7 ]-2,2-dimethanol and the like.

[0043] [ka]

[0044] In addition, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), is 6 is represented by the following general formula (IIa) (wherein R 7 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples of such isomers include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol.

[0045] [ka]

[0046] The alicyclic dihydroxy compounds represented by the general formula (II), tricyclodecanediol and pentacyclopentadecanediol, are compounds represented by the general formula (II), 6 includes various isomers represented by the following general formula (IIb) (wherein n represents 0 or 1).

[0047] [ka]

[0048] The alicyclic dihydroxy compound represented by the general formula (II), decalindiol or tricyclotetradecanediol, is a compound represented by the general formula (II), 6 is represented by the following general formula (IIc) (wherein m represents 0 or 1). Specific examples of such isomers include 2,6-decalindiol, 1,5-decalindiol, and 2,3-decalindiol.

[0049] [ka]

[0050] The norbornanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), is a compound represented by the general formula (II) in which R 6 is represented by the following general formula (IId) (wherein p represents 1 or 2). Specifically, when P=1, bicyclo[2.2.1]heptane-2,3-diol (2,3-norbornanediol), bicyclo[2.2.1]heptane-2,5-diol, etc. are used.

[0051] [ka]

[0052] In formula (IId), when p=2, the alicyclic dihydroxy compound represented by general formula (II) is bicyclooctanediol, which is a compound represented by general formula (II), 6 These include various isomers represented by the following general formula (IId): Specific examples of such isomers include bicyclo[2,2,2]octane-1,4-diol represented by the following formula (IId-1):

[0053] [ka]

[0054] The adamantanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), is a compound represented by the general formula (II) in which R 6 The isomers include various isomers represented by the following general formula (IIe). 3,7 ]-1,3-diol, tricyclo[3,3,1,1 3,7 ]-2,2-diol and the like.

[0055] [ka]

[0056] The above-mentioned exemplary compounds are merely examples of usable alicyclic dihydroxy compounds, and the present invention is not limited thereto. These alicyclic dihydroxy compounds may be used alone or in combination of two or more. When two or more alicyclic dihydroxy compounds are used in combination, the copolymeric polycarbonate resin will have structural units derived from each of the alicyclic dihydroxy compounds. In this case, the structural units derived from each of the alicyclic dihydroxy compounds are collectively referred to as structural unit (A).

[0057] Among the alicyclic dihydroxy compounds containing one or more five- or six-membered ring structures as part of the above-mentioned structure, compounds containing two or more five- or six-membered ring structures as part of the structure are preferred from the viewpoint of a more rigid molecular skeleton and further improving the heat resistance, shape retention, and moldability of the copolymer polycarbonate resin. In this case, the multiple rings may be fused rings or spiro rings. Preferred specific examples of such compounds include ADDM represented by the following formula (3), BODM represented by the following formula (4), and TCDDM represented by the following formula (5).

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] Among the above-mentioned alicyclic dihydroxy compounds containing one or more 5-membered ring structures or 6-membered ring structures as part of the structure, from the viewpoint of easy availability, one or more compounds selected from the group consisting of CHDM, TCDDM, BODM, and ADDM represented by the following formula (6) are preferred.

[0062] [ka]

[0063] Of the alicyclic dihydroxy compounds containing one or more 5-membered or 6-membered ring structures as part of the above structure, from the viewpoint of being able to impart heat resistance to the polycarbonate, one or more compounds selected from the group consisting of TCDDM, BODM, and ADDM are preferred, and from the viewpoint of being able to impart crystallinity in addition to heat resistance, BODM and / or ADDM are more preferred.

[0064] Examples of heteroatoms contained in the heteroalicyclic dihydroxy compound include oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. From the viewpoints of low water absorption, coloration prevention, and light resistance, the heteroatom is preferably an oxygen atom and / or a sulfur atom. From the viewpoints of coloration prevention and light resistance, the heteroatom is more preferably an oxygen atom.

[0065] The heteroalicyclic dihydroxy compound is not particularly limited, but examples thereof include a dihydroxy compound having a cyclic ether structure, a dihydroxy compound having a cyclic thioether structure, etc. From the viewpoints of preventing coloration and preventing the generation of acidic substances, the heteroalicyclic dihydroxy compound is preferably a dihydroxy compound having a cyclic ether structure.

[0066] Specific examples of the dihydroxy compound having a cyclic ether structure include a dihydroxy compound represented by the following formula (1) and a dihydroxy compound represented by the following formula (2).

[0067] [ka]

[0068] [ka]

[0069] In the formula (2), R1 ~R 4 are each independently an alkyl group having 1 to 3 carbon atoms.

[0070] Examples of the dihydroxy compound represented by the formula (1) include isosorbide, isomannide, and isoidet, which are stereoisomers, and these may be used alone or in combination of two or more. Among these dihydroxy compounds, isosorbide, which is obtained by dehydration condensation of sorbitol, which is produced from various starches that are abundant and easily available as a plant-derived resource, is most preferred in terms of availability and ease of production, light resistance, optical properties, moldability, heat resistance, and carbon neutrality.

[0071] Examples of dihydroxy compounds represented by formula (2) include 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane (common name: spiroglycol), 3,9-bis(1,1-diethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(1,1-dipropyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and dioxangulol. These compounds may be used alone or in combination of two or more. Spiroglycol is preferred as the dihydroxy compound represented by formula (2) because it is easily available and increases the glass transition temperature of the resin.

[0072] Among dihydroxy compounds having a cyclic ether structure, compounds containing a total of two or more five-membered or six-membered ring structures as part of the structure are preferred from the viewpoint of having a more rigid molecular skeleton and further improving the heat resistance and moldability of the copolymer polycarbonate resin. In this case, the multiple rings may be fused rings or spiro rings. Preferred examples of such compounds include dihydroxy compounds represented by the above formula (1) and dihydroxy compounds represented by the above formula (2).

[0073] From the viewpoints of further improving the heat resistance and moldability of the copolymeric polycarbonate resin and facilitating the availability of raw materials, the dihydroxy compound having a cyclic ether structure is more preferably a dihydroxy compound represented by the above formula (1) and / or a dihydroxy compound represented by the above formula (2).

[0074] From the viewpoint of improving the heat resistance, shape retention, and moldability of the copolymer polycarbonate resin, the structural unit (A) is preferably a structural unit derived from an alicyclic dihydroxy compound containing one or more 5-membered or 6-membered ring structures as part of its structure and / or a structural unit derived from a dihydroxy compound having a cyclic ether structure, and more preferably a structural unit derived from an alicyclic dihydroxy compound containing a total of two or more 5-membered or 6-membered ring structures as part of its structure and / or a structural unit derived from a dihydroxy compound having a cyclic ether structure containing a total of two or more 5-membered or 6-membered ring structures as part of its structure. From a similar viewpoint, the structural unit (A) is preferably a structural unit derived from one or more dihydroxy compounds selected from the group consisting of CHDM, TCDDM, BODM, ADDM, dihydroxy compounds represented by the formula (1) above, and dihydroxy compounds represented by the formula (2) above, and it is more preferable that the structural unit (A) is a structural unit derived from one or more dihydroxy compounds selected from the group consisting of TCDDM, BODM, ADDM, dihydroxy compounds represented by the formula (1) above, and dihydroxy compounds represented by the formula (2) above.

[0075] When the structural unit (A) contains a structural unit derived from an alicyclic dihydroxy compound containing two or more 5-membered or 6-membered ring structures as part of its structure and / or a dihydroxy compound having a cyclic ether structure containing two or more 5-membered or 6-membered ring structures as part of its structure, the structural unit (A) can further contain a structural unit derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound that is different from the alicyclic dihydroxy compound containing two or more 5-membered or 6-membered ring structures as part of its structure and the dihydroxy compound having a cyclic ether structure containing two or more 5-membered or 6-membered ring structures as part of its structure. When the structural unit (A) contains a structural unit derived from an alicyclic dihydroxy compound containing two or more 5-membered or 6-membered ring structures as part of its structure and / or a dihydroxy compound having a cyclic ether structure containing two or more 5-membered or 6-membered ring structures as part of its structure, it is preferable that the structural unit (A) further contains a structural unit derived from an alicyclic dihydroxy compound containing only one 5-membered or 6-membered ring structure in its structure. In this case, the heat storage capacity of the copolymer polycarbonate resin may be further improved. A preferred specific example of a structural unit derived from an alicyclic dihydroxy compound containing only one 5-membered ring structure or one 6-membered ring structure in the structure includes the structural unit derived from CHDM described above.

[0076] From the viewpoint of achieving a copolymeric polycarbonate resin with a better balance of heat storage capacity, heat resistance, shape retention, and moldability, and from the viewpoint of easy availability of raw materials, it is particularly preferred that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (1) above, or consists of structural units derived from the dihydroxy compound represented by formula (1) above and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving heat storage capacity, it is most preferred that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (1) above, or consists of structural units derived from the dihydroxy compound represented by formula (1) above and structural units derived from CHDM.

[0077] From the viewpoint of further improving the heat storage capacity and heat resistance of the copolymer polycarbonate resin, it is particularly preferable that the structural unit (A) consists solely of structural units derived from ADDM, or consists solely of structural units derived from ADDM and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving the heat storage capacity, it is most preferable that the structural unit (A) consists solely of structural units derived from ADDM, or consists solely of structural units derived from ADDM and structural units derived from CHDM.

[0078] From the viewpoint of further improving the heat storage capacity and heat resistance of the copolymeric polycarbonate resin, it is particularly preferable that the structural unit (A) consists solely of structural units derived from BODM, or consists of structural units derived from BODM and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving the heat storage capacity, it is most preferable that the structural unit (A) consists solely of structural units derived from BODM, or consists of structural units derived from BODM and structural units derived from CHDM.

[0079] From the viewpoints of further improving the heat storage capacity, heat resistance, and shape retention of the copolymer polycarbonate resin, and of easy availability of raw materials, it is particularly preferable that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (2) above, or consists of structural units derived from the dihydroxy compound represented by formula (2) above and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving the heat storage capacity, it is most preferable that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (2) above, or consists of structural units derived from the dihydroxy compound represented by formula (2) above and structural units derived from CHDM.

[0080] The weight ratio of the structural unit (A) to the total weight of the polycarbonate resin is not particularly limited, but is preferably 5% by weight or more and 75% by weight or less. The lower limit of the weight ratio of the structural unit (A) is more preferably 15% by weight, even more preferably 20% by weight, and particularly preferably 30% by weight. On the other hand, the upper limit is more preferably 70% by weight, even more preferably 60% by weight, and particularly preferably 45% by weight. When the weight ratio of the structural unit (A) is within the above range, a better balance of heat storage capacity, heat resistance, and mold retention is achieved. In this specification, the weight ratio of a structural unit derived from a dihydroxy compound in a copolymer polycarbonate resin (e.g., structural unit (A), structural unit (B) described below, etc.) refers to a structural unit containing one carbonyl group as a linking group, i.e., a repeating structural unit.

[0081] ·Constituent unit (B) The copolymeric polycarbonate resin has a structural unit (B) derived from a polyoxyalkylene glycol. The dihydroxy compound (specifically, polyoxyalkylene glycol) that forms the structural unit (B) is one in which the number of carbon atoms m1 of the alkylene group R in the repeating unit represented by formula (7) contained in the polyoxyalkylene glycol and the number average molecular weight of the polyoxyalkylene glycol satisfy the relationship of any one of the above formulas (α1) to (α3).

[0082] [ka] (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

[0083] The copolymer polycarbonate resin has a large fusion enthalpy and excellent heat storage capacity due to the inclusion of the structural unit (B). Furthermore, as described below, the present inventors have discovered that the melting peak temperature can be adjusted by selecting a polyoxyalkylene glycol having two or more carbon atoms in the repeating unit into which the structural unit (B) is introduced so as to satisfy specific conditions. In this specification, the repeating unit of polyoxyalkylene glycol refers to the partial structural unit enclosed in parentheses in the following formula (8).

[0084] [ka] (In formula (8), R represents an alkylene group, and n represents the number of repetitions of polyoxyalkylene glycol.)

[0085] The weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is more than 20% by weight and not more than 99% by weight. When the weight ratio of the structural unit (B) exceeds 20% by weight, the crystallinity of the copolymeric polycarbonate resin increases and the enthalpy of fusion increases, resulting in excellent heat storage properties for the copolymeric polycarbonate resin. When the weight ratio of the structural unit (B) is 99% by weight or less, the copolymeric polycarbonate resin exhibits excellent heat resistance and shape retention. From the viewpoint of further improving the heat storage properties of the copolymeric polycarbonate resin, the weight ratio of the structural unit (B) is preferably 25% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and particularly preferably 65% ​​by weight or more. On the other hand, from the viewpoint of further improving the heat resistance and shape retention of the copolymer polycarbonate resin, the weight ratio of the structural unit (B) is preferably 95% by weight or less, more preferably 90% by weight or less, even more preferably 88% by weight or less, and particularly preferably 85% by weight or less. In this specification, the "weight ratio of the structural unit (B) relative to the total weight of the copolymer polycarbonate resin" is essentially the same as the "weight ratio of the structural unit (B) relative to all structural units constituting the copolymer polycarbonate resin." Similarly, the "weight ratio of the structural unit (A) relative to the total weight of the copolymer polycarbonate resin" is essentially the same as the "weight ratio of the structural unit (A) relative to all structural units constituting the copolymer polycarbonate resin." Furthermore, a carbonate structural unit refers to a structural unit containing a carbonyl group, and the weight ratio of structural units derived from dihydroxy compounds in a copolymeric polycarbonate resin is for structural units containing one carbonyl group that serves as a linking group, i.e., repeating structural units. Therefore, the weight ratio of structural units (i.e., structural unit A, structural unit B) to all structural units that constitute a copolymeric polycarbonate resin is essentially synonymous with the weight ratio of carbonate structural units (i.e., carbonate structural unit A, carbonate structural unit B) to all structural units that constitute a copolymeric polycarbonate resin.

[0086] It is preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 2 to 3 carbon atoms, and that the number-average molecular weight of the polyoxyalkylene glycol is 3,000 to 20,000. In this case, the copolymer polycarbonate resin exhibits a peak melting temperature (i.e., a peak melting temperature exceeding 35°C) higher than room temperature (specifically, 20 to 35°C) and exhibits excellent heat storage properties in the high-temperature range (specifically, above 35°C to 80°C). Therefore, the copolymer polycarbonate resin is preferably used as a heat storage material that requires heat storage performance in the high-temperature range (specifically, above 35°C to 80°C). From the same viewpoint, it is more preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 2 to 3 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 3,500 or more and 15,000 or less, and it is particularly preferable that the alkylene group R in the repeating unit represented by formula (7) has 2 to 3 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 4,000 or more and 12,000 or less.

[0087] Furthermore, it is preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 4 to 6 carbon atoms, and that the number average molecular weight of the polyoxyalkylene glycol is 1,500 or more and 20,000 or less. In this case, the copolymer polycarbonate resin exhibits a melting peak temperature close to room temperature (specifically, 20 to 35°C) and exhibits excellent heat storage properties at room temperature. Therefore, the copolymer polycarbonate resin is preferably used as a heat storage material that requires heat storage performance at room temperature (specifically, 20 to 35°C). From a similar viewpoint, it is more preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 4 to 6 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 2,000 or more and 15,000 or less, it is even more preferable that the alkylene group R in the repeating unit represented by formula (7) has 4 to 6 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 2,500 or more and 10,000 or less, and it is particularly preferable that the alkylene group R in the repeating unit represented by formula (7) has 4 to 6 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 3,500 or more and 7,000 or less.

