Polycarbonate resin, and resin composition and molded article containing same

Abstract

One embodiment of the present invention provides a polycarbonate resin containing: a constitutional unit (A) derived from a compound represented by general formula (1); and a constitutional unit (B) derived from a compound represented by general formula (2).

Description

Polycarbonate resin, resin composition containing the same, and molded articles

[0001] This invention relates to polycarbonate resin, as well as resin compositions and molded articles containing the same.

[0002] While resins are used in a variety of applications, polycarbonate resins, in particular, are widely used in electrical and electronic equipment, office automation equipment, optical media, automotive parts, and building materials due to their excellent mechanical strength, heat resistance, electrical properties, dimensional stability, flame retardancy, and transparency. In recent years, with growing concern for environmental issues, there has been a movement to manufacture resins using environmentally friendly raw materials. For example, biomass-derived raw materials with properties such as biodegradability and renewable potential are attracting attention as environmentally friendly raw materials, and attempts are being made to manufacture resins using these as monomers (for example, Patent Documents 1 and 2).

[0003] Special table 2022-505403 publication Special table 2022-505672 publication

[0004] Against this backdrop, there is a need for resins that possess excellent properties while using biomass-derived raw materials.

[0005] Therefore, the inventors have diligently researched and found a polycarbonate resin that has excellent properties (for example, low oxygen permeability, low water vapor permeability, etc.) while using biomass-derived raw materials in at least part of the raw materials. The present invention is as follows, for example: [1] A polycarbonate resin comprising a constituent unit (A) derived from a compound represented by the following general formula (1) and a constituent unit (B) derived from a compound represented by the following general formula (2): [In general formula (1), m and n each independently represent integers from 0 to 5.] [In general formula (2), R ａ and R ｂ Each independently represents an alkylene group having 1 to 8 carbon atoms, which may have substituents; x1 and x2 each independently represent an integer from 0 to 10; R １ ~R ４is, independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; X represents a single bond, —O—, —S—, —SO—, —SO ２ —, —CO—, or a divalent group represented by any one of the following general formulas (3) to (8): (In general formula (3), R ８ to R １７ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent; in general formulas (4) to (8), R １８ and R １９ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, where R １８ and R １９ may be linked to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, each of which may have a substituent; R ２０ represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer of 1 to 20, and d represents an integer of 1 to 500)]. [2] The polycarbonate resin according to [1], wherein the molar ratio [(A) / (B)] of the structural unit (A) and the structural unit (B) in the polycarbonate resin is 0.01 / 99.99 to 99.99 / 0.01. [3] The polycarbonate resin according to [1] or [2], wherein m and n in the compound represented by the general formula (1) are both 1. [4] The polycarbonate resin according to any one of [1] to [3], wherein the compound represented by the general formula (2) is any one or more selected from the group consisting of the compounds represented by the following formulas (9) to (21). [5] The polycarbonate resin according to [4], wherein the compound represented by the general formula (2) is the compound represented by formula (9) and / or the compound represented by formula (13). [6] The polycarbonate resin according to any one of [1] to [5], wherein the weight-average molecular weight (Mw) of the polycarbonate resin is 10,000 to 100,000. [7] The polycarbonate resin according to any one of [1] to [6], wherein the glass transition temperature (Tg) of the polycarbonate resin is 0 to 200°C. [8] The polycarbonate resin according to any one of [1] to [7], wherein the compound represented by the general formula (1) is a biomass-derived compound. [9] A resin composition comprising the polycarbonate resin according to any one of [1] to [8].

[10] A molded article comprising the polycarbonate resin according to any one of [1] to [8].

[11] A polycarbonate resin consisting of constituent units (A) derived from the compound represented by the following general formula (1): [In general formula (1), m and n are each an independent integer between 0 and 5.]

[12] In general formula (2), x1 and x2 are both 0; R １ ~R ４ Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, or each may have a substituent, and is an alkyl group having 1 to 3 carbon atoms; X represents a single bond, -O-, -S-, or a divalent group represented by the following general formulas (3) or (4): [In general formula (3), R ８ ~R １７ Each independently represents a hydrogen atom or a C1-C3 alkyl group which may have substituents; in general formula (4), R １８ and R １９ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have substituents, or an aryl group having 6 to 12 carbon atoms which may have substituents, where R １８ and R １９The carbon atoms may be linked to each other to form a carbon ring having 3 to 20 carbon atoms, which may have substituents; c is 1], the polycarbonate resin according to any one of [1] to [8].