[0088] Furthermore, it is preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 7 or more carbon atoms, and that the number-average molecular weight of the polyoxyalkylene glycol is 800 or more and 20,000 or less. In this case, the copolymer polycarbonate resin exhibits a peak melting temperature higher than room temperature (20°C to 35°C) (i.e., a peak melting temperature exceeding 35°C) and exhibits excellent heat storage properties in the high-temperature range. Therefore, the copolymer polycarbonate resin is preferably used as a heat storage material that requires heat storage performance in the high-temperature range (specifically, above 35°C and below 80°C). From a similar viewpoint, it is more preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 7 or more and 15 or less carbon atoms, and that the number average molecular weight of the polyoxyalkylene glycol is 800 or more and 15,000 or less; it is even more preferable that the alkylene group R in the repeating unit represented by formula (7) has 8 or more and 12 or less carbon atoms, and that the number average molecular weight of the polyoxyalkylene glycol is 800 or more and 10,000 or less; and it is particularly preferable that the alkylene group R in the repeating unit represented by formula (7) has 9 or more and 10 or less carbon atoms, and that the number average molecular weight of the polyoxyalkylene glycol is 900 or more and 8,000 or less.

[0089] The number average molecular weight of the polyoxyalkylene glycol can be calculated, for example, by a method of measurement using gel permeation chromatography (GPC) or a method of determining from the hydroxyl value of the terminal group, etc. Furthermore, the number average molecular weight of the polyoxyalkylene glycol constituting the structural unit (B) in the copolymer polycarbonate resin can be calculated, for example, from the area ratio of the main chain signal of the structural unit (B) to the terminal signal of the structural unit (B) in a 1H or 13C-NMR spectrum.

[0090] The polyalkylene glycol can be produced by, for example, the production method described in Example 1 of JP 2018-165343 A. Specifically, a polyalkylene glycol having an alkylene chain with an appropriate number of carbon atoms is first produced from an alkylene diol having an alkylene chain with an appropriate number of carbon atoms, as in the production of polydecamethylene glycol using a polycondensation reaction using 1,10-decanediol as a raw material. This polyalkylene glycol is then hydrolyzed in an acidic or basic aqueous solution while adjusting conditions such as temperature, catalyst type, catalyst amount, polymerization temperature, and polymerization reaction time, thereby obtaining a polyalkylene glycol having an appropriate number of carbon atoms in the alkylene chain and an appropriate molecular weight.

[0091] In the copolymer polycarbonate resin, the structural unit (B) preferably contains a structural unit derived from polyethylene glycol having a number-average molecular weight of 3,000 or more and 20,000 or less. In this case, the copolymer polycarbonate resin exhibits a peak melting temperature (i.e., a peak melting temperature exceeding 35°C) higher than room temperature (specifically, 20°C to 35°C) and exhibits excellent heat storage properties in high-temperature ranges. Therefore, the copolymer polycarbonate resin is preferably used as a heat storage material that requires heat storage performance in high-temperature ranges (specifically, above 35°C and 80°C or less). From the same perspective, the structural unit (B) more preferably contains a structural unit derived from polyethylene glycol having a number-average molecular weight of 3,500 or more and 15,000 or less, and particularly preferably contains a structural unit derived from polyethylene glycol having a number-average molecular weight of 4,000 or more and 12,000 or less.

[0092] In the copolymer polycarbonate resin, the structural unit (B) preferably contains a structural unit derived from polytetramethylene glycol (i.e., PTMG) having a number-average molecular weight of 1,500 to 20,000. In this case, the copolymer polycarbonate resin exhibits a melting peak temperature close to room temperature (specifically, 20 to 35°C) and exhibits excellent heat storage properties at room temperature. Therefore, the copolymer polycarbonate resin is preferably used as a heat storage material that requires heat storage performance at room temperature (specifically, 20 to 35°C). From the same perspective, the structural unit (B) more preferably contains a structural unit derived from PTMG having a number-average molecular weight of 2,000 to 15,000, more preferably contains a structural unit derived from PTMG having a number-average molecular weight of 2,500 to 10,000, even more preferably contains a structural unit derived from PTMG having a number-average molecular weight of 3,000 to 8,000, and particularly preferably contains a structural unit derived from PTMG having a number-average molecular weight of 3,500 to 8,000.

[0093] PTMG is commercially available and can be produced by the method described in Example 1 of JP-A-2004-161893, for example.

[0094] The copolymeric polycarbonate resin preferably contains a structural unit (B) derived from polyhexamethylene glycol (i.e., PHMG) having a number-average molecular weight of 1,500 or more and 20,000 or less. In this case, the copolymeric polycarbonate resin exhibits a melting peak temperature in the room temperature to high temperature range (specifically, 20°C to 80°C) and exhibits excellent heat storage properties in the room temperature to high temperature range. Therefore, the copolymeric polycarbonate resin is preferably used as a heat storage material that requires heat storage performance in the room temperature to high temperature range. From the same viewpoint, the structural unit (B) more preferably contains a structural unit derived from PHMG having a number-average molecular weight of 2,000 to 15,000, and particularly preferably contains a structural unit derived from PHMG having a number-average molecular weight of 2,500 to 10,000.

[0095] The copolymeric polycarbonate resin preferably contains a structural unit (B) derived from polynonamethylene glycol (i.e., PNMG) having a number-average molecular weight of 800 to 20,000. In this case, the copolymeric polycarbonate resin exhibits a peak melting temperature in the high-temperature range (specifically, a peak melting temperature exceeding 35°C) and exhibits excellent heat storage properties in the high-temperature range (specifically, above 35°C to 80°C). Therefore, the copolymeric polycarbonate resin is preferably used as a heat storage material that requires heat storage performance in the high-temperature range (specifically, above 35°C to 80°C). From the same perspective, the structural unit (B) more preferably contains a structural unit derived from PNMG having a number-average molecular weight of 900 to 15,000, and particularly preferably contains a structural unit derived from PNMG having a number-average molecular weight of 1,000 to 10,000.

[0096] The copolymeric polycarbonate resin preferably contains a structural unit (B) derived from polydecamethylene glycol (i.e., PDMG) having a number-average molecular weight of 800 to 20,000. In this case, the copolymeric polycarbonate resin exhibits a peak melting temperature in the high-temperature range (specifically, a peak melting temperature above 35°C) and exhibits excellent heat storage properties in the high-temperature range (specifically, above 35°C to 80°C). Therefore, the copolymeric polycarbonate resin is preferably used as a heat storage material that requires heat storage performance in the high-temperature range (specifically, above 35°C to 80°C). From the same perspective, the structural unit (B) more preferably contains a structural unit derived from PDMG having a number-average molecular weight of 900 to 15,000, and particularly preferably contains a structural unit derived from PDMG having a number-average molecular weight of 1,000 to 10,000.

[0097] The copolymer polycarbonate resin may contain structural units other than the structural units (A) and (B). Hereinafter, structural units other than the structural units (A) and (B) may be referred to as "structural units (C)." The dihydroxy compounds forming the structural unit (C) do not include the dihydroxy compounds forming the structural unit (A) and the dihydroxy compounds forming the structural unit (B). Examples of dihydroxy compounds forming the structural unit (C) include acetal-containing dihydroxy compounds other than the dihydroxy compounds represented by the formula (2). Furthermore, hydroxy compounds containing three or more hydroxy groups in the molecule may also be used as compounds forming the structural unit (C). The polycarbonate resin may also contain structural units derived from diester compounds. Polycarbonate resins partially incorporating structural units derived from diester compounds are referred to as polyestercarbonate resins. In this specification, the term "polycarbonate resin" encompasses polyestercarbonate resins.

[0098] Examples of diester compounds include the following dicarboxylic acids: aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. These dicarboxylic acids can be used as raw materials for polyester carbonate resins as dicarboxylic acids themselves, but depending on the production method, dicarboxylic acid esters such as methyl esters and phenyl esters of dicarboxylic acids, or dicarboxylic acid derivatives such as dicarboxylic acid halides can also be used as raw materials.

[0099] Examples of hydroxy compounds containing three or more hydroxy groups in the molecule include the following hydroxy compounds: polyhydric alcohols having three hydroxy groups, such as glycerin, trimethylolpropane, and triethanolamine; polyhydric alcohols having four hydroxy groups, such as pentaerythritol, diglycerin, xylose, and sorbitan; polyhydric alcohols having five hydroxy groups, such as xylitol, triglycerin, glucose, and fructose; polyhydric alcohols having six hydroxy groups, such as sorbitol, malbitol, tetraglycerin, and inositol; disaccharides having more than six hydroxy groups, such as polyglycerin, sucrose, trehalose, and lactose; and trisaccharides, such as maltotriose. These compounds may be used alone or in combination of two or more. Among these, trimethylolpropane and glycerin are preferred.

[0100] When the structural unit (C) is introduced into the copolymeric polycarbonate resin, the content of the structural unit (C) is preferably kept relatively small, and is used for the purpose of improving heat storage capacity, for example.

[0101] When the copolymeric polycarbonate resin contains the structural unit (C), the weight ratio of the structural unit (C) to the total weight of the copolymeric polycarbonate resin is preferably 1% by weight or more, more preferably 3% by weight or more, from the viewpoint of being able to more sufficiently improve heat storage capacity. Furthermore, from the viewpoint of being more balanced and excellent in heat storage capacity and shape retention capacity, the weight ratio of the structural unit (C) to the total weight of the copolymeric polycarbonate resin is preferably 10% by weight or less, more preferably 7% by weight or less.

[0102] When the copolymeric polycarbonate resin contains, as the structural unit (C), a structural unit derived from a hydroxy compound containing three or more hydroxy groups in the molecule, the weight ratio of the structural unit derived from a hydroxy compound containing three or more hydroxy groups in the molecule to the total weight of the copolymeric polycarbonate resin is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, from the viewpoint of achieving a better balance between heat storage capacity and shape retention. From the same viewpoint, the weight ratio of the structural unit derived from a hydroxy compound containing three or more hydroxy groups in the molecule is preferably 3% by weight or less, more preferably 1% by weight or less.

[0103] From the viewpoint of further improving heat storage capacity, the copolymeric polycarbonate resin preferably has a melting enthalpy (hereinafter sometimes referred to as ΔH(L)) observed by differential scanning calorimetry in the temperature range of -30°C to 80°C of 20 J / g or more, more preferably 30 J / g or more, even more preferably 40 J / g or more, even more preferably 50 J / g or more, and particularly preferably 55 J / g or more. From the viewpoint of difficulty in realizing this, ΔH(L) is usually 500 J / g or less, more preferably 200 J / g or less, and particularly preferably 150 J / g or less.

[0104] In this specification, the enthalpy of fusion is the heat of fusion obtained by analyzing a portion of a melting curve within a specific temperature range measured by differential scanning calorimetry according to the method of JIS K7122-1987. When there are multiple melting peaks within a specific temperature range, the enthalpy of fusion is the sum of the peak areas within the temperature range.

[0105] In this specification, the temperature range of 160° C. to 280° C. may be selected in differential scanning calorimetry, and the fusion enthalpy may be measured in addition to the fusion enthalpy ΔH(L) observed in the temperature range of −30° C. to 80° C. In this specification, the fusion enthalpy observed in the temperature range of 160° C. to 280° C. by differential scanning calorimetry may be referred to as ΔH(H).

[0106] The copolymer polycarbonate resin may have ΔH(H) in addition to ΔH(L). The former is the melting enthalpy mainly derived from the structural unit (B), and the latter is presumed to be the melting enthalpy mainly derived from structural units other than the structural unit (B) (specifically, the structural unit (A) and the like). When the copolymer polycarbonate resin has the above ΔH(H), from the viewpoint of moldability and shape retention, ΔH(H) is preferably 1 J / g or more, more preferably 5 J / g or more, and even more preferably 15 J / g. From the viewpoint of further improving shape retention and moldability, ΔH(H) is usually 100 J / g or less, preferably 70 J / g or less, and particularly preferably 50 J / g or less.

[0107] ΔH(L) can be adjusted to fall within the above range, for example, by increasing or decreasing the content or type of the structural unit (B). Specifically, increasing the content of the structural unit (B) tends to increase ΔH(L), while decreasing the content of the structural unit (B) tends to decrease ΔH(L). Furthermore, selecting the type of structural unit (B) can increase ΔH(L). ΔH(H) can be adjusted within the above range, for example, by increasing or decreasing the content of the structural unit (A) or by selecting the type of structural unit (A). Specifically, by increasing the content of the structural unit (A), ΔH(H) tends to increase, and by decreasing the content of the structural unit (A), ΔH(H) tends to decrease. Furthermore, by selecting a structural unit (A) with high crystallinity, ΔH(H) tends to increase, and by selecting a structural unit (A) with low crystallinity, ΔH(H) tends to decrease. By increasing the amount of the structural unit (A), ΔH(H) tends to increase, and by decreasing the amount of the structural unit (A), ΔH(H) tends to decrease. The desired enthalpy of fusion can be adjusted by selecting the types and content ratios of the structural units (A) and (B).

[0108] The enthalpy of fusion (ΔH(L) and ΔH(H)) is measured as follows. For samples with a melting peak temperature (Tm) below 200°C, an aluminum sample pan containing approximately 10 mg of a sample (specifically, a copolymer polycarbonate resin) is cooled to -120°C under a nitrogen atmosphere using an EXSTAR 6220 differential scanning calorimeter manufactured by SII Nanotechnology. The sample is then heated from approximately -120°C at a rate of 20°C / min to 200°C. The sample is then cooled at a rate of 20°C / min to -120°C. The sample is then heated again at a rate of 20°C / min to 200°C. The differential scanning calorimetric curve obtained from the second heating run is used as the measurement curve. ΔH(L) is obtained by analyzing the temperature range of -30°C to 80°C in accordance with the method of JIS K7122:1987.

[0109] If the melting peak temperature (Tm) is higher than 200°C, the upper limit of the measurement temperature is changed to, for example, 300°C, while maintaining the same conditions (e.g., starting temperature, heating rate, cooling rate, and hold time). For example, if the melting peak temperature (Tm) is below 280°C, an aluminum sample pan containing approximately 10 mg of the sample (specifically, copolymer polycarbonate resin) is first cooled to -120°C under a nitrogen atmosphere using an SII NanoTechnology EXSTAR 6220 differential scanning calorimeter. The sample is then heated from approximately -120°C at a heating rate of 20°C / min to 280°C. The sample is then cooled at a heating rate of 20°C / min to -120°C. The sample is then heated again at a heating rate of 20°C / min to 280°C. The differential scanning calorimetry curve obtained from the second heating run is used as the measurement curve. ΔH(L) is obtained by analyzing the temperature range of -30°C to 80°C, and ΔH(H) is obtained by analyzing the temperature range of 160°C to 280°C according to the method of JIS K7122:1987.

[0110] As shown in Figure 9, when the melting peak temperatures (Tm) of the structural units (A) and (B) are close to each other, multiple peaks of melting enthalpy may be present on a single baseline (i.e., inseparable). Figure 9 shows an example in which two peaks exist: a first peak (specifically, the peak of structural unit (B)) and a second peak (specifically, the peak of structural unit (A)). In this case, the individual peaks are separated by a perpendicular line L2 drawn from the point where the data between the peaks is maximum (e.g., the point on the DSC curve at 35 °C between the first and second peaks in Figure 9) to the baseline L1. This method of peak separation is called "vertical division." The point where the data between the first and second peaks is maximum (e.g., the point on the DSC curve at 35 °C in Figure 9) is the peak end of the first peak and the peak start of the second peak. The peak start of the first peak is set to the same point as the base start on the lower temperature side (for example, the point on the DSC curve at -14°C in Figure 9). Each peak area is the area of ​​the region surrounded by the DSC curve, the dividing line (i.e., the perpendicular line L2), and the baseline L1, and the melting enthalpy can be found by calculating this area. The first peak on the low temperature side is the melting enthalpy derived from the structural unit (B), and the second peak on the high temperature side is the melting enthalpy derived from the structural unit (A). Figure 9 shows an example of the DSC curve during the second heating and the results of peak separation by vertical division (specifically, Example 15 described below).