[13] In the general formula (2), x1 and x2 are both 0; R １ ~R ４ Each is independently either a hydrogen atom or a methyl group; X represents a single bond, a -O-, or a divalent group represented by the following general formulas (3) or (4): [In general formula (3), R ８ ~R １７ Each independently represents a hydrogen atom or a methyl group which may have a substituent; in general formula (4), R １８ and R １９ [1] The polycarbonate resin according to any one of [1] to [8], wherein m and n are both 1 in the general formula (1).

[0006] According to the present invention, it is possible to provide a polycarbonate resin having excellent properties while using biomass-derived raw materials as at least a portion of the raw materials.

[0007] Embodiments of the present invention will be described in detail below. According to one embodiment, the polycarbonate resin of the present invention comprises a constituent unit (A) derived from a compound represented by the following general formula (1) and a constituent unit (B) derived from a compound represented by the following general formula (2): [In general formula (1), m and n each independently represent integers from 0 to 5.] [In general formula (2), R ａ and R ｂ Each independently represents an alkylene group having 1 to 8 carbon atoms, which may have substituents; x1 and x2 each independently represent an integer from 0 to 10; R １ ~R ４Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, or each may have substituents, such as a C1-C20 alkyl group, a C6-C12 aryl group, a C2-C12 alkenyl group, a C1-C5 alkoxy group, or a C7-C17 aralkyl group; X is a single bond, -O-, -S-, -SO-, -SO ２ -, -CO-, or any of the following general formulas (3) to (8) represent a divalent group: (In general formula (3), R ８ ~R １７ Each independently represents a hydrogen atom or a C1-C3 alkyl group which may have substituents; in general formulas (4) to (8), R １８ and R １９ Each independently represents a hydrogen atom, a halogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C5 alkoxy group, an optionally substituted C6-C12 aryl group, an optionally substituted C7-C17 aralkyl group, or an optionally substituted C2-C15 alkenyl group, where R １８ and R １９ These may be linked together to form a carbon ring having 3 to 20 carbon atoms or a heterocycle having 1 to 20 carbon atoms, each of which may have substituents; R ２０ (wherein c represents an alkylene group having 1 to 9 carbon atoms, which may have substituents; c represents an integer from 1 to 20; and d represents an integer from 1 to 500).

[0008] The compound represented by the above general formula (1) is a biomass-derived compound and possesses environmentally favorable properties such as biodegradability and renewable potential. It has been found that polymerizing a material containing this compound to produce a polycarbonate resin yields excellent properties, including low oxygen and water vapor permeability. Furthermore, because the glass transition temperature (Tg) is relatively low, the energy required during molding can be reduced, thereby reducing the environmental burden. In addition to the compound represented by general formula (1), for example, the compound represented by the above general formula (2) can be used as a monomer. By further using the compound represented by the above general formula (2) to form a copolymer, an increase in the glass transition temperature (Tg) is observed, making it possible to obtain a polycarbonate resin with a practically favorable Tg while reducing the environmental burden.

[0009] The following describes in detail the constituent elements, manufacturing method, physical properties, and applications of the polycarbonate resin material according to the embodiment. [1] Polycarbonate resin (i) Constituent unit (A) derived from the compound represented by general formula (1) The polycarbonate resin according to the embodiment includes a constituent unit (A) derived from the compound represented by the following general formula (1).

[0010] In general formula (1), m and n each independently represent an integer from 0 to 5. Preferably, m and n are each independently integers from 0 to 3, more preferably integers from 0 to 2, and particularly preferably both m and n are 1. The compound represented by general formula (1) may further have substituents, and such substituents include, but are not limited to, halogen atoms, cyano groups, C1 to C20 alkyl groups, C6 to C12 aryl groups, C2 to C12 alkenyl groups, C1 to C5 alkoxy groups, and C7 to C17 aralkyl groups.

[0011] The polycarbonate resin may contain only the constituent units derived from the compound represented by the general formula (1) above. That is, according to one embodiment, a polycarbonate resin consisting of constituent units (A) derived from the compound represented by the general formula (1) above is provided. Such a polycarbonate resin has the advantage of having particularly low oxygen permeability. In this case, the definition of each group in general formula (1) and possible substituents are the same as above. Constituent units (A) are preferably included in the polycarbonate resin in a proportion of 1 to 100% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, and particularly preferably 25 to 75% by mass, relative to all constituent units of the polycarbonate resin.

[0012] (ii) Constituent units (B) derived from a compound represented by general formula (2) The polycarbonate resin according to the embodiment preferably contains constituent units (B) derived from a compound represented by the following general formula (2).

[0013] In general formula (2), R ａ and R ｂ Each of these independently represents an alkylene group having 1 to 8 carbon atoms, which may have substituents. ａ and R ｂ The alkylene group is preferably independently selected from an alkylene group having 1 to 5 carbon atoms, more preferably from an alkylene group having 1 to 2 carbon atoms. x1 and x2 each independently represent an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 1, and particularly preferably both x1 and x2 are 0. １ ~R ４ R is a group bonded to a carbon atom constituting a benzene ring, and each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, or each may have a substituent, representing a C1-C20 alkyl group, a C6-C12 aryl group, a C2-C12 alkenyl group, a C1-C5 alkoxy group, or a C7-C17 aralkyl group. １ ~R ４R is preferably independently selected from a hydrogen atom, a C1-C5 alkyl group, a C6-C10 aryl group, a C2-C6 alkenyl group, a C1-C3 alkoxy group, and a C7-C10 aralkyl group, and more preferably a hydrogen atom or a methyl group. ａ , R ｂ , R １ ~R ４ Examples of substituents that may further be present include, but are not limited to, halogen atoms, cyano groups, C1-C20 alkyl groups, and C6-C12 aryl groups.

[0014] X is a single bond, -O-, -S-, -SO-, -SO ２ It represents a divalent group represented by -, -CO-, or any of the following general formulas (3) to (8).

[0015] In general formula (3), R ８ ~R １７ Each of these independently represents a C1-C3 alkyl group which may have a hydrogen atom or a substituent. However, R ８ ~R １７ Preferably, at least one of them represents a C1-C3 alkyl group which may have substituents. When X is a divalent group represented by the above general formula (3), R ８ ~R １７ R is, for example, a hydrogen atom or a methyl group. ８ ~R １７ Each of these may independently be a hydrogen atom, methyl, ethyl, n-propyl, or isopropyl, and R ８ ~R １７ At least one of these may be methyl, ethyl, n-propyl, or isopropyl.

[0016] In general formulas (4) to (8), R １８ and R １９Each of these independently represents a hydrogen atom, a halogen atom, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-C5 alkoxy group, an optionally substituted C6-C12 aryl group, an optionally substituted C7-C17 aralkyl group, or an optionally substituted C2-C15 alkenyl group.

[0017] If X is a divalent group represented by the above general formulas (4) to (8), then R １８ and R １９ Preferably, the group is independently selected from the group consisting of a hydrogen atom, a halogen, an optionally substituted C1-C10 alkyl group, an optionally substituted C1-C3 alkoxy group, an optionally substituted C6-C8 aryl group, an optionally substituted C7-C12 aralkyl group, and an optionally substituted C2-C5 alkenyl group. １８ and R １９ These may be linked to each other to form a carbon ring having 3 to 20 carbon atoms or a heterocycle having 1 to 20 carbon atoms, which may have substituents, and preferably a carbon ring having 3 to 12 carbon atoms or a heterocycle having 1 to 12 carbon atoms. In particular, it is preferable that such a ring is formed in general formula (4). When X is a divalent group represented by the above general formula (8), R ２０ 1 to 9 alkylene groups which may have substituents, and preferably 1 to 5 alkylene groups which may have substituents.

[0018] When X is a divalent base represented by the above general formula (4), c represents an integer from 1 to 20, preferably an integer from 1 to 6, and particularly preferably c is 1. When X is a divalent base represented by the above general formula (8), d represents an integer from 1 to 500, preferably an integer from 1 to 300, and more preferably an integer from 1 to 100.

[0019] In general formula (2), X is preferably a single bond, -O-, -S-, or a divalent group represented by any of the above general formulas (3) to (4), and more preferably a divalent group represented by the above general formula (4). ８ ~R ２０Examples of substituents that may further be present include, but are not limited to, halogen atoms, cyano groups, C1-C20 alkyl groups, and C6-C12 aryl groups.

[0020] According to one embodiment, in the general formula (2), x1 and x2 are both 0; R １ ~R ４ Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, or each may have a substituent, and is an alkyl group having 1 to 3 carbon atoms; X represents a single bond, -O-, -S-, or a divalent group represented by the following general formulas (3) or (4): [In general formula (3), R ８ ~R １７ Each independently represents a hydrogen atom or a C1-C3 alkyl group which may have substituents; in general formula (4), R １８ and R １９ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have substituents, or an aryl group having 6 to 12 carbon atoms which may have substituents, where R １８ and R １９ These may be linked together to form a carbon ring having 3 to 20 carbon atoms, each of which may have substituents; c is 1.