[0111] [Physical properties of copolymer polycarbonate resin] The copolymer polycarbonate resin is not particularly limited with respect to its physical properties, but it is preferable that the copolymer polycarbonate resin satisfies the following physical properties.

[0112] Reduced viscosity The molecular weight of a copolymer polycarbonate resin can be expressed by reduced viscosity, with a higher reduced viscosity indicating a larger molecular weight. From the viewpoint of further improving the shape retention of the copolymer polycarbonate resin, the reduced viscosity is preferably 0.30 dL / g or more, and more preferably 0.40 dL / g or more. On the other hand, from the viewpoint of further improving productivity and moldability and further improving the strength of molded articles, since molded articles can be produced while maintaining the fluidity of the copolymer polycarbonate resin during molding, the reduced viscosity is preferably 2.0 dL / g or less, more preferably 1.50 dL / g or less, and even more preferably 1.00 dL / g or less.

[0113] The reduced viscosity of a copolymer polycarbonate resin is measured as follows. First, a copolymer polycarbonate resin is dissolved in 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 is used as the solvent. The mixing ratio of phenol to 1,1,2,2-tetrachloroethane is 1:1 by mass. The reduced viscosity is measured using an Ubbelohde viscometer at a temperature of 30.0°C ± 0.1°C. Details of the reduced viscosity measurement method will be explained in the Examples.

[0114] Glass transition temperature (Tg) When the copolymer polycarbonate resin has a glass transition temperature (Tg), from the viewpoint of further improving the shape retention and heat resistance of the copolymer polycarbonate resin, Tg is preferably 80° C. or higher, more preferably 100° C. or higher. Moreover, from the viewpoint of difficulty in realizing such a temperature, Tg is preferably 300° C. or lower, more preferably 200° C. or lower.

[0115] The glass transition temperature is measured according to the method specified in JIS K7121-1987. Specifically, the measurement is performed using a differential scanning calorimeter (e.g., EXSTAR 6220 manufactured by SII NanoTechnology Inc.). The measurement conditions are as follows: an aluminum sample pan containing approximately 10 mg of copolymer polycarbonate resin sample is cooled to -120°C under a nitrogen atmosphere, then heated from -120°C at a heating rate of 20°C / min to 200°C. The sample is then cooled to -120°C at a cooling rate of 20°C / min. It is then heated again at a heating rate of 20°C / min to 200°C. The extrapolated glass transition onset temperature can be determined from the DSC data obtained from the second heating run. The midpoint glass transition onset temperature is determined from the temperature at which the curve representing the stepwise change in the glass transition intersects with a line equidistant along the vertical axis from the line extending the low-temperature baseline and the high-temperature baseline. This midpoint glass transition onset temperature is taken as the glass transition temperature Tg. If the glass transition temperature Tg is higher than 200°C, the upper limit temperature for measurement is changed to, for example, 300°C, and measurement is performed under the same conditions (for example, starting temperature, rate of temperature increase, rate of temperature decrease, holding time).

[0116] The glass transition temperature of the copolymer polycarbonate can be adjusted, for example, by the copolymerization composition of the structural unit (A) and the structural unit (B).

[0117] Peak melting temperature (Tm) In this specification, the melting peak temperature (Tm) refers to the temperature at the top of the melting peak obtained by analyzing a melting curve measured by differential scanning calorimetry in the same manner as in the case of the glass transition temperature, in accordance with JIS K7121-1987. In this specification, the melting peak temperature obtained by analyzing the temperature range of -30°C to 80°C in accordance with JIS K7121-1987 is defined as Tm(L), and the melting peak temperature obtained by similarly analyzing the temperature range of 160°C to 280°C in accordance with JIS K7121-1987 is defined as Tm(H). Copolymer polycarbonate resins usually have a Tm(L), but may have both a Tm(L) and a Tm(H). The former is presumably a melting peak temperature derived primarily from the structural unit (B), while the latter is presumably a melting peak temperature derived primarily from structural units other than the structural unit (B) (specifically, the structural unit (A), etc.). Furthermore, each of Tm(L) and Tm(H) may have multiple melting peak temperatures.

[0118] From the viewpoint of improving the heat storage performance of a heat storage material containing a copolymeric polycarbonate resin, the Tm(L) of the copolymeric polycarbonate resin is preferably 10° C. or more and 100° C. or less. From the viewpoint of further improving the heat storage performance around a practical temperature range (specifically, 10 to 100° C.) and making it more practical as a heat storage material, the lower limit of Tm(L) of the copolymeric polycarbonate resin is more preferably 15° C., and even more preferably 20° C. From the same viewpoint, the upper limit is more preferably 80° C., and even more preferably 60° C.

[0119] When the copolymer polycarbonate resin has the above Tm(H), from the viewpoint of further improving shape retention, moldability, processability, and heat resistance, Tm(H) is preferably 150°C or more and 350°C or less, and more preferably 200°C or more and 300°C or less.

[0120] [II] Regarding the second aspect Next, a copolymer polycarbonate resin according to a second embodiment of the present disclosure will be described. The second embodiment of the present disclosure is, as described above, a copolymer polycarbonate resin having at least structural units (A) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and heteroalicyclic dihydroxy compounds, and structural units (B) derived from polyoxyalkylene glycol, The copolymer polycarbonate resin is characterized in that the alkylene group R in the repeating unit represented by the following formula (7), which constitutes the polyoxyalkylene glycol, has 7 or more carbon atoms, and the number average molecular weight of the polyoxyalkylene glycol is 800 or more and 20,000 or less. [ka] (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

[0121] Structural unit (A) The structural unit (A) in the second embodiment is the same as in the first embodiment described above.

[0122] ·Constituent unit (B) The copolymer polycarbonate resin has a structural unit (B) derived from polyoxyalkylene glycol. The polyoxyalkylene glycol contains a repeating unit represented by formula (7), in which the alkylene group R in the repeating unit represented by formula (7) has 7 or more carbon atoms, and the number-average molecular weight of the polyoxyalkylene glycol is 800 to 2000. As a result, the copolymer polycarbonate resin exhibits a melting peak temperature (i.e., a melting peak temperature exceeding 35°C) higher than room temperature (specifically, 20 to 35°C) and exhibits excellent heat storage properties in a high-temperature range (specifically, above 35°C to 80°C). Therefore, the copolymer polycarbonate resin can be preferably used as a heat storage material that requires heat storage performance in a high-temperature range (specifically, above 35°C to 80°C). From the same viewpoint, it is preferable that the alkylene group R in the repeating unit represented by formula (7) has 7 or more and 15 or less carbon atoms and the number average molecular weight is 800 or more and 15,000 or less, it is more preferable that the repeating unit has 8 or more and 12 or less carbon atoms and the number average molecular weight is 800 or more and 10,000 or less, and it is particularly preferable that the repeating unit has 9 or more and 10 or less carbon atoms and the number average molecular weight is 900 or more and 8,000 or less.

[0123] The weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is not particularly limited, but is preferably more than 20% by weight and not more than 99% by weight. When the weight ratio of the structural unit (B) exceeds 20% by weight, the crystallinity increases and the enthalpy of fusion becomes larger, thereby improving heat storage capacity. When the weight ratio of the structural unit (B) is 99% by weight or less, heat resistance and shape retention are improved. From the viewpoint of further improving heat storage capacity, the weight ratio of the structural unit (B) is more preferably 25% by weight or more, even more preferably 30% by weight or more, even more preferably 50% by weight or more, and particularly preferably 65% ​​by weight or more. On the other hand, from the viewpoint of further improving heat resistance and shape retention, the weight ratio of the structural unit (B) is more preferably 95% by weight or less, even more preferably 90% by weight or less, and particularly preferably 85% by weight or less.

[0124] Other preferred embodiments of the structural unit (B) in the second embodiment are the same as those in the first embodiment described above.

[0125] [Physical properties of copolymer polycarbonate resin] From the viewpoint of improving the heat storage performance of a heat storage material containing a copolymeric polycarbonate resin, the Tm(L) of the copolymeric polycarbonate resin is preferably 20° C. or more and 100° C. or less. From the viewpoint of excellent heat storage performance near the high temperature range (specifically, above 35° C. and 80° C. or less) and excellent practicality as a heat storage material, the lower limit of Tm(L) of the copolymeric polycarbonate resin is more preferably 30° C., and even more preferably 40° C. From the same viewpoint, the upper limit is more preferably 80° C., and even more preferably 70° C. Other physical properties of the copolymeric polycarbonate resin of the second embodiment are the same as those of the first embodiment described above.

[0126] [III] Regarding the third aspect Next, the copolymer polycarbonate resin according to the third aspect of the present disclosure will be described. The third aspect of the present disclosure is, as described above, a copolymer polycarbonate resin having at least a structural unit (A) derived from a dihydroxy compound and a structural unit (B) derived from a polyoxyalkylene glycol, The alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol has 2 or more carbon atoms, The polycarbonate resin has a weight ratio of the structural unit (B) of more than 50% by weight and not more than 99% by weight relative to the total weight of the copolymeric polycarbonate resin.

[0127] Structural unit (A) The copolymer polycarbonate resin has a structural unit (A) derived from a dihydroxy compound. The dihydroxy compound forming the structural unit (A) is not particularly limited. Examples include an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound. The structural unit (A) preferably contains a structural unit derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound. In this case, shape retention and moldability are further improved.

[0128] ·Constituent unit (B) The copolymeric polycarbonate resin has a structural unit (B) derived from polyoxyalkylene glycol. The weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is, as described above, more than 50% by weight and not more than 99% by weight. From the viewpoint of further improving heat storage capacity due to higher crystallinity and larger enthalpy of fusion, the weight ratio of the structural unit (B) is preferably 55% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight or more. On the other hand, from the viewpoint of further improving heat resistance and shape retention, the weight ratio of the structural unit (B) is preferably 95% by weight or less, more preferably 90% by weight or less, and particularly preferably 85% by weight or less. Other aspects of the constitutional units in the third embodiment are the same as those in the first embodiment described above.

[0129] [IV] Regarding the fourth aspect Next, the copolymer polycarbonate resin according to the fourth embodiment of the present disclosure will be described. The fourth embodiment of the present disclosure is as described above, and comprises at least a structural unit (A) derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from polytetramethylene glycol having a number average molecular weight of 1,500 to 20,000, The copolymer polycarbonate resin has a melting enthalpy ΔH(L) of 20 J / g or more as measured within a temperature range of -30°C to 80°C by differential scanning calorimetry.

[0130] [Copolymer polycarbonate resin] The copolymer polycarbonate resin has at least a structural unit (A) derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from polytetramethylene glycol (also referred to as polytetramethylene ether glycol; hereinafter, sometimes referred to as "PTMG") having a number average molecular weight (hereinafter, sometimes referred to as "Mn") of 1,500 or more and 20,000 or less, and has a melting enthalpy of 20 J / g or more as measured by differential scanning calorimetry within a temperature range of -30°C or more and 80°C or less.

[0131] The copolymer polycarbonate resin has a melting enthalpy (hereinafter sometimes referred to as ΔH(L)) of 20 J / g or more, as measured by differential scanning calorimetry within a temperature range of -30°C to 80°C. ΔH(L) is preferably 30 J / g or more, more preferably 40 J / g or more, even more preferably 50 J / g or more, and particularly preferably 55 J / g or more. From the viewpoint of difficulty in realizing this, ΔH(L) is usually 500 J / g or less, more preferably 200 J / g or less, and particularly preferably 150 J / g or less. When ΔH(L) is within the above range, the copolymer polycarbonate resin has excellent heat storage properties.

[0132] In this specification, the enthalpy of fusion is the heat of fusion obtained by analyzing a portion of a melting curve within a specific temperature range measured by differential scanning calorimetry according to the method of JIS K7122-1987. When there are multiple melting peaks within a specific temperature range, the enthalpy of fusion is the sum of the peak areas within the temperature range.

[0133] In this specification, the temperature range of 160° C. to 280° C. may be selected in differential scanning calorimetry, and the fusion enthalpy may be measured in addition to the fusion enthalpy ΔH(L) observed in the temperature range of −30° C. to 80° C. In this specification, the fusion enthalpy observed in the temperature range of 160° C. to 280° C. by differential scanning calorimetry may be referred to as ΔH(H).

[0134] The copolymer polycarbonate resin may have ΔH(H) in addition to ΔH(L). The former is the melting enthalpy mainly derived from structural units derived from PTMG and repeating structural units comprising carbonyl groups, while the latter is presumed to be the melting enthalpy mainly derived from structural units derived from dihydroxy compounds other than PTMG (specifically, alicyclic dihydroxy compounds, heteroalicyclic dihydroxy compounds, etc.) and repeating structural units comprising carbonyl groups. When the copolymer polycarbonate resin has the above ΔH(H), from the viewpoints of moldability and shape retention, ΔH(H) is preferably 1 J / g or more, more preferably 5 J / g or more, and even more preferably 15 J / g. ΔH(H) is usually 100 J / g or less, more preferably 70 J / g or less, and particularly preferably 50 J / g or less.

[0135] The enthalpy of fusion (ΔH(L) and ΔH(H)) is measured as follows. For samples with a melting peak temperature (Tm) below 200°C, an aluminum sample pan containing approximately 10 mg of a sample (specifically, a copolymer polycarbonate resin) is cooled to -120°C under a nitrogen atmosphere using an EXSTAR 6220 differential scanning calorimeter manufactured by SII Nanotechnology. The sample is then heated from approximately -120°C at a rate of 20°C / min to 200°C. The sample is then cooled at a rate of 20°C / min to -120°C. The sample is then heated again at a rate of 20°C / min to 200°C. The differential scanning calorimetric curve obtained from the second heating run is used as the measurement curve. ΔH(L) is obtained by analyzing the temperature range of -30°C to 80°C in accordance with the method of JIS K7122:1987.

[0136] If the melting peak temperature (Tm) is higher than 200°C, the upper limit of the measurement temperature is changed to, for example, 300°C, while maintaining the same conditions (e.g., starting temperature, heating rate, cooling rate, and hold time). For example, if the melting peak temperature (Tm) is below 280°C, an aluminum sample pan containing approximately 10 mg of the sample (specifically, copolymer polycarbonate resin) is first cooled to -120°C under a nitrogen atmosphere using an SII NanoTechnology EXSTAR 6220 differential scanning calorimeter. The sample is then heated from approximately -120°C at a heating rate of 20°C / min to 280°C. The sample is then cooled at a heating rate of 20°C / min to -120°C. The sample is then heated again at a heating rate of 20°C / min to 280°C. The differential scanning calorimetry curve obtained from the second heating run is used as the measurement curve. ΔH(L) is obtained by analyzing the temperature range of -30°C to 80°C, and ΔH(H) is obtained by analyzing the temperature range of 160°C to 280°C according to the method of JIS K7122:1987.

[0137] Structural unit (A) The copolymeric polycarbonate resin has a structural unit (A) derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound. That is, the copolymeric polycarbonate resin has at least one structural unit derived from an alicyclic dihydroxy compound or a structural unit derived from a heteroalicyclic dihydroxy compound. The copolymeric polycarbonate resin may also have both a structural unit derived from an alicyclic dihydroxy compound and a structural unit derived from a heteroalicyclic dihydroxy compound, in which case these structural units are collectively referred to as structural unit (A).

[0138] The dihydroxy compound that forms the structural unit (A) is an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound.

[0139] In this specification, an alicyclic dihydroxy compound is defined as a carbocyclic dihydroxy compound that does not have aromaticity. Also, in this specification, a heteroalicyclic dihydroxy compound is defined as a cyclic dihydroxy compound that contains one or more heteroatoms as ring-constituting atoms. In this specification, a heteroalicyclic dihydroxy compound is a concept that does not include the above-mentioned alicyclic dihydroxy compounds.

[0140] When the copolymer polycarbonate resin contains structural units derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound, a rigid ring structure is introduced into the molecular chain, which improves the glass transition temperature of the resin and provides it with excellent heat resistance, shape retention, and moldability.

[0141] The alicyclic dihydroxy compound is not particularly limited, but examples thereof include dihydroxy compounds containing one or more 4-membered ring structures as part of their structure, and dihydroxy compounds containing one or more 5-membered or 6-membered ring structures as part of their structure. The 6-membered ring structure may be fixed in a chair or boat shape by a covalent bond. When the alicyclic dihydroxy compound contains at least one 5-membered or 6-membered ring structure in its structure, the resulting polycarbonate resin may have higher heat resistance. Therefore, the alicyclic dihydroxy compound is preferably a compound containing one or more 5-membered or 6-membered ring structures as part of its structure. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. An excessively large number of carbon atoms increases heat resistance, but tends to make synthesis and purification difficult and increase costs. The smaller the carbon number, the easier it is to purify and obtain.

[0142] Specific examples of alicyclic dihydroxy compounds containing one or more 5-membered ring structures or 6-membered ring structures as part of their structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II): HOCH2-R 5 -CH2OH (I) HO-R 6 -OH (II) (However, in formula (I) and formula (II), R 5 and R 6 each independently represents a substituted or unsubstituted divalent group containing a cycloalkyl structure having 4 to 30 carbon atoms.

[0143] The cyclohexanedimethanol (hereinafter, sometimes referred to as "CHDM"), which is an alicyclic dihydroxy compound represented by the general formula (I), is a compound represented by the general formula (I) in which R 5 is represented by the following general formula (Ia) (wherein R 7represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples of such isomers include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.

[0144] [ka]

[0145] Tricyclodecane dimethanol (hereinafter, sometimes referred to as "TCDDM") and pentacyclopentadecanedimethanol, which are alicyclic dihydroxy compounds represented by the general formula (I), can be prepared by the following general formula (I): 5 is represented by the following general formula (Ib) (wherein n represents 0 or 1).

[0146] [ka]

[0147] The alicyclic dihydroxy compound represented by the general formula (I), decalin dimethanol or tricyclotetradecane dimethanol, is a compound represented by the general formula (I), 5 is represented by the following general formula (Ic) (wherein m represents 0 or 1). Specific examples of such isomers include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, etc.

[0148] [ka]

[0149] Furthermore, the norbornane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (I), is a compound represented by the general formula (I) in which R 5is represented by the following general formula (Id) (wherein p represents 1 or 2). Specific examples of such isomers include, when p=1, bicyclo[2.2.1]heptane-2,3-dimethanol (2,3-norbornane dimethanol), bicyclo[2.2.1]heptane-2,5-dimethanol, etc.

[0150] [ka]

[0151] When p=2, the alicyclic dihydroxy compound bicyclooctanedimethanol is a compound represented by the general formula (I): 5 These include various isomers represented by the following general formula (Id): Specific examples of such isomers include bicyclo[2,2,2]octane-1,4-dimethanol (hereinafter sometimes referred to as "BODM") represented by the following formula (Id-1):

[0152] [ka]

[0153] Adamantane dimethanol (hereinafter, sometimes referred to as "ADDM"), which is an alicyclic dihydroxy compound represented by general formula (I), is a compound represented by general formula (I) in which R 5 is represented by the following general formula (Ie): 3,7 ]-1,3-dimethanol, tricyclo[3,3,1,1 3,7 ]-2,2-dimethanol and the like.

[0154] [ka]

[0155] In addition, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), is 6 is represented by the following general formula (IIa) (wherein R 7 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples of such isomers include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol.

[0156] [ka]

[0157] The alicyclic dihydroxy compounds represented by the general formula (II), tricyclodecanediol and pentacyclopentadecanediol, are compounds represented by the general formula (II), 6 includes various isomers represented by the following general formula (IIb) (wherein n represents 0 or 1).

[0158] [ka]

[0159] The alicyclic dihydroxy compound represented by the general formula (II), decalindiol or tricyclotetradecanediol, is a compound represented by the general formula (II), 6 is represented by the following general formula (IIc) (wherein m represents 0 or 1). Specific examples of such isomers include 2,6-decalindiol, 1,5-decalindiol, and 2,3-decalindiol.

[0160] [ka]

[0161] The norbornanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), is a compound represented by the general formula (II) in which R 6 is represented by the following general formula (IId) (wherein p represents 1 or 2). Specifically, when P=1, bicyclo[2.2.1]heptane-2,3-diol (2,3-norbornanediol), bicyclo[2.2.1]heptane-2,5-diol, etc. are used.

[0162] [ka]

[0163] In formula (IId), when p=2, the alicyclic dihydroxy compound represented by general formula (II) is bicyclooctanediol, which is a compound represented by general formula (II), 6 These include various isomers represented by the following general formula (IId): Specific examples of such isomers include bicyclo[2,2,2]octane-1,4-diol represented by the following formula (IId-1):

[0164] [ka]

[0165] The adamantanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), is a compound represented by the general formula (II) in which R 6 The isomers include various isomers represented by the following general formula (IIe). 3,7 ]-1,3-diol, tricyclo[3,3,1,1 3,7 ]-2,2-diol and the like.

[0166] [ka]

[0167] The above-mentioned exemplary compounds are merely examples of usable alicyclic dihydroxy compounds, and the present invention is not limited thereto. These alicyclic dihydroxy compounds may be used alone or in combination of two or more. When two or more alicyclic dihydroxy compounds are used in combination, the copolymeric polycarbonate resin will have structural units derived from each of the alicyclic dihydroxy compounds. In this case, the structural units derived from each of the alicyclic dihydroxy compounds are collectively referred to as structural unit (A).

[0168] Among the alicyclic dihydroxy compounds containing one or more five- or six-membered ring structures as part of the above-mentioned structure, compounds containing two or more five- or six-membered ring structures as part of the structure are preferred from the viewpoint of a more rigid molecular skeleton and further improving the heat resistance, shape retention, and moldability of the copolymer polycarbonate resin. In this case, the multiple rings may be fused rings or spiro rings. Preferred specific examples of such compounds include ADDM represented by the following formula (3), BODM represented by the following formula (4), and TCDDM represented by the following formula (5).

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] Among the above-mentioned alicyclic dihydroxy compounds containing one or more 5-membered ring structures or 6-membered ring structures as part of the structure, from the viewpoint of easy availability, one or more compounds selected from the group consisting of CHDM, TCDDM, BODM, and ADDM represented by the following formula (6) are preferred.

[0173] [ka]

[0174] Of the alicyclic dihydroxy compounds containing one or more 5-membered or 6-membered ring structures as part of the above structure, from the viewpoint of being able to impart heat resistance to the polycarbonate, one or more compounds selected from the group consisting of TCDDM, BODM, and ADDM are preferred, and from the viewpoint of being able to impart crystallinity in addition to heat resistance, BODM and / or ADDM are more preferred.

[0175] Examples of heteroatoms contained in the heteroalicyclic dihydroxy compound include oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. From the viewpoints of low water absorption, coloration prevention, and light resistance, the heteroatom is preferably an oxygen atom and / or a sulfur atom. From the viewpoints of coloration prevention and light resistance, the heteroatom is more preferably an oxygen atom.

[0176] The heteroalicyclic dihydroxy compound is not particularly limited, but examples thereof include a dihydroxy compound having a cyclic ether structure, a dihydroxy compound having a cyclic thioether structure, etc. From the viewpoints of preventing coloration and preventing the generation of acidic substances, the heteroalicyclic dihydroxy compound is preferably a dihydroxy compound having a cyclic ether structure.

[0177] Specific examples of the dihydroxy compound having a cyclic ether structure include a dihydroxy compound represented by the following formula (1) and a dihydroxy compound represented by the following formula (2).

[0178] [ka]

[0179] [ka]

[0180] In the formula (2), R1 ~R 4 are each independently an alkyl group having 1 to 3 carbon atoms.

[0181] Examples of the dihydroxy compound represented by the formula (1) include isosorbide, isomannide, and isoidet, which are stereoisomers, and these may be used alone or in combination of two or more. Among these dihydroxy compounds, isosorbide, which is obtained by dehydration condensation of sorbitol, which is produced from various starches that are abundant and easily available as a plant-derived resource, is most preferred in terms of availability and ease of production, light resistance, optical properties, moldability, heat resistance, and carbon neutrality.

[0182] Examples of dihydroxy compounds represented by the formula (2) include 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane (common name: spiroglycol), 3,9-bis(1,1-diethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(1,1-dipropyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and dioxangulol. These compounds may be used alone or in combination of two or more. Spiroglycol is preferred from the viewpoints of easy availability and the fact that it increases the glass transition temperature of the resin.

[0183] Among dihydroxy compounds having a cyclic ether structure, compounds containing a total of two or more five-membered or six-membered ring structures as part of the structure are preferred from the viewpoint of having a more rigid molecular skeleton and further improving the heat resistance and moldability of the copolymer polycarbonate resin. In this case, the multiple rings may be fused rings or spiro rings. Preferred examples of such compounds include dihydroxy compounds represented by the above formula (1) and dihydroxy compounds represented by the above formula (2).

[0184] From the viewpoints of improving the heat resistance and moldability of the copolymeric polycarbonate resin and facilitating the availability of raw materials, the dihydroxy compound having a cyclic ether structure is more preferably a dihydroxy compound represented by the above formula (1) and / or a dihydroxy compound represented by the above formula (2).

[0185] From the viewpoint of improving the heat resistance, shape retention, and moldability of the copolymer polycarbonate resin, the structural unit (A) is preferably a structural unit derived from an alicyclic dihydroxy compound containing one or more 5-membered or 6-membered ring structures as part of its structure and / or a structural unit derived from a dihydroxy compound having a cyclic ether structure, and more preferably a structural unit derived from an alicyclic dihydroxy compound containing a total of two or more 5-membered or 6-membered ring structures as part of its structure and / or a structural unit derived from a dihydroxy compound having a cyclic ether structure containing a total of two or more 5-membered or 6-membered ring structures as part of its structure. From a similar viewpoint, the structural unit (A) is preferably a structural unit derived from one or more dihydroxy compounds selected from the group consisting of CHDM, TCDDM, BODM, ADDM, dihydroxy compounds represented by the formula (1) above, and dihydroxy compounds represented by the formula (2) above, and it is more preferable that the structural unit (A) is a structural unit derived from one or more dihydroxy compounds selected from the group consisting of TCDDM, BODM, ADDM, dihydroxy compounds represented by the formula (1) above, and dihydroxy compounds represented by the formula (2) above.

[0186] When the structural unit (A) contains a structural unit derived from an alicyclic dihydroxy compound containing two or more 5-membered or 6-membered ring structures as part of its structure and / or a dihydroxy compound having a cyclic ether structure containing two or more 5-membered or 6-membered ring structures as part of its structure, the structural unit (A) can further contain a structural unit derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound that is different from the alicyclic dihydroxy compound containing two or more 5-membered or 6-membered ring structures as part of its structure and the dihydroxy compound having a cyclic ether structure containing two or more 5-membered or 6-membered ring structures as part of its structure. When the structural unit (A) contains a structural unit derived from an alicyclic dihydroxy compound containing two or more 5-membered or 6-membered ring structures as part of its structure and / or a dihydroxy compound having a cyclic ether structure containing two or more 5-membered or 6-membered ring structures as part of its structure, it is preferable that the structural unit (A) further contains a structural unit derived from an alicyclic dihydroxy compound containing only one 5-membered or 6-membered ring structure in its structure. In this case, the heat storage capacity of the copolymer polycarbonate resin may be further improved. A preferred specific example of a structural unit derived from an alicyclic dihydroxy compound containing only one 5-membered ring structure or one 6-membered ring structure in the structure includes the structural unit derived from CHDM described above.

[0187] From the viewpoint of achieving a copolymeric polycarbonate resin with a better balance of heat storage capacity, heat resistance, shape retention, and moldability, and from the viewpoint of easy availability of raw materials, it is particularly preferred that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (1) above, or consists of structural units derived from the dihydroxy compound represented by formula (1) above and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving heat storage capacity, it is most preferred that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (1) above, or consists of structural units derived from the dihydroxy compound represented by formula (1) above and structural units derived from CHDM.

[0188] From the viewpoint of achieving superior heat storage capacity and heat resistance of the copolymeric polycarbonate resin, it is particularly preferred that the structural unit (A) consists solely of structural units derived from ADDM, or consists solely of structural units derived from ADDM and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving heat storage capacity, it is most preferred that the structural unit (A) consists solely of structural units derived from ADDM, or consists solely of structural units derived from ADDM and structural units derived from CHDM.

[0189] From the viewpoint of achieving superior heat storage capacity and heat resistance of the copolymeric polycarbonate resin, it is particularly preferred that the structural unit (A) consists solely of structural units derived from BODM, or consists of structural units derived from BODM and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving heat storage capacity, it is most preferred that the structural unit (A) consists solely of structural units derived from BODM, or consists of structural units derived from BODM and structural units derived from CHDM.

[0190] From the viewpoints of achieving superior heat storage capacity, heat resistance, and shape retention of the copolymeric polycarbonate resin, and of easy availability of raw materials, it is particularly preferred that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (2) above, or consists of structural units derived from the dihydroxy compound represented by formula (2) above and structural units derived from TCDDM and / or CHDM. From the viewpoint of further improving heat storage capacity, it is most preferred that the structural unit (A) consists solely of structural units derived from the dihydroxy compound represented by formula (2) above, or consists of structural units derived from the dihydroxy compound represented by formula (2) above and structural units derived from CHDM.

[0191] The weight ratio of the structural unit (A) to the total weight of the polycarbonate resin is not particularly limited, but is preferably 5% by weight or more and 75% by weight or less. The lower limit of the weight ratio of the structural unit (A) is more preferably 15% by weight, even more preferably 20% by weight, and particularly preferably 30% by weight. On the other hand, the upper limit is more preferably 70% by weight, even more preferably 60% by weight, and particularly preferably 45% by weight. When the weight ratio of the structural unit (A) is within the above range, the heat storage capacity, heat resistance, and mold retention are better balanced and excellent. In this specification, the weight ratio of structural units derived from dihydroxy compounds in the copolymer polycarbonate resin (e.g., structural unit (A), structural unit (B) described below, etc.) refers to structural units containing one carbonyl group as a linking group, i.e., repeating structural units.

[0192] ·Constituent unit (B) The copolymer polycarbonate resin has a structural unit (B) derived from polytetramethylene glycol (PTMG) having a number average molecular weight of 1,500 or more and 20,000 or less. As the dihydroxy compound that forms the structural unit (B), PTMG having a number average molecular weight of 1,500 or more and 20,000 or less is used. By including structural units derived from PTMG having a number-average molecular weight of 1,500 to 20,000, the copolymer polycarbonate resin has a large fusion enthalpy and excellent heat storage properties, and the peak melting temperature can be kept within a practical temperature range.