[0021] In another embodiment, in the general formula (2), x1 and x2 are both 0; R １ ~R ４ Each is independently either a hydrogen atom or a methyl group; X represents a single bond, a -O-, or a divalent group represented by the following general formulas (3) or (4): [In general formula (3), R ８ ~R １７ Each independently represents a hydrogen atom or a methyl group which may have a substituent; in general formula (4), R １８ and R １９Each of these independently represents a hydrogen atom, an optionally substituted methyl group (e.g., a halogen atom), or an optionally substituted phenyl group; c is 1.

[0022] The compound represented by general formula (2) is more specifically selected from the following compounds. The polycarbonate resin according to the embodiment may contain two or more of the following compounds as the compound represented by general formula (2).

[0023] Of the above, the compound represented by general formula (2) is more preferably the compound represented by formula (9) and / or formula (13). The proportion of constituent unit (B) in the polycarbonate resin is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, and particularly preferably 25 to 75% by mass, relative to the total of constituent units (A) and (B) constituting the polycarbonate resin. Furthermore, the molar ratio of constituent unit (A) to constituent unit (B) [(A) / (B)] in the polycarbonate resin is preferably 0.01 / 99.99 to 99.99 / 0.01, more preferably 10 / 90 to 90 / 10, even more preferably 20 / 80 to 80 / 20, and particularly preferably 25 / 75 to 75 / 25.

[0024] (iii) Other constituent units The polycarbonate resin according to the embodiment may contain constituent units other than the constituent units (A) and (B) described above. Other constituent units are not particularly limited, but include constituent units derived from polyethylene, polyamide, polyether, etc. The other constituent units are preferably included in a proportion of 1 to 20% by mass, more preferably 1 to 10% by mass, relative to the total constituent units constituting the polycarbonate resin. The effects of the present invention are not impaired by such proportions. The polycarbonate resin according to the embodiment may have any of the structures of random, block, or alternating copolymers.

[0025] [2] Method for producing polycarbonate resin The method for producing polycarbonate resin is not particularly limited and can be produced by conventionally known methods using a dihydroxy compound and a carbonate binder as raw materials. For example, methods include directly reacting a dihydroxy compound with phosgene (interfacial polymerization method, phosgene method) and transesterifying a dihydroxy compound with a diester carbonate in a molten state (transesterification method, melting method).

[0026] As the dihydroxy compound, the compound represented by general formula (1) and the compound represented by general formula (2) described above may be used. If necessary, other dihydroxy compounds may be used in combination. When manufactured by interfacial polymerization, the dihydroxy compound and phosgene are usually reacted in the presence of an acid binder and a solvent. As the acid binder, for example, alkali metal hydroxides such as pyridine, sodium hydroxide, and potassium hydroxide are used, and as the solvent, for example, methylene chloride and chloroform are used. To promote the condensation polymerization reaction, tertiary amine catalysts such as triethylamine and quaternary ammonium salts such as benzyltriethylammonium chloride may be used.

[0027] In the above manufacturing method, it is preferable to further add monofunctional compound such as phenol, p-t-butylphenol (PTBP), p-cumylphenol, long-chain alkyl-substituted phenol, alkoxy-substituted phenol, or benzotriazole-substituted phenol to the reaction system as a molecular weight modifier (end-stopper). The timing of adding the molecular weight modifier (end-stopper) is not particularly limited; it may be added during the reaction of the dihydroxy compound or after the reaction of the dihydroxy compound.

[0028] The amount of molecular weight modifier used is usually 0.95 moles or more, preferably 1.5 moles or more, and usually 10 moles or less, preferably 5 moles or less, per 100 moles of the dihydroxy compound.

[0029] By adding a molecular weight modifier, an end structure derived from the molecular weight modifier is introduced to the ends of the polycarbonate resin (polymer). In one embodiment, the amount of the end structure derived from the molecular weight modifier is usually 0.95 moles or more, preferably 1.5 moles or more, and usually 10 moles or less, preferably 5 moles or less, per 100 moles of the constituent units derived from the dihydroxy compound (i.e., the total of constituent units (A) to (D) and other constituent units derived from dihydroxy compounds), and is usually 10 moles or less, preferably 5 moles or less. In one embodiment of the present invention, the end structure of the polycarbonate resin (polymer) is derived from a compound selected from phenol, p-t-butylphenol (PTBP), p-cumylphenol, long-chain alkyl-substituted phenol, alkoxy-substituted phenol, and benzotriazole-substituted phenol. Adding a molecular weight modifier is preferable because it makes it possible to adjust the viscosity-average molecular weight (Mv) of the polycarbonate resin to a desired range, and also because it can impart unique physical properties derived from the structure of the molecular weight modifier to the polycarbonate resin.

[0030] Examples of alkoxy-substituted phenols include compounds represented by the following general formula (T1)'. By using the compound of the above general formula (T1)', an end structure represented by the following general formula (T1) is introduced to the end of the main chain of the polycarbonate resin.

[0031] In equation (T1)' and equation (T1), R Ａ R represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, which may have substituents. Ｂ and R Ｃ Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Z represents an ether bond, a carbonyl group, an ester bond, or a single bond; a is an integer from 1 to 3; and * represents the bond position to the main chain of the polycarbonate resin.

[0032] Examples of the compound represented by the above general formula (T1)' include, but are not limited to, p-hydroxyphenethyl alcohol (PHEP), m-hydroxyphenethyl alcohol, o-hydroxyphenethyl alcohol, o-hydroxybenzyl alcohol (i.e., salicylic alcohol), p-hydroxybenzyl alcohol, m-hydroxybenzyl alcohol, vanillyl alcohol, homovanillyl alcohol, 3-(4-hydroxy-3-methoxyphenyl)-1-propanol, sinapyl alcohol, coniferyl alcohol, p-coumaryl alcohol, etc. Among them, p-hydroxyphenethyl alcohol and p-hydroxybenzyl alcohol are preferable from the viewpoint of reactivity, and p-hydroxyphenethyl alcohol is more preferable. These alkoxy-substituted phenols are excellent in that they can introduce a hydroxyl group to the terminal of the main chain of the obtained polycarbonate resin and impart reactivity to the polycarbonate resin.

[0033] Alternatively, the molecular weight regulator may be a compound represented by the following general formula (T2)'. By using the compound of the above general formula (T2)', a terminal structure represented by the following general formula (T2) is introduced to the terminal of the main chain of the polycarbonate resin. In the formula (T2)' and the formula (T2), R Ｄ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R Ｅ is an alkylene group having 1 to 6 carbon atoms, R Ｆ is a hydrogen atom or a methyl group, R Ｇ is a hydrogen atom or a halogen atom. * represents the bonding position with the main chain of the polycarbonate resin.

[0034] Among them, as the compound represented by the above general formula (T2)', the compound represented by the following general formula (T3)' is preferable. By blending the compound of the general formula (T3)', a terminal structure represented by the following general formula (T3) is introduced to the terminal of the main chain of the polycarbonate resin. In the formula (T3)' and the formula (T3), R Ｄ* represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * represents the bonding position to the main chain of the polycarbonate resin. These benzotriazole-substituted phenols are excellent in that they can impart reactivity derived from the methacrylic group and ultraviolet absorption performance derived from the benzotriazole group to the resulting polycarbonate resin.

[0035] In terms of reactivity during synthesis, availability, and cost, it is preferable to use a compound selected from the group consisting of p-t-butylphenol (PTBP), compounds represented by the above general formula (T1)' (particularly p-hydroxyphenethyl alcohol (PHEP)), and compounds represented by the above general formula (T2)' (particularly compounds represented by formula (T3)') as a molecular weight modifier.

[0036] In one embodiment of the present invention, the polycarbonate resin includes an end structure selected from the end structure represented by the above general formula (T1) (in particular, an end structure derived from p-hydroxyphenethyl alcohol (PHEP)), an end structure represented by the above general formula (T2) (in particular, an end structure represented by the above general formula (T3)), and an end structure represented by the following formula (T4).

[0037] In one embodiment of the present invention, the polycarbonate resin includes an end structure represented by the above formula (T4). The end structure represented by formula (T4) is obtained, for example, by adding p-t-butylphenol (PTBP). In one embodiment of the present invention, the polycarbonate resin includes an end structure represented by the above general formula (T1) (in particular, an end structure derived from p-hydroxyphenethyl alcohol (PHEP)). In one embodiment of the present invention, the polycarbonate resin includes an end structure represented by the above general formula (T2) (in particular, an end structure represented by general formula (T3)).

[0038] Furthermore, if desired, small amounts of antioxidants such as sodium sulfite and hydrosulfite, and branching agents such as phloroglucin, isatin bisphenol, and trisphenolethane may be added.

[0039] When polycarbonate resin is produced by transesterification or melting, a dihydroxy compound is usually reacted with a diester carbonate in the presence of a transesterification catalyst. Specific examples of diester carbonates include aromatic diester carbonates such as diphenyl carbonate, ditolyl carbonate, bis(2-chlorophenyl) carbonate, dinaphthyl carbonate, and bis(4-phenylphenyl) carbonate. At least one alkali metal compound and an alkaline earth metal compound can be used as the transesterification catalyst. Additionally, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used in combination. One type of transesterification catalyst may be used, or multiple types may be used in combination.