[0193] The number average molecular weight of PTMG is more preferably at least 2000, even more preferably at least 2500, and particularly preferably at least 3500. The number average molecular weight of PTMG is more preferably at most 20000, even more preferably at most 15000, particularly preferably at most 10000, and most preferably at most 7000. When the number average molecular weight of PTMG is within the above range, the crystallinity is high and the enthalpy of fusion is larger, resulting in better heat storage properties.

[0194] The number average molecular weight of PTMG can be calculated, for example, by a method of measurement using gel permeation chromatography (GPC) or a method of determining from the hydroxyl value of the terminal group, etc. Furthermore, the number average molecular weight of PTMG constituting the structural unit (B) in the copolymer polycarbonate resin can be calculated, for example, from the area ratio of the main chain signal of the structural unit (B) to the terminal signal of the structural unit (B) in a 1H or 13C-NMR spectrum.

[0195] PTMG can be commercially available and can be produced by the method described in Example 1 of JP-A-2004-161893, for example.

[0196] The weight ratio of the structural unit (B) to the total weight of the copolymer polycarbonate resin is not particularly limited, but is preferably 25% by weight or more and 99% by weight or less. The lower limit of the weight ratio of the structural unit (B) is more preferably 30% by weight, even more preferably 50% by weight, and particularly preferably 65% ​​by weight. On the other hand, the upper limit is more preferably 95% by weight, even more preferably 90% by weight, particularly preferably 85% by weight, and most preferably 80% by weight. If it is above the lower limit, crystallinity will be high and the enthalpy of fusion will be large, thereby further improving heat storage capacity. If it is below the upper limit, a better balance between heat resistance and shape retention will be achieved.

[0197] The copolymer polycarbonate resin may contain structural units other than the structural units (A) and (B). Hereinafter, structural units other than the structural units (A) and (B) may be referred to as "structural units (C)." The dihydroxy compounds forming the structural unit (C) do not include the dihydroxy compounds forming the structural unit (A) and the dihydroxy compounds forming the structural unit (B). Examples of dihydroxy compounds forming the structural unit (C) include acyclic aliphatic dihydroxy compounds, acyclic ether-containing dihydroxy compounds, and acetal-containing dihydroxy compounds other than the dihydroxy compounds represented by (2) above. Furthermore, hydroxy compounds containing three or more hydroxy groups in the molecule may also be used as compounds forming the structural unit (C). Polycarbonate resins partially incorporating structural units derived from diester compounds are referred to as polyester carbonate resins. In this specification, the term "polycarbonate resin" encompasses polyester carbonate resins.

[0198] Examples of acyclic aliphatic dihydroxy compounds include the following dihydroxy compounds: straight-chain aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; and branched-chain aliphatic dihydroxy compounds such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

[0199] Examples of the acyclic ether-containing dihydroxy compound include oxyalkylene glycols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

[0200] Examples of diester compounds include the following dicarboxylic acids: aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. These dicarboxylic acid components can be used as raw materials for polyester carbonate resins as dicarboxylic acids themselves, but depending on the production method, dicarboxylic acid esters such as methyl esters and phenyl esters, or dicarboxylic acid derivatives such as dicarboxylic acid halides can also be used as raw materials.

[0201] Examples of hydroxy compounds containing three or more hydroxy groups in the molecule include the following: polyhydric alcohols having three hydroxy groups, such as glycerin, trimethylolpropane, and triethanolamine; polyhydric alcohols having four hydroxy groups, such as pentaerythritol, diglycerin, xylose, and sorbitan; polyhydric alcohols having five hydroxy groups, such as xylitol, triglycerin, glucose, and fructose; polyhydric alcohols having six hydroxy groups, such as sorbitol, malbitol, tetraglycerin, and inositol; disaccharides having more than six hydroxy groups, such as polyglycerin, sucrose, trehalose, and lactose; and trisaccharides, such as maltotriose. These compounds may be used alone or in combination of two or more. Among these, trimethylolpropane and glycerin are preferred.

[0202] When the structural unit (C) is introduced into a polycarbonate resin, it is preferable to use a relatively small amount of the structural unit (C) for purposes such as improving heat storage capacity. Among the structural units (C), linear aliphatic dihydroxy compounds having 6 to 30 carbon atoms are preferred from the viewpoint of further improving the fusion enthalpy. The structural units formed by such linear aliphatic dihydroxy compounds may crystallize, further improving the fusion enthalpy of the resin. From the same viewpoint, linear aliphatic dihydroxy compounds having 8 to 20 carbon atoms are more preferred.

[0203] When the polycarbonate resin contains the structural unit (C), the weight ratio of the structural unit (C) to the total weight of the polycarbonate resin is preferably 1% by weight or more, more preferably 3% by weight or more, and is preferably 10% by weight or less, more preferably 7% by weight or less. Within this range, heat storage and shape retention are well balanced and excellent.

[0204] When the polycarbonate resin contains, as the structural unit (C), a structural unit derived from a hydroxy compound containing three or more hydroxy groups in the molecule, the weight ratio of the structural unit derived from a hydroxy compound containing three or more hydroxy groups in the molecule to the total weight of the polycarbonate resin is preferably 0.1% by weight or more, more preferably 0.3% by weight or more. Also, it is preferably 3% by weight or less, more preferably 1% by weight or less. Within this range, heat storage and shape retention are well balanced and excellent.

[0205] [Manufacturing method of copolymer polycarbonate resin] The method for producing the copolymeric polycarbonate resin of the fourth embodiment will be explained, but the same applies to the first to third embodiments. The copolymeric polycarbonate resin can be synthesized by a step of polycondensing the dihydroxy compound forming the structural unit (A), the dihydroxy compound forming the structural unit (B), and a carbonate diester through transesterification reaction as raw materials. More specifically, the copolymeric polycarbonate resin can be obtained by removing, from the system, the monohydroxy compound and other by-products produced in the transesterification reaction during the polycondensation.

[0206] In this step, the dihydroxy compound that forms the structural unit (A) and the dihydroxy compound that forms the structural unit (B) are the same as those described above.

[0207] The transesterification reaction proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst will be referred to as a "polymerization catalyst.") The type of polymerization catalyst can have a significant effect on the reaction rate of the transesterification reaction and the quality of the resulting polycarbonate resin.

[0208] The polymerization catalyst is not particularly limited as long as it can satisfy the transparency, color tone, heat resistance, weather resistance, and mechanical properties of the resulting polycarbonate resin. Examples of the polymerization catalyst that can be used include metal compounds of Group I or Group II (hereinafter simply referred to as "Group 1" and "Group 2") in the long periodic table, as well as basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds, with Group 1 metal compounds and / or Group 2 metal compounds being preferred.

[0209] Examples of Group 1 metal compounds include the following compounds: 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 phenylborohydride, and boron phenylide. Examples of the Group 1 metal compound include potassium, lithium boron phenylide, cesium boron phenylide, 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, alcoholates and phenolates of sodium, potassium, lithium and cesium, and disodium salt, dipotassium salt, dilithium salt and dicesium salt of bisphenol A. As the Group 1 metal compound, lithium compounds are preferred from the viewpoints of polymerization activity and the color tone of the resulting polycarbonate resin.

[0210] Examples of Group 2 metal compounds include the following compounds: 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. As the Group 2 metal compound, magnesium compounds, calcium compounds, or barium compounds are preferred, and from the viewpoints of polymerization activity and the color tone of the resulting polycarbonate resin, magnesium compounds and / or calcium compounds are more preferred, and calcium compounds are most preferred.

[0211] Although it is 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 Group 1 metal compound and / or Group 2 metal compound, it is more preferable to use only a Group 1 metal compound and / or a Group 2 metal compound, and from the viewpoint of the color tone of the resulting polycarbonate resin, it is most preferable to use only a Group 2 metal compound.

[0212] The amount of the polymerization catalyst used is preferably 1 μmol or more, more preferably 5 μmol or more, and particularly preferably 25 μmol or more per mol of the total dihydroxy compounds used in the reaction, and is preferably 500 μmol or less, more preferably 300 μmol or less, and particularly preferably 100 μmol or less per mol of the total dihydroxy compounds used in the reaction.

[0213] By adjusting the amount of polymerization catalyst used within the above-mentioned range, the polymerization rate can be increased, making it possible to obtain a polycarbonate resin with a desired molecular weight without necessarily increasing the polymerization temperature, thereby suppressing deterioration in the color tone of the polycarbonate resin. Furthermore, it is possible to prevent unreacted raw materials from volatilizing during the polymerization, which would cause the molar ratio of the dihydroxy compound and the carbonate diester to be disrupted, thereby more reliably obtaining a resin with a desired molecular weight and copolymerization ratio. Furthermore, it is possible to suppress the occurrence of side reactions, thereby further preventing deterioration in the color tone of the polycarbonate resin or discoloration during molding.

[0214] Considering the adverse effects of sodium, potassium, and cesium, among the Group 1 metals, on the color tone of the polycarbonate resin, and the adverse effects of iron on the color tone of the polycarbonate resin, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is preferably 1 ppm by weight or less. In this case, deterioration of the color tone of the polycarbonate resin can be further prevented, and the color tone of the polycarbonate resin can be further improved. From the same perspective, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is more preferably 0.5 ppm by weight or less. Note that these metals may be mixed in not only from the catalyst used but also from raw materials or reaction equipment. Regardless of their origin, the total amount of compounds of these metals in the polycarbonate resin, as the total content of sodium, potassium, cesium, and iron, is preferably within the above-mentioned range.

[0215] The polycondensation of a dihydroxy compound and a carbonate diester is carried out in multiple stages using multiple reactors in the presence of the above-mentioned catalyst. The reaction may be carried out in a batchwise manner, a continuous manner, or a combination of a batchwise manner and a continuous manner, but it is preferable to adopt a continuous manner, which allows the production of a polycarbonate resin with less thermal history and is therefore excellent in productivity.

[0216] From the viewpoint of controlling the polymerization rate and the quality of the resulting polycarbonate resin, it is important to appropriately select the jacket temperature, internal temperature, and pressure in the reaction system according to the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stage of the polycondensation reaction, and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the later stage of the reaction. In this case, distillation of unreacted monomers is suppressed, and it becomes easier to adjust the molar ratio of the dihydroxy compound to the carbonate diester to the desired ratio. As a result, a decrease in the polymerization rate can be suppressed. Furthermore, it becomes possible to more reliably obtain a polymer with the desired molecular weight and terminal groups.

[0217] Adjusting the temperature of the polycondensation reaction can improve productivity and prevent the product from being subjected to increased heat history. Furthermore, it is possible to further prevent volatilization of the monomer and decomposition and discoloration of the polycarbonate resin. Specifically, the following reaction conditions can be adopted for the first-stage reaction. The maximum internal temperature of the polymerization reactor is set within the range of usually 160 to 230°C, preferably 170 to 220°C, and more preferably 180 to 210°C. The pressure of the polymerization reactor (hereinafter, "pressure" refers to absolute pressure) is set within the range of usually 1 to 110 kPa, preferably 5 to 50 kPa, and more preferably 7 to 30 kPa. The reaction time is set within the range of usually 0.1 to 10 hours, preferably 1 to 5 hours. The first-stage reaction is preferably carried out while distilling off the generated monohydroxy compound from the reaction system.

[0218] From the second stage onwards, it is preferable to gradually reduce the pressure of the reaction system from the pressure of the first stage, and ultimately reduce the pressure (absolute pressure) of the reaction system to 1 kPa or less while continuously removing the generated monohydroxy compound from the reaction system. The maximum internal temperature of the polymerization reactor is set within the range of usually 200 to 260°C, preferably 210 to 250°C, and particularly preferably 215 to 240°C. The reaction time is set within the range of usually 0.1 to 10 hours, preferably 0.5 to 5 hours, and particularly preferably 1 to 3 hours.

[0219] Once the desired melt viscosity (molecular weight) has been confirmed using the stirring power as an indicator, the polymerization reaction is terminated by introducing nitrogen into the reactor to return the pressure to normal pressure or by withdrawing the molten resin from the reactor. The molten resin is discharged from the die head in the form of strands, cooled and solidified, and pelletized using a rotary cutter or the like. If necessary, extrusion devolatilization, extrusion kneading, and extrusion filtration processes may be added before pelletization. In these processes, additives are mixed into the resin, low molecular weight components are devolatilized using a vacuum vent, and foreign matter is removed using a polymer filter. Note that in the examples described below, some resins do not solidify at room temperature. In such cases, the molten resin after the polymerization reaction is withdrawn in a block form, and the resin is cut into pellets for use in molding or evaluation.

[0220] [Physical properties of copolymer polycarbonate resin] There are no particular limitations on the physical properties of the polycarbonate resin, as long as the melting enthalpy observed within the temperature range of -30°C to 80°C by differential scanning calorimetry as described above is 20 J / g or more. However, it is preferable that the polycarbonate resin satisfy the following physical properties:

[0221] Reduced viscosity The molecular weight of a polycarbonate resin can be expressed by reduced viscosity, with a higher reduced viscosity indicating a larger molecular weight. The reduced viscosity is typically 0.30 dL / g or higher, preferably 0.40 dL / g or higher. In this case, the shape retention of the heat storage material can be further improved. On the other hand, the reduced viscosity is typically 2.0 dL / g or lower, more preferably 1.50 dL / g or lower, and even more preferably 1.00 dL / g or lower. In these cases, the strength of the molded body can be improved while maintaining fluidity during molding, thereby further improving productivity and moldability.

[0222] The reduced viscosity of copolymer polycarbonate resin is measured as follows. First, polycarbonate resin is dissolved in 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 is used as the solvent. The mixture ratio of phenol to 1,1,2,2-tetrachloroethane is 1:1 by mass. The value measured using an Ubbelohde viscometer at a temperature of 30.0°C ± 0.1°C is used. Details of the reduced viscosity measurement method are explained in the examples.

[0223] Glass transition temperature (Tg) When the copolymer polycarbonate resin has a glass transition temperature (Tg), from the viewpoint of further improving shape retention and heat resistance, Tg is preferably 100° C. or higher, more preferably 120° C. or higher. Furthermore, from the viewpoint of difficulty in realizing this, Tg is preferably 300° C. or lower, more preferably 200° C. or lower. By keeping Tg within this range, the heat resistance of the resin is more excellent.

[0224] The glass transition temperature was measured according to the method specified in JIS K7121-1987. More specifically, the measurement was performed using a differential scanning calorimeter (EXSTAR 6220, manufactured by SII NanoTechnology, Inc.). The measurement conditions were as follows: an aluminum sample pan containing approximately 10 mg of polycarbonate sample was cooled to -120 °C under a nitrogen atmosphere, then heated from -120 °C at a heating rate of 20 °C / min to 200 °C. The sample was then cooled to -120 °C at a cooling rate of 20 °C / min. The sample was then heated again to 200 °C at a heating rate of 20 °C / min. The extrapolated glass transition onset temperature was determined from the DSC data obtained in the second heating run. The midpoint glass transition onset temperature was calculated from the temperature at which the curve representing the stepwise change in the glass transition intersects with a line equidistant along the vertical axis from the line extending the low-temperature and high-temperature baselines. This midpoint glass transition onset temperature was taken as the glass transition temperature (Tg). If the glass transition temperature Tg is higher than 200°C, the upper limit temperature for measurement is changed to, for example, 300°C, and measurement is performed under the same conditions (for example, starting temperature, rate of temperature increase, rate of temperature decrease, holding time).

[0225] The glass transition temperature of the copolymer polycarbonate can be adjusted, for example, by the copolymerization composition of the structural unit (A) and the structural unit (B).