[0040] In the polycarbonate resin according to this embodiment, aryl alcohols produced as by-products during the polycondensation reaction may remain. Examples of such aryl alcohols include phenol. The aryl alcohol content in the polycarbonate resin is 1 to 3000 ppm by mass, 5 to 2500 ppm by mass, 10 to 2000 ppm by mass, or 30 to 1000 ppm by mass, based on 100% by mass of the polycarbonate resin.

[0041] [3] Physical properties of polycarbonate resin (1) Glass transition temperature (Tg) The glass transition temperature (Tg) of the polycarbonate resin according to the embodiment is, for example, 0 to 200°C, 20 to 180°C, 50 to 150°C, or 70 to 130°C. The glass transition temperature (Tg) of the polycarbonate resin can be measured by the method described in the examples below.

[0042] (2) Polystyrene-equivalent weight-average molecular weight (Mw) The polystyrene-equivalent weight-average molecular weight (Mw) of the polycarbonate resin according to the embodiment is preferably 10,000 to 100,000. More preferably, the polystyrene-equivalent weight-average molecular weight (Mw) is 20,000 to 80,000, and even more preferably 20,000 to 60,000 or 20,000 to 50,000. The polystyrene-equivalent weight-average molecular weight (Mw) can be measured by the method described in the examples below.

[0043] By setting Mw to 10,000 or more, sufficient strength can be obtained when the resin is molded. By setting Mw to 100,000 or less, an appropriate melt viscosity can be achieved during the production of the resin, and the resin can be taken out without problems after production. Also, in the molten state, fluidity suitable for molding the resin can be obtained.

[0044] (3) Polystyrene-reduced number average molecular weight (Mn) The polystyrene-reduced number average molecular weight (Mn) of the resin is preferably 1,000 to 50,000. More preferably, the polystyrene-reduced number average molecular weight (Mn) is 2,000 to 30,000, and even more preferably 5,000 to 20,000. The polystyrene-reduced number average molecular weight (Mn) can be measured by the method described in the examples below. <7000000>

[0045] By setting Mn to 1,000 or more, sufficient strength can be obtained when the resin is molded. By setting Mn to 50,000 or less, an appropriate melt viscosity can be achieved during the production of the resin, and the resin can be taken out without problems after production. Also, in the molten state, fluidity suitable for molding the resin can be obtained.

[0046] (4) Oxygen permeability The oxygen permeability of the polycarbonate resin according to the embodiment, when measured by the method described in the examples below, is preferably 50 cc / m ２ ·day or less (for example, 20 - 500 cc / m ２ ·day), more preferably 400 cc / m ２ ·day or less (for example, 20 - 400 cc / m ２ ·day), particularly preferably 300 cc / m ２ ·day or less (for example, 20 - 300 cc / m ２ ·day), 200 cc / m ２ ·day or less (for example, 20 - 200 cc / m ２ ·day), or 100 cc / m ２ ·day or less (for example, 20 - 100 cc / m ２ ·day). Therefore, the polycarbonate resin according to the embodiment can be suitably used in applications where oxygen permeation is not required.

[0047] (5) Water vapor permeability The polycarbonate resin according to the embodiment preferably has a water vapor permeability of 100 g / m³ when measured by the method described in the examples below. ２ - Less than 20-100 g / m² (for example, 20-100 g / m²) ２ (More preferably 60 g / m²) ２ - Less than 20-60 g / m² (for example, 20-60 g / m²) ２ ・ (days), particularly preferably 55 g / m² ２ - Less than 20-55 g / m² (for example, 20-55 g / m²) ２ ・day), 40g / m ２ - Less than 20-40 g / m² (for example, 20-40 g / m²) ２ ・ (day), or 35 g / m² ２ - Less than 20-35 g / m² (for example, 20-35 g / m²) ２ (This is the case in Japan.) Therefore, the polycarbonate resin according to this embodiment can be suitably used in applications where it is required that water vapor does not permeate.

[0048] [4] Polycarbonate Resin Composition The polycarbonate resin according to the embodiment can be mixed with other materials to form a resin composition. That is, according to one embodiment, a resin composition containing the above-described polycarbonate resin is provided. The resin composition may be, for example, a thermoplastic resin composition.

[0049] Antioxidants are examples of additives that the resin composition may contain. While commercially available antioxidants can be used, it is preferable to include at least one of, for example, an acid-phenol antioxidant and a phosphite-based antioxidant.