[0226] Peak melting temperature (Tm) In this specification, the melting peak temperature (Tm) refers to the temperature at the top of the melting peak obtained by analyzing a melting curve measured by differential scanning calorimetry in the same manner as in the case of the glass transition temperature, in accordance with JIS K7121-1987. In this specification, the melting peak temperature obtained by analyzing the temperature range of -30°C to 80°C in accordance with JIS K7121-1987 is defined as Tm(L), and the melting peak temperature obtained by similarly analyzing the temperature range of 160°C to 280°C in accordance with JIS K7121-1987 is defined as Tm(H). Copolymer polycarbonate resins usually have a Tm(L), but may have both a Tm(L) and a Tm(H). The former is presumably the melting peak temperature derived primarily from repeating units comprising structural units derived from PTMG and carbonyl groups, while the latter is presumably the melting peak temperature derived primarily from repeating units comprising structural units derived from dihydroxy compounds other than PTMG (specifically, alicyclic dihydroxy compounds, heteroalicyclic dihydroxy compounds, etc.) and carbonyl groups. Furthermore, each of Tm(L) and Tm(H) may have multiple melting peak temperatures.

[0227] The Tm(L) of the copolymer polycarbonate resin is preferably 10°C or more and 50°C or less so that the heat storage performance of the heat storage material containing the copolymer polycarbonate resin is better. The lower limit of the Tm(L) of the copolymer polycarbonate resin is more preferably 15°C, and even more preferably 20°C. On the other hand, the upper limit is more preferably 45°C, and even more preferably 40°C. When the Tm(L) is in the above range, the heat storage performance around room temperature is further improved, and the practicality as a heat storage material is superior.

[0228] When the copolymer polycarbonate resin has the above Tm(H), from the viewpoint of further improving shape retention, moldability, processability, and heat resistance, Tm(H) is preferably 150° C. or higher and 350° C. or lower, and more preferably 200° C. or higher and 300° C. or lower. When the Tm(H) is within the above range, the shape retention, moldability, processability, and heat resistance are more excellent.

[0229] [Uses of copolymer polycarbonate resin] Copolymer polycarbonate resins are suitable for use as heat storage materials because they have excellent heat storage properties, heat resistance, moldability, shape retention, etc. The same applies to the first to third aspects.

[0230] [Polycarbonate resin composition] The copolymer polycarbonate resin may contain various additives to the extent that the effects are not impaired. Examples of the additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, fillers and other fillers, neutralizing agents, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, crosslinking agents, crosslinking aids, metal deactivators, molecular weight modifiers, antibacterial agents, antifungal agents, fluorescent brighteners, and light diffusing agents such as organic diffusing agents and inorganic diffusing agents.

[0231] Furthermore, the copolymer polycarbonate resin can be blended with other resins different from the copolymer polycarbonate resin, as long as the effect is not impaired. Specific examples of other resins include polyethylene, polypropylene, polyester, polyester carbonate, aromatic polycarbonate, polyamide, polyimide, ABS, PMMA, PET, etc. From the viewpoint of improving shape retention, it is preferable to blend the copolymer polycarbonate resin with other resins different from this copolymer polycarbonate resin.

[0232] [Method for producing polycarbonate resin composition] The polycarbonate resin composition can be produced, for example, by mechanically melt-kneading the above-mentioned components constituting the resin composition. Examples of melt-kneading machines that can be used include single-screw extruders, twin-screw extruders, Brabender mixers, Banbury mixers, kneader blenders, and roll mills. The kneading may involve kneading all the components at once, or a multi-stage division kneading method in which an optional component is kneaded and then the remaining components are added and kneaded. Among these, a method in which each component is continuously added to a twin-screw extruder equipped with a vacuum vent to continuously obtain a resin composition is preferred from the viewpoints of productivity and quality uniformity. The lower limit of the kneading temperature is usually 150°C, preferably 180°C, and more preferably 200°C. The upper limit of the kneading temperature is usually 280°C, preferably 260°C, more preferably 250°C, and particularly preferably 240°C. This range can suppress thermal degradation due to heating by the kneader or shear heat generation, while also increasing productivity (kneading processing speed). The description of the polycarbonate resin composition also applies to the first to third aspects.

[0233] [V] Regarding the fifth aspect Next, a heat storage material according to a fifth aspect of the present disclosure will be described. As described above, the fifth aspect of the present disclosure is a heat storage material containing a copolymer polycarbonate resin (specifically, the copolymer polycarbonate resin according to the first to fourth aspects).

[0234] [Heat storage material] The heat storage material is not particularly limited as long as it contains the above-mentioned copolymer polycarbonate resin, but is preferably the above-mentioned polycarbonate resin composition.

[0235] [VI] Regarding the sixth aspect Next, a heat storage molded body according to the sixth aspect of the present disclosure will be described. As described above, the sixth aspect of the present disclosure is a heat storage molded body obtained by molding a heat storage material. In other words, the sixth aspect of the present disclosure is a heat storage molded body made from a heat storage material.

[0236] [Heat storage molding] The heat storage molded body is obtained by molding the heat storage material. Specifically, it is produced by molding the heat storage material into various shapes such as sheets, plates, granules, pellets, and tubes. Common molding methods, such as extrusion molding, injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, etc.), blow molding, vacuum molding, pressure molding, and press molding, can be used. Specifically, the components are mixed during the production of the heat storage material, and the molten material is poured into a mold either as is or after slight cooling to form the desired sheet or plate shape. Since the heat storage material solidifies at a temperature lower than its flow initiation temperature, it can be molded into a block shape and then cut into sheets or plates. Furthermore, the heat storage material can be attached to, coated on, or impregnated into films, cloth, fibers, particle board, etc. to form sheets or plates. It can also be packed in polyethylene bags or other similar bags and cooled to form sheets, plates, or rods. Alternatively, the material may be extruded into a sheet or plate using an extruder. The material may be extruded into a rod or pipe shape and then cut into granules or pellets. In each of the extrusion methods, the apparatus and processing conditions are not particularly limited.

[0237] The shape of the molded product is not particularly limited, and examples thereof include a sheet, film, plate, particle, lump, fiber, rod, porous body, foam, etc., with a sheet, film, or plate being preferred. The molded film can also be uniaxially or biaxially stretched. Examples of stretching methods include a roll method, a tenter method, and a tubular method. Furthermore, surface treatments commonly used in industry, such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, can also be applied.

[0238] When obtaining a molded body by extrusion molding, the heat storage material is fed into an extruder that has reached a temperature at which it is sufficiently melted, kneaded while melting, and discharged from a die of various shapes, followed by cooling by air or water to obtain the desired molded body. Either a single-screw or twin-screw extruder may be used as the extruder, but from the viewpoint of dispersibility, a twin-screw extruder is preferred. In this case, the extruder temperature is preferably 100°C or higher and 200°C or lower, more preferably 110°C or higher and 190°C or lower, and even more preferably 120°C or higher and 180°C or lower. When the extruder temperature is within this range, volatilization of the heat storage component during kneading and extrusion molding can be suppressed.

[0239] When a molded article is obtained by injection molding, the heat storage material or the like is fed into an extruder at a temperature at which it is sufficiently melted, and then injected into a mold of various shapes to obtain a desired molded article. The molding temperature in this case is also preferably in the same range as in the case of extrusion molding.

[0240] [Uses of heat storage molded products] The uses of the heat storage molded body are not particularly limited, but because it has excellent heat storage performance, heat resistance, moldability, and shape retention, it can be suitably used, for example, as a product or component that directly or indirectly requires heat or cold insulation performance.

[0241] Examples of products or components that directly or indirectly require heat or cold insulation performance include building materials, furniture, interior goods, bedding, bathroom materials, vehicles, air conditioning equipment, electrical appliances, thermal containers, food packaging films, clothing, daily necessities, agricultural materials, fermentation systems, thermoelectric conversion systems, and heat transfer media. The above descriptions of the heat storage material and heat storage molded article also apply to the first to third aspects.

[0242] [VII] Regarding the seventh aspect Next, a seventh aspect of the present disclosure will be described. As described above, the seventh aspect of the present disclosure is a phase change material composed of a polymer having carbonate bonds in the molecular chain and having a melting enthalpy ΔH(L) of 20 J / g or more as measured in a temperature range of −30° C. to 80° C. by differential scanning calorimetry.

[0243] A phase change material (i.e., PCM) is a material that stores and releases heat by utilizing latent heat that accompanies a phase change of a substance. The phase change material of the present disclosure is composed of, for example, a copolymer polycarbonate resin. That is, the polymer is, for example, a copolymer polycarbonate resin. Such a phase change material is a resin-type phase change material, and stores and releases heat by utilizing latent heat that accompanies a solid-to-solid phase transition, rather than the latent heat that accompanies a solid-to-liquid phase transition as in conventional paraffin-type phase change materials.

[0244] The polymer constituting the phase transition material has a melting enthalpy ΔH(L) of 20 J / g or more as measured by differential scanning calorimetry in the temperature range of -30°C to 80°C. This gives the phase transition material excellent heat storage properties. From the viewpoint of further improving heat storage properties, the melting enthalpy ΔH(L) of the polymer is preferably 30 J / g or more, more preferably 40 J / g or more, even more preferably 50 J / g or more, and particularly preferably 55 J / g or more. From the viewpoint of difficulty in realizing this, the ΔH(L) of the polymer is usually 500 J / g or less, more preferably 200 J / g or less, and particularly preferably 150 J / g or less.

[0245] It is preferable that the polymer contains at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and heteroalicyclic dihydroxy compounds, and a structural unit (B) derived from a polyoxyalkylene glycol, which further improves shape retention and moldability.

[0246] The weight ratio of the structural unit (B) to the total weight of the polymer constituting the phase change material is preferably more than 20% by weight and not more than 99% by weight. When the weight ratio of the structural unit (B) exceeds 20% by weight, the crystallinity of the phase change material increases and the enthalpy of fusion increases, thereby further improving the heat storage capacity of the phase change material. When the weight ratio of the structural unit (B) is 99% by weight or less, the heat resistance and shape retention of the phase change material are further improved. From the viewpoint of further improving the heat storage capacity of the phase change material, the weight ratio of the structural unit (B) is preferably 25% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and particularly preferably 65% ​​by weight or more. On the other hand, from the viewpoint of further improving the heat resistance and shape retention of the phase change material, the weight ratio of the structural unit (B) is preferably 95% by weight or less, more preferably 90% by weight or less, and particularly preferably 85% by weight or less.

[0247] The alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol preferably has 2 to 3 carbon atoms and a number-average molecular weight of 3,000 to 20,000. In this case, the phase transition material exhibits a peak melting temperature (i.e., a peak melting temperature exceeding 35°C) higher than room temperature (specifically, 20 to 35°C) and exhibits excellent heat storage properties in a high-temperature range (specifically, above 35°C to 80°C). Therefore, the phase transition material is preferably used as a heat storage material that requires heat storage performance in a high-temperature range (specifically, above 35°C to 80°C). From the same viewpoint, it is more preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 2 to 3 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 3,500 or more and 15,000 or less, and it is particularly preferable that the alkylene group R in the repeating unit represented by formula (7) has 2 to 3 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 4,000 or more and 12,000 or less.

[0248] [ka] (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

[0249] Furthermore, it is preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 4 to 6 carbon atoms and a number average molecular weight of 1,500 to 20,000. In this case, the phase transition material exhibits a melting peak temperature close to room temperature (specifically, 20 to 35°C) and exhibits excellent heat storage properties at room temperature. Therefore, the phase transition material is preferably used as a heat storage material that requires heat storage performance at room temperature (specifically, 20 to 35°C). From a similar viewpoint, it is more preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 4 to 6 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 2,000 or more and 15,000 or less, it is even more preferable that the alkylene group R in the repeating unit represented by formula (7) has 4 to 6 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 2,500 or more and 10,000 or less, and it is particularly preferable that the alkylene group R in the repeating unit represented by formula (7) has 4 to 6 carbon atoms and the number average molecular weight of the polyoxyalkylene glycol is 3,500 or more and 7,000 or less.

[0250] Furthermore, it is preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 7 or more carbon atoms and a number average molecular weight of 800 to 20,000. In this case, the phase transition material exhibits a melting peak temperature (i.e., a melting peak temperature exceeding 35°C) higher than room temperature (specifically, 20°C to 35°C) and exhibits excellent heat storage properties in the high temperature range (specifically, above 35°C to 80°C). Therefore, the copolymer polycarbonate resin is preferably used as a heat storage material that requires heat storage performance in the high temperature range (specifically, above 35°C to 80°C). From a similar viewpoint, it is more preferable that the alkylene group R in the repeating unit represented by formula (7) constituting the polyoxyalkylene glycol has 7 or more and 15 or less carbon atoms, and that the number average molecular weight of the polyoxyalkylene glycol is 800 or more and 15,000 or less; it is even more preferable that the alkylene group R in the repeating unit represented by formula (7) has 8 or more and 12 or less carbon atoms, and that the number average molecular weight of the polyoxyalkylene glycol is 800 or more and 10,000 or less; and it is particularly preferable that the alkylene group R in the repeating unit represented by formula (7) has 9 or more and 10 or less carbon atoms, and that the number average molecular weight of the polyoxyalkylene glycol is 900 or more and 8,000 or less.

[0251] Other configurations of the phase change material are the same as those of the first embodiment. Furthermore, since the phase change material can be considered a heat storage material, reference is made to the heat storage material and heat storage molded article in the fourth embodiment for other configurations. [Example]

[0252] The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, "%" indicates "% by weight".

[0253] [Evaluation method] The physical properties and characteristics of the polycarbonate resin compositions and molded articles were evaluated by the following methods.

[0254] (1) Press film creation The resulting polycarbonate resin copolymer was used without drying. A spacer was prepared by hollowing out a metal plate (specifically, a SUS plate) measuring 10 cm in length and 10 cm in width, leaving a 1 cm width, and cutting out an inner section measuring 8 cm in length and 8 cm in width. This spacer was sandwiched between two Teflon® films measuring 15 cm in length and 15 cm in width and 1 mm in thickness. Approximately 4 g of pellets were placed within the spacer frame and heat-pressed. The heat-press temperature was 150°C, the preheating time was 5-7 minutes, and the molding pressure was 40 MPa. The molding pressure time was 1 minute. After heat-pressing, the sheet-like sample, including the mirror plate and spacer, was removed and cooled under pressure at 20 MPa for 3 minutes in a water-tube-cooled press. Films with thicknesses of 400 to 500 μm were produced. When the solidification of the polycarbonate resin was slow, the resin was left overnight to solidify, and then a film was obtained.

[0255] (2) Glass transition temperature (Tg, unit °C), melting peak temperature (Tm, unit °C), melting enthalpy (ΔH, unit J / g) Measurements were performed using an SII NanoTechnology EXSTAR 6220 differential scanning calorimeter. The resulting polycarbonate copolymer was used as the measurement sample without drying. Specifically, an aluminum sample pan containing approximately 10 mg of the measurement sample was cooled to -120°C under a nitrogen atmosphere, then heated from approximately -120°C at a heating rate of 20°C / min to 200°C. The sample was then further cooled to -120°C at a cooling rate of 20°C / min. The sample was then heated again to 200°C at a heating rate of 20°C / min. The differential scanning calorimetry curve obtained in the second heating was analyzed as the measurement curve. The glass transition temperature and melting peak temperature were analyzed in accordance with JIS K7121:1987. The midpoint glass transition onset temperature was determined from the temperature at which a line equidistant in the vertical direction from a line extending the low-temperature baseline and the high-temperature baseline intersects with the curve of the step-like change in the glass transition. This midpoint glass transition onset temperature was treated as the glass transition temperature Tg. The melting peak temperature Tm was taken as the apex of the melting peak. The enthalpy of fusion was analyzed in accordance with the method of JIS K7122:1987 for ΔH(L) in the temperature range of -30°C to 80°C, and for ΔH(H) in the temperature range of 160°C to 280°C.

[0256] (3) Reduced viscosity Polycarbonate resin was dissolved in a solvent to prepare a polycarbonate solution with a concentration of 1.00 g / dL. The solvent used was a mixture of phenol and 1,1,2,2-tetrachloroethane. The phenol:1,1,2,2-tetrachloroethane ratio was 1:1 by mass. Dissolution in the mixed solvent was carried out over 30 minutes with stirring at 110°C. After cooling, the polycarbonate solution was used for reduced viscosity measurements. Reduced viscosity measurements were performed using a Chuo Rika Ubbelohde viscometer (DT-504 Automatic Viscometer) at a temperature of 30.0°C ± 0.1°C. The relative viscosity ηrel was calculated from the solvent transit time t0 and the solution transit time t using the following equation (α). The specific viscosity ηsp (unit: g·cm-1·sec-1) was then calculated from the relative viscosity ηrel using the following equation (β). Note that η0 in equation (β) is the viscosity of the solvent. The specific viscosity ηsp was then divided by the concentration c (g / dL) of the polycarbonate solution to calculate the reduced viscosity η (η=ηsp / c). A higher value indicates a higher molecular weight. ηrel=t / t0 (α) ηsp=(η-η0) / η0=ηrel-1 ···(β)

[0257] (4) Shape retention evaluation The press film formed in (1) was kept at 30°C for one day and the change in shape was observed. If the film shape after press forming did not flow or deform, it was judged to have good shape retention and was rated as "Good". On the other hand, if the film shape flowed and deformed, it was rated as "Poor".

[0258] <nmr> Approximately 30 mg of the 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). 1H-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.

[0259] [Synthesis Example] <GPC (Gel Permeation Chromatography) Measurement> Columns: Two TSKgel GMHHR-N (Tosoh, 7.8·300 mm, 9 mm) Column oven temperature: 40°C Mobile phase: THF 1 mL / min Analysis time: 30 min Detection: RI detector Sample: 50 μL injection Calibration method: Polystyrene conversion Calibration curve approximation formula: Cubic equation

[0260] ·Synthesis Example 1 <Production Example of PDMG Mn1000> 250 g (1.43 mol) of 1,10-decanediol was charged into a four-necked flask equipped with a distillation tube, a nitrogen inlet tube, a thermocouple, and a stirrer while supplying nitrogen at 0.20 NL / min. While stirring, 5.50 g (28.9 mmol) of p-toluenesulfonic acid monohydrate was slowly added. The flask was immersed in an oil bath and heated to reach an internal liquid temperature of 170 °C in about 0.5 - 1 hour. When the internal liquid temperature of the flask reached 170 °C, the reaction was started, and thereafter, the liquid temperature was maintained at 168 - 172 °C and reacted for 13 hours. The water generated by the reaction was carried away with nitrogen and distilled off. 25 g of a 10 wt% aqueous sodium hydroxide solution was poured into the reaction solution cooled to around 90 °C, and refluxed and heated at 110 °C for 15 hours to carry out hydrolysis of the ester. It was cooled to around 90 °C and 250 g of ion-exchanged water was poured in. Stirred at 90 °C for about 15 minutes, allowed to stand for 1 - 2 hours, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was withdrawn. The conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil-water separation were repeated a total of 7 times until the conductivity reached 0 - 10 μS / cm. After taking out the oil layer, it was dried under reduced pressure at 170 °C for 2 hours at 5 torr to obtain the target polydimethylenether glycol. The number average molecular weight determined by GPC was 1040, the mass average molecular weight was 1810, the molecular weight distribution was 1.74, the terminal olefination rate determined by NMR was 0.524%, and the terminal esterification rate was below the NMR detection limit.

[0261] ·Synthesis Example 2 <Production Example of PDMG Mn2700> 250 g (1.43 mol) of 1,10-decanediol was charged into a four-necked flask equipped with a distillation tube, a nitrogen inlet tube, a thermocouple, and a stirrer while supplying nitrogen at 0.20 NL / min. While stirring, 5.50 g (28.9 mmol) of p-toluenesulfonic acid monohydrate was slowly added. The flask was immersed in an oil bath and heated to reach an internal liquid temperature of 190 °C in about 1 hour. When the internal liquid temperature of the flask reached 170 °C, the reaction was started, and thereafter, the liquid temperature was maintained at 188 - 192 °C for 9 hours for the reaction. The water generated by the reaction was carried away by nitrogen and distilled off. 250 g of 1 wt% sodium hydroxide aqueous solution was poured into the reaction solution cooled to around 90 °C, and reflux heating was carried out at 110 °C for 15 hours to perform hydrolysis of the ester. It was cooled to around 90 °C and 250 g of ion-exchanged water was poured. After stirring at 90 °C for about 15 minutes and allowing to stand for 1 - 2 hours to confirm separation into an oil layer and an aqueous layer, the aqueous layer was withdrawn. The conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil-water separation were repeated 7 times until the conductivity reached 0 - 10 μS / cm. Thereafter, 500 mL of ethanol was added, heated and dissolved at 60 °C, cooled to room temperature, and then filtered to remove unreacted 1,10-decanediol and low molecular weight polydecamethylene ether glycol of about dimer to trimer. The obtained solid was dried in vacuo at 70 °C for 6 hours to obtain the target polydecamethylene ether glycol. The number average molecular weight determined by GPC was 2670, the mass average molecular weight was 3600, the molecular weight distribution was 1.35, the terminal olefination rate determined by NMR was 1.48%, and the terminal esterification rate was below the NMR detection limit.

[0262] ·Synthesis Example 3 <Production Example of PNMG Mn1000> 450 g (2.81 mol) of 1,9-nonanediol was charged into a four-necked flask equipped with a distillation tube, a nitrogen inlet tube, a thermocouple, and a stirrer while supplying nitrogen at 0.20 NL / min. While stirring, 9.90 g (52.0 mmol) of p-toluenesulfonic acid monohydrate was slowly added. The flask was immersed in an oil bath and heated to reach an internal liquid temperature of 170 °C in about 0.5 - 1 hour. When the internal liquid temperature of the flask reached 170 °C, the reaction was started, and thereafter, the liquid temperature was maintained at 168 - 172 °C for 19 hours for the reaction. The water generated by the reaction was carried away by nitrogen and distilled off. 45 g of a 10 wt% aqueous sodium hydroxide solution was poured into the reaction solution cooled to around 90 °C, and reflux heating was carried out at 110 °C for 20 hours to perform hydrolysis of the ester. It was cooled to around 90 °C and 450 g of ion-exchanged water was poured. After stirring at 80 °C for about 15 minutes and allowing to stand for 1 - 2 hours to confirm separation into an oil layer and an aqueous layer, the aqueous layer was withdrawn. The conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil-water separation were repeated 10 times until the conductivity reached 0 - 10 μS / cm. After taking out the oil layer, it was dried under reduced pressure at 150 °C for 2 hours at 5 torr to obtain the target polynonamethylene ether glycol. The number average molecular weight determined by GPC was 1016, the mass average molecular weight was 1760, the molecular weight distribution was 1.73, the terminal olefination rate determined by NMR was 0.447%, and the terminal esterification rate was below the NMR detection limit.

[0263] ·Synthesis Example 4 <Production Example of PHMG Mn1000> 450 g (3.81 mol) of 1,6 - hexanediol was charged into a four - necked flask equipped with a distillation tube, a nitrogen inlet tube, a thermocouple, and a stirrer while supplying nitrogen at 0.20 NL / min. While stirring, 9.90 g (52.0 mmol) of p - toluenesulfonic acid monohydrate was slowly added. The flask was immersed in an oil bath and heated to reach an internal liquid temperature of 170 °C in about 0.5 - 1 hour. When the internal liquid temperature of the flask reached 170 °C, the reaction was started, and thereafter, the liquid temperature was maintained at 168 - 172 °C for 23 hours of reaction. The water and by - products generated by the reaction were carried away by nitrogen and distilled off. 45 g of a 10 wt% aqueous sodium hydroxide solution was poured into the reaction solution cooled to around 90 °C, and reflux heating was carried out at 110 °C for 23 hours to perform hydrolysis of the ester. It was cooled to around 55 °C and 400 g of ion - exchanged water was poured in. After stirring at 55 °C for about 15 minutes and allowing to stand for 1 - 2 hours to confirm separation into an oil layer and an aqueous layer, the aqueous layer was withdrawn. The conductivity of the aqueous layer was measured, and the addition of ion - exchanged water and oil - water separation were repeated 30 times until the conductivity reached 0 - 10 μS / cm. Further, it was washed by liquid separation 4 times with 1 L of hexane at around 50 °C. The obtained compound was dried under reduced pressure at 130 °C for 2 hours at 1 torr to obtain the target polyhexamethylene ether glycol. The number - average molecular weight determined by GPC was 1055, the mass - average molecular weight was 1690, the molecular weight distribution was 1.60, the terminal olefination rate determined by NMR was 0.789%, and the terminal esterification rate was below the NMR detection limit.

[0264] · Synthesis Example 5 <Production Example of PHMG Mn2700> 450 g (3.81 mol) of 1,6-hexanediol was charged into a four-neck flask equipped with a distillation tube, nitrogen inlet tube, thermocouple, and stirrer while supplying nitrogen at 0.20 nL / min. 22.25 g (116.97 mmol) of p-toluenesulfonic acid monohydrate was slowly added while stirring. The flask was immersed in an oil bath and heated until the liquid temperature in the flask reached 170°C over approximately 0.5-1 hour. The reaction started when the liquid temperature in the flask reached 170°C. The liquid temperature was then maintained at 168-172°C for 28 hours. Water and by-products produced during the reaction were distilled off using nitrogen. After cooling to approximately 90°C, 104 g of 10 wt% aqueous sodium hydroxide solution was poured into the reaction mixture and heated under reflux at 110°C for 78 hours. Next, a solution of 4.50 g of tetrabutylammonium bromide dissolved in 5.58 g of 10 wt% aqueous sodium hydroxide was poured into the mixture, which was then refluxed at 110°C for 28 hours to hydrolyze the ester. The mixture was allowed to cool to around 80°C, and 500 g of ion-exchanged water was poured into the mixture. The mixture was stirred at 80°C for approximately 60 minutes, allowed to stand for 15 to 60 minutes, and after confirming separation into an oil layer and an aqueous layer, the aqueous layer was removed. The conductivity of the aqueous layer was measured, and the addition of ion-exchanged water and oil-water separation were repeated a total of 52 times until the conductivity reached 0 to 10 μS / cm. The mixture was then dissolved in 604 g of cyclohexane at around 50°C, and 1384 g of heptane was added at 25°C. The mixture was allowed to stand for 2 hours to crystallize. The solid was filtered and dried under reduced pressure at 80°C for 8 hours at 1 torr to obtain the desired polyhexamethylene ether glycol. The number average molecular weight, mass average molecular weight, and molecular weight distribution determined by GPC were 2672, 5123, and 1.92, respectively. The terminal olefination rate and terminal esterification rate determined by NMR were 0.501% and 0.357%, respectively.

[0265] [Production and Evaluation of Copolymer Polycarbonate Resin] (Raw materials used) The raw materials used in the production of the polycarbonate copolymer in the following Examples and Comparative Examples are as follows: DPC: Diphenyl carbonate manufactured by Mitsubishi Chemical Corporation. ISB: Isosorbide (Rocket Fleuret) CHDM: 1,4-cyclohexanedimethanol manufactured by SK Chemicals TCDDM: Tricyclodecane dimethanol, manufactured by Oxea DPC: Diphenyl carbonate manufactured by Mitsubishi Chemical Corporation SPG: Spiroglycol manufactured by Mitsubishi Gas Chemical Company, Inc. ADDM: Tricyclo[3,3,1,1 3,7 ]-1,3-dimethanol, Channelpharm Ltd BODM: Bicyclo[2,2,2]octane-1,4-dimethanol, manufactured by Ark Pharm, Inc. Calcium acetate monohydrate (Ca(CH3COO)2·H2O): manufactured by Kishida Chemical Co., Ltd. PEG4000 (Polyethylene Glycol Mn4000): Fujifilm Wako Pure Chemical Corporation PTMG1000 (Polytetramethylene Glycol Mn1000): Mitsubishi Chemical Corporation PTMG3000 (Polytetramethylene Glycol Mn3000): Mitsubishi Chemical Corporation PTMG4000 (Polytetramethylene Glycol Mn4000): Mitsubishi Chemical Corporation VELVETOL H2700 (Polytrimethylene Glycol (PO3G) Mn2700): Manufactured by Allessa Chemie PDMG1000 Polydecamethylene glycol obtained in Synthesis Example 1 Mn1070 PDMG2700 Polydecamethylene glycol obtained in Synthesis Example 2 Mn2700 PNMG1000 Polynonamethylene glycol Mn1000 obtained in Synthesis Example 3 PHMG1000 Polyhexamethylene glycol Mn1000 obtained in Synthesis Example 4 PHMG2700 Polyhexamethylene glycol obtained in Synthesis Example 5 Mn2700 1,10-DD: 1,10-decanediol manufactured by Tokyo Chemical Industry Co., Ltd. 1,12-DD: 1,12-dodecanediol manufactured by Tokyo Chemical Industry Co., Ltd. 1,18-OD: 1,18-octadecanediol This can be synthesized according to known methods (for example, RSC ADVANCES, 3(15), p. 4927-4934; 2013).

[0266] The compositions and evaluation results of the copolymerized polycarbonate resins are shown in Tables 1 to 7. The weight ratios and molar ratios of the structural units derived from dihydroxy compounds in Tables 1 to 7 were calculated assuming that each repeating structural unit contains one carbonyl group.

[0267] [Example 1] 6.26 g (0.0016 mol) of PTMG4000, 7.39 g (0.0506 mol) of ISB, 11.61 g (0.0542 mol) of DPC, and 2.76 × 10 calcium acetate monohydrate as a catalyst. -3 g (1.56 × 10 -5 mol) was charged into a reaction vessel as a 2 wt % aqueous solution, and the heating bath was heated to 150°C under a nitrogen atmosphere, with stirring as necessary, and the temperature was raised to 220°C over 60 minutes at normal pressure to dissolve the raw materials (molar ratio of DPC / ISB / PTMG4000 = 104 / 97 / 3). In the first step of the reaction, the temperature was maintained at 220°C, and the pressure was reduced from atmospheric pressure to 13.3 kPa over 40 minutes. Then, the pressure was maintained at 13.3 kPa for 60 minutes, and the generated phenol was removed from the reaction vessel. In the second step, the heating bath temperature was increased to 240°C over 20 minutes, and the generated phenol was removed from the reaction vessel while controlling the pressure to 0.200 kPa or less over 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. The reduced viscosity of the obtained polycarbonate copolymer was 0.822 dl / g, Tm(L) was 27°C, and ΔH(L) was 27 J / g. Tg was 156°C. Tm(H) was not observed, and ΔH(H) was 0. The obtained polycarbonate was pressed at 150°C to obtain a pressed film. Shape retention was good.