[0050] As phenolic antioxidants, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine e-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Examples include pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxospiro[5.5]undecane, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and preferably pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0051] Phosphate antioxidants include 2-ethylhexyldiphenyl phosphite, isodecyldiphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenbis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, and Examples include ris(2,4-ditert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and preferably 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. As an antioxidant, one of the above types may be used alone, or a mixture of two or more types may be used.

[0052] In the resin composition, the antioxidant is preferably contained in an amount of 1 ppm by weight to 3000 ppm by weight, based on the weight of the resin composition. The antioxidant content in the resin composition is more preferably 50 ppm by weight to 2500 ppm by weight, even more preferably 100 ppm by weight to 2000 ppm by weight, particularly preferably 150 ppm by weight to 1500 ppm by weight, and even more preferably 200 ppm by weight to 1200 ppm by weight, based on the weight of the resin composition.

[0053] Furthermore, the resin composition preferably contains a release agent as an additive. Examples of release agents include ester compounds, such as glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acids, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, and full or mono fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids. When using an ester of aliphatic polyhydric alcohol and an aliphatic carboxylic acid as a release agent, monoesters, full esters, etc., can all be used, but other than full esters such as monoesters may also be used.

[0054] Specific examples of release agents include the following: sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate; propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; and higher alcohol fatty acid esters such as stearyl stearate. Monoglycerides including glycerin monohydroxystearate, glycerin mono-12-hydroxystearate, glycerin monooleate, glycerin monobehenate, glycerin monocaprylate, glycerin monocaprate, glycerin monolaurate, and other monoglycerides; mono-diglycerides including glycerin mono-distearate, glycerin mono-distearate, glycerin mono-dibehenate, glycerin mono-diolate, and other monoglycerides containing glycerin fatty acid ester monoglycerides; glycerin fatty acid ester acetylated monoglycerides such as glycerin diacetone monolaurate; glycerin fatty acid ester organic acid monoglycerides such as citrate fatty acid monoglyceride, succinate fatty acid monoglyceride, and diacetyltartrate fatty acid monoglyceride; Examples include polyglycerin fatty acid esters such as diglycerin stearate, diglycerin laurate, diglycerin oleate, diglycerin monostearate, diglycerin monolaurate, diglycerin monomyristate, diglycerin monooleate, tetraglycerin stearate, decaglycerin laurate, decaglycerin oleate, and polyglycerin polyricinolate.

[0055] In the resin composition, the release agent is preferably contained in an amount of 1 ppm by weight to 5,000 ppm by weight based on the weight of the resin composition. The release agent content in the resin composition is more preferably 50 ppm by weight to 4,000 ppm by weight, even more preferably 100 ppm by weight to 3,500 ppm by weight, particularly preferably 500 ppm by weight to 13,000 ppm by weight, and even more preferably 1,000 ppm by weight to 2,500 ppm by weight based on the total weight of the resin composition.

[0056] The above thermoplastic resin composition may contain other additives in addition to the antioxidant and release agent described above.Such additives include, for example, compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, UV absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents (specifically, sorbitol derivatives, hydroxy fatty acid amides, triaminobenzene compounds, nonitol compounds, various celluloses, etc.), starches (specifically, corn starch, waxy corn starch, high-amylose corn starch, wheat starch, rice starch, potato starch, sweet potato starch, tapioca starch, pea starch, etc.), and lightfasteners (specifically This includes bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) decandyoate, reaction products of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4- Piperidyl) sebacate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}] and other hin Examples include dardamine-based stabilizers, end capping agents, and inorganic fillers (specifically, anhydrous silica, mica, talc, titanium dioxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, wollastonite, calcined perlite, silicates such as calcium silicate and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate, and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, and barium sulfate).

[0057] The content of additives other than antioxidants and release agents in the above thermoplastic resin composition is preferably 10 ppm to 5.0% by weight, more preferably 100 ppm to 2.0% by weight, and even more preferably 1000 ppm to 1.0% by weight, based on the weight of the thermoplastic resin composition, but is not limited thereto. It is preferable to add the additives in an amount that does not impair the effects of the present invention, and it is desirable that the total amount of other additives be within the above range.

[0058] The polycarbonate resin according to the embodiment may be mixed with other resins. The other resins are not particularly limited, but examples include at least one resin selected from the group consisting of polycarbonate resin, polyester resin (e.g., polybutylene adipate terephthalate), polyester carbonate resin, (meth)acrylic resin, polyamide resin, polystyrene resin, cycloolefin resin, acrylonitrile-butadiene-styrene copolymer resin, vinyl chloride resin, polyphenylene ether resin, polysulfone resin, polyacetal resin, and methyl methacrylate-styrene copolymer resin. Various known resins can be used, and one or more can be added to the polycarbonate resin.