[0268] [Example 2] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that PTMG3000 was used as the polytetramethylene glycol and the molar ratio of DPC / ISB / PTMG3000 was 104 / 95 / 5. The reduced viscosity of the obtained polycarbonate copolymer was 0.415 dl / g, Tm(L) was 18°C, and ΔH(L) was 25 J / g. Tg was 111°C. Tm(H) was not observed, and ΔH(H) was 0. The obtained polycarbonate was pressed at 150°C to obtain a pressed film. Shape retention was good.

[0269] [Examples 3 to 6] Polycarbonate copolymers were obtained in the same manner as in Example 1, except that the molar ratio of ISB / PTMG4000 was set to the ratio shown in Table 2. The NMR spectra of the polycarbonate copolymers obtained in Examples 4 and 6 are shown in Figures 1 and 2, respectively.

[0270] [Example 7] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, CHDM was used as the alicyclic dihydroxy compound, and the molar ratio of DPC / ISB / PTMG4000 / CHDM was 104 / 63 / 10 / 27. The NMR spectrum of this polycarbonate copolymer is shown in FIG.

[0271] [Examples 8 to 9] Polycarbonate copolymers were obtained in the same manner as in Example 10, except that ISB was used as the heteroalicyclic dihydroxy compound, TCDDM was used as the alicyclic dihydroxy compound, and the molar ratio of ISB / PTMG4000 / TCDDM was set to the composition shown in Table 2. NMR spectra of these polycarbonate copolymers are shown in Figures 7 and 8.

[0272] [Example 10] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that PTMG2000 was used as the polytetramethylene glycol and the molar ratio of DPC / ISB / PTMG2000 was 104 / 90 / 10.

[0273] [Comparative Example 1] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that PTMG1000 was used as the polytetramethylene glycol and the molar ratio of DPC / ISB / PTMG1000 was 104 / 90 / 10.

[0274] Comparative Example 2 A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, CHDM was used as the alicyclic dihydroxy compound, PTMG1000 was used as the polytetramethylene glycol, and the molar ratio of DPC / ISB / PTMG1000 / CHDM was 104 / 72 / 10 / 18.

[0275] Comparative Example 3 A polycarbonate copolymer was obtained in the same manner as in Example 1, except that VELVETOL H2700 was used as the polytrimethylene glycol and the molar ratio of DPC / ISB / H2700 was 104 / 95 / 5.

[0276] [Example 11] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PEG4000 was used as the polyethylene glycol, and the molar ratio of DPC / ISB / PEMG4000 was 104 / 90 / 10.

[0277] [Example 12] Except for using BODM as the alicyclic dihydroxy compound and setting the molar ratio of DPC / BODM / PTMG4000 to 104 / 90 / 10, a polycarbonate copolymer was obtained in the same manner as in Example 1. The NMR spectrum of this polycarbonate copolymer is shown in FIG.

[0278] [Example 13] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ADDM was used as the alicyclic dihydroxy compound and the molar ratio of DPC / ADDM / PTMG4000 was 104 / 90 / 10. The NMR spectrum of this polycarbonate copolymer is shown in Figure 4. Multiple melting peaks were observed as Tm(H). Specifically, they were observed at 209°C, 249°C, and 267°C.

[0279] [Example 14] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that SPG was used as the heteroalicyclic dihydroxy compound and the molar ratio of DPC / SPG / PTMG4000 was 104 / 90 / 10. The NMR spectrum of this polycarbonate copolymer is shown in Figure 5. Multiple melting peaks were observed as Tm(H). Specifically, they were observed at 209°C, 227°C, and 253°C.

[0280] [Example 15] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that 1,10-DD was used as the aliphatic dihydroxy compound and the molar ratio of DPC / 1,10-DD / PTMG4000 was 104 / 90 / 10. ΔH(L) was analyzed by analyzing the results of the second heating. Figure 9 shows the DSC curve of Example 15 and the results of peak separation by vertical splitting. In this example, as shown in Figure 9, the melting peak temperature (Tm) of the 1,10-DD-derived structural unit (A) and the melting peak temperature (Tm) of the PTMG4000-derived structural unit (B) were close to each other, and two unseparated (unseparated) peaks of melting enthalpy were present on a single baseline L1. Of these, the lower temperature side was designated as the first peak (i.e., the peak of structural unit (B)), and the higher temperature side was designated as the second peak (i.e., the peak of structural unit (A)). Each peak was divided by a perpendicular line L2 drawn from the point where the data between the first and second peaks was maximum (i.e., the point on the DSC curve at 35°C between the first and second peaks in Figure 9) to the baseline L1. In other words, the above-mentioned vertical division was performed. The point where the data between the first and second peaks was maximum (i.e., the point on the DSC curve at 35°C in Figure 9) was the peak end of the first peak and the peak start of the second peak. The peak start of the first peak was determined by the base start on the low temperature side (i.e., the base start at -14°C in Figure 9). The area of ​​each peak is the area of ​​the region surrounded by the DSC curve, the dividing line (i.e., the perpendicular line L2), and the baseline L1, and the melting enthalpy was determined by calculating this area. As shown in FIG. 9, the area of ​​the first peak on the low-temperature side is the melting enthalpy of the PTMG4000-derived structural unit (B), and the area of ​​the second peak on the high-temperature side is the melting enthalpy of the 1,10-DD-derived structural unit (A). Table 4 shows the Tm(L) and ΔH(L) of the first peak, and the Tm(L) and ΔH(L) of the second peak. The ΔH(L) of Example 15 was calculated as the sum of the ΔH(L) of the first peak and the ΔH(L) of the second peak, and was 71 J / g.

[0281] [Example 16] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that 1,12-DD was used as the aliphatic dihydroxy compound and the molar ratio of DPC / 1,12-DD / PTMG4000 was 104 / 90 / 10. The enthalpy of fusion ΔH(L) was calculated by separating the mixture by vertical partitioning in the same manner as in Example 15.

[0282] [Example 17] Except for using 1,18-OD as the aliphatic dihydroxy compound and setting the molar ratio of DPC / 1,18-OD / PTMG4000 to 104 / 85 / 15, a polycarbonate copolymer was obtained in the same manner as in Example 1. The melting enthalpy ΔH(L) was calculated by separating the mixture by vertical partitioning in the same manner as in Example 15.

[0283] [Example 18] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that 1,18-OD was used as the aliphatic dihydroxy compound and the molar ratio of DPC / 1,18-OD / PTMG3000 was set to 104 / 90 / 10. The enthalpy of fusion ΔH(L) was calculated by separating the mixture by vertical partitioning in the same manner as in Example 15.

[0284] [Example 19] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PDMG2700 was used as the polydecamethylene glycol, and the molar ratio of DPC / ISB / PDMG2700 was 104 / 98 / 2.

[0285] [Example 20] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PDMG1000 was used as the polydecamethylene glycol, and the molar ratio of DPC / ISB / PDMG1000 was 104 / 88 / 12.

[0286] [Example 21] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, CHDM was used as the alicyclic dihydroxy compound, PDMG1000 was used as the polydecamethylene glycol, and the molar ratio of DPC / ISB / CHDM / PDMG1000 was 102 / 72 / 18 / 10.

[0287] [Example 22] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PNMG1000 was used as the polynonamethylene glycol, and the molar ratio of DPC / ISB / PNMG1000 was 104 / 90 / 10.

[0288] [Example 23] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, CHDM was used as the alicyclic dihydroxy compound, PNMG1000 was used as the polynonamethylene glycol, and the molar ratio of DPC / ISB / CHDM / PDMG1000 was 102 / 69.6 / 17.4 / 13.

[0289] [Example 24] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PHMG2700 was used as the polyhexamethylene glycol, and the molar ratio of DPC / ISB / PHMG2700 was 104 / 97 / 3.

[0290] Comparative Example 4 A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PHMG1000 was used as the polyhexamethylene glycol, and the molar ratio of DPC / ISB / PHMG1000 was 102 / 90 / 10.

[0291] [Example 25] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PDMG1000 was used as the polydecamethylene glycol, and the molar ratio of DPC / ISB / PDMG1000 was 104 / 70 / 30.

[0292] [Example 26] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PDMG1000 was used as the polydecamethylene glycol, and the molar ratio of DPC / ISB / PDMG1000 was 104 / 50 / 50.

[0293] [Example 27] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PNMG1000 was used as the polynonamethylene glycol, and the molar ratio of DPC / ISB / PNMG1000 was 104 / 70 / 30.

[0294] [Example 28] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PNMG1000 was used as the polynonamethylene glycol, and the molar ratio of DPC / ISB / PNMG1000 was 102 / 50 / 50.

[0295] [Example 29] A polycarbonate copolymer was obtained in the same manner as in Example 1, except that ISB was used as the heteroalicyclic dihydroxy compound, PHMG2700 was used as the polyhexamethylene glycol, and the molar ratio of DPC / ISB / PHMG2700 was 104 / 90 / 10.

[0296] [Table 1]

[0297] [Table 2]

[0298] [Table 3]

[0299] [Table 4]

[0300] [Table 5]

[0301] [Table 6]

[0302] [Table 7]

[0303] As can be seen from Tables 1 and 2, the copolymeric polycarbonate resins of Examples 1 to 13 containing specific structural units were excellent in heat storage capacity, heat resistance, and shape retention. In contrast, the copolymeric polycarbonate resins of Comparative Examples 1 to 3, which did not contain specific structural units, had insufficient heat storage capacity.

[0304] As can be seen from Table 1, when the number average molecular weight of PTMG was too small, the heat storage property was insufficient. Furthermore, as can be seen from a comparison between Examples 1 and 3 and Comparative Example 3, even when the weight ratios of the structural units derived from polyether were similar and the number average molecular weights of the polyethers were close, when polytrimethylene glycol (PO3G) was used instead of PTMG as the dihydroxy compound, the copolymer polycarbonate resin did not have heat storage property and could not retain its shape.

[0305] As can be seen from Tables 3 and 4, in Examples 12 to 14, which contain structural units of the alicyclic dihydroxy compounds ADDM, BODM, and SPG, Tm(H) derived from each structural unit of ADDM, BODM, and SPG is expressed, and Tm(L) derived from the structural unit of PTMG4000 is expressed, resulting in the expression of ΔH(L). It can be seen that these copolymer polycarbonate resins have excellent heat storage capacity, heat resistance, and shape retention. Furthermore, in Examples 15 to 18, which contain structural units of the aliphatic dihydroxy compounds 1,10-DD, 1,12-DD, and 1,18-OD, Tm(L) derived from the structural units of PTMG4000 and PTMG3000 is expressed, resulting in the expression of ΔH(L). Furthermore, Tm(L) derived from the structural units of 1,10-DD, 1,12-DD, and 1,18-OD is expressed, resulting in the expression of ΔH(L), demonstrating excellent heat storage capacity, heat resistance, and shape retention.

[0306] As can be seen from Tables 5 to 7, the copolymer polycarbonate resins of Examples 19 to 29 containing specific structural units are excellent in heat storage capacity, heat resistance, and shape retention. In contrast, in Comparative Example 4, where the molecular weight of PHMG was small (specifically, 1000), the heat storage capacity was insufficient. The copolymer polycarbonate resins having structural units PNMG1000 and PDMG1000, in which the alkylene group R in the repeating unit represented by formula (7), which constitutes polyoxyalkylene glycol, has 9 and 10 carbon atoms, respectively, are excellent in heat storage capacity, heat resistance, and shape retention.< / nmr>

Claims

1. A copolymeric polycarbonate resin having at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from a polyoxyalkylene glycol, the weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is more than 20% by weight and 99% by weight or less; The number of carbon atoms m of the alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol 1 and the number average molecular weight of the polyoxyalkylene glycol satisfy any one of the following relationships (α1) to (α3): m １ is 2 or 3, and the number average molecular weight is 3,000 or more and 20,000 or less (α1) m １ is 4, 5, or 6, and the number average molecular weight is 1,500 or more and 20,000 or less (α2) m １ is an integer of 7 or more, and the number average molecular weight is 800 or more and 20,000 or less (α3) 【Chemical 1】 (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

2. A copolymeric polycarbonate resin having at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from a polyoxyalkylene glycol, a copolymer polycarbonate resin in which the number of carbon atoms in the alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol is 7 or more, and the number average molecular weight of the polyoxyalkylene glycol is 800 or more and 20,000 or less: 【Chemistry 2】 (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

3. 3. The copolymeric polycarbonate resin according to claim 1, wherein the melting enthalpy ΔH(L) measured by differential scanning calorimetry within a temperature range of −30° C. to 80° C. is 20 J / g or more.

4. The copolymeric polycarbonate resin according to any one of claims 1 to 3, wherein the dihydroxy compound is an alicyclic dihydroxy compound containing one or more 5-membered ring structures or 6-membered ring structures as part of its structure and / or a dihydroxy compound having a cyclic ether structure.

5. The copolymeric polycarbonate resin according to any one of claims 1 to 4, wherein the dihydroxy compound is one or more compounds selected from the group consisting of the following formulas (1) to (6): 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】

6. The copolymer comprises at least a structural unit (A) derived from an alicyclic dihydroxy compound and / or a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from polytetramethylene glycol having a number average molecular weight of 1,500 or more and 20,000 or less, A copolymer polycarbonate resin having a melting enthalpy ΔH(L) of 20 J / g or more as measured in a temperature range of -30°C to 80°C by differential scanning calorimetry.

7. 7. The copolymeric polycarbonate resin according to claim 6, wherein the weight ratio of the structural unit (B) to the total weight of the copolymeric polycarbonate resin is 25% by weight or more and 99% by weight or less.

8. 8. The copolymeric polycarbonate resin according to claim 6 or 7, wherein the structural unit (A) is a structural unit derived from an alicyclic dihydroxy compound containing one or more five-membered ring structures or six-membered ring structures as part of its structure and / or a structural unit derived from a dihydroxy compound having a cyclic ether structure.

9. The copolymeric polycarbonate resin according to any one of claims 6 to 8, wherein the structural unit (A) is a structural unit derived from one or more dihydroxy compounds selected from the group consisting of dihydroxy compounds represented by the following formulas (1) to (6): 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】

10. The copolymeric polycarbonate resin according to any one of claims 6 to 9, wherein the number average molecular weight of the polytetramethylene glycol is 2,000 or more and 10,000 or less.

11. A heat storage material comprising the copolymeric polycarbonate resin according to any one of claims 1 to 10.

12. A heat storage molded body obtained by molding the heat storage material according to claim 11.

13. A phase transition material comprising a polymer having carbonate bonds in the molecular chain and having a melting enthalpy ΔH(L) of 20 J / g or more as observed in a temperature range of -30°C to 80°C by differential scanning calorimetry.

14. 14. The phase change material according to claim 13, wherein the polymer has at least a structural unit (A) derived from one or more dihydroxy compounds selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heteroalicyclic dihydroxy compound, and a structural unit (B) derived from a polyoxyalkylene glycol.

15. 15. The phase transition material according to claim 14, wherein the weight ratio of the structural unit (B) to the total weight of the polymer constituting the phase transition material is more than 20% by weight and not more than 99% by weight.

16. 16. The phase change material according to claim 14, wherein the alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol has 2 to 3 carbon atoms and a number average molecular weight of 3,000 or more and 20,000 or less: 【Chemistry 16】 (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

17. 16. The phase change material according to claim 14, wherein the alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol has 4 to 6 carbon atoms and a number average molecular weight of 1,500 or more and 20,000 or less: 【Chemistry 17】 (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

18. 16. The phase change material according to claim 14 or 15, wherein the alkylene group R in the repeating unit represented by the following formula (7) constituting the polyoxyalkylene glycol has a carbon number of 7 or more and a number average molecular weight of 800 or more and 20,000 or less: 【Chemistry 18】 (In formula (7), R represents an alkylene group, and n represents the number of repeating units.)

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