[0059] The polycarbonate resin or resin composition according to the embodiment can be used by processing it into various molded articles such as films, sheets, laminates, fibers, nonwoven fabrics, yarns, and laminates. According to one embodiment, a molded article containing the above-described polycarbonate resin or resin composition is provided.

[0060] Specific applications include helmets, various bags such as shopping bags, packaging materials for magnetic tape cassette products such as video and audio, flexible disc packaging materials, printing plate materials, packaging bands, adhesive tapes, tapes, yarn, cups, trays, cartons, lunch boxes, prepared food containers, food and confectionery packaging materials, food wrap materials, internal coating materials for food and beverage packs, shrink film for PET bottles, trays for fresh food, fast food containers and lunch boxes, garbage bags, cups, plates, chopsticks, spoons, forks, straws, cosmetic and fragrance wrap materials, shopping bags, diapers, sanitary napkins, pharmaceutical wrap materials, pharmaceutical packaging materials, surgical adhesive patch packaging materials for conditions such as stiff shoulders and sprains, various packaging materials for food, electronics, medical, pharmaceuticals, cosmetics, etc., parts of artificial hair and wigs, artificial turf, body bags, etc. If the material has a film-like shape, it can also be heat-sealed.

[0061] Agricultural mulch films are used to cover the soil surface for purposes such as retaining soil heat and controlling weeds, preventing pest damage, and creating an environment suitable for growing vegetables and fruits by creating fine irregularities on the film surface to diffuse sunlight. Films stretched on the outside of greenhouses are used to suppress the generation of fog and mist, improve heat retention, and prevent dust. Other agricultural materials include multipurpose films, pots and strings for plants, fertilizer coating materials, slow-release covering materials, horticultural films, pesticide wrap films, greenhouse films, fertilizer bags, transplanting seedling pots, seedling pots, waterproof sheets, sandbags, construction films, weed control sheets, vegetation nets made of tape and yarn, water-retaining films for greening barren land and deserts, sandbags, vegetation nets, fishing lines, fishing nets, seaweed nets, and artificial bait, among other materials used in agriculture, civil engineering, and fisheries. They can also be used as garbage bags and compost bags.

[0062] It can be used as a medical and hygiene product, for example, as medical materials such as sutures and bandages, and as hygiene materials such as disposable diapers and some sanitary products (superabsorbent polymers, waterproof films). It can also be used as disposable leisure goods such as golf, fishing, and marine sports equipment, and as water treatment materials such as precipitating agents, dispersing agents, and detergents.

[0063] The present invention will be described in detail below with reference to examples, but the content of the present invention is not limited thereto. (Example 1) 20.013 g (0.15 mol) of tetrahydro-2,5-frangimethanol (THFDM) as a raw material diol monomer, 32.440 g (0.15 mol) of diphenyl carbonate (DPC), and cesium carbonate (Cs) as a catalyst. ２ CO ３ , 5 × 10 for the total moles of THFDM ―６ The mol of the substance was accurately weighed into a 100 mL four-necked flask and dried under reduced pressure at room temperature and in a vacuum for 1 hour. After that, the reaction system was purged with nitrogen to create a nitrogen atmosphere.

[0064] A stirrer and distillation apparatus were attached to the four-necked flask described above, and the mixture was heated to 170°C under a nitrogen atmosphere (pressure: 101.3 kPa). After heating, complete dissolution of the starting monomer was confirmed, and then the pressure in the reactor was reduced to 4.0 kPa and stirred for 2 hours. At this time, the start of distillation of the by-product phenol was confirmed. Subsequently, the pressure was reduced to 2.7 kPa and stirred for 30 minutes. Then, the temperature was raised to 200°C over 30 minutes, and then the pressure was adjusted to 1.3 kPa and stirred for 10 minutes. After that, the pressure was adjusted to 1 kPa or less, and stirred for a further 60 minutes to complete the reaction (final reaction temperature = 200°C). After the reaction was complete, nitrogen was introduced into the reactor to return to atmospheric pressure, and the produced polycarbonate resin was removed.

[0065] (Example 2) 7.715 g (0.058 mol) of THFDM and 13.328 g (0.058 mol) of bisphenol A (BPA) as raw material diol monomers, 25.013 g (0.117 mol) of DPC, and sodium bicarbonate (NaHCO₃) as a catalyst. ３ , 10 × 10 for the total moles of THFDM and BPA －６ A polycarbonate resin was obtained in the same manner as in Example 1, except that mol of mol was used and the final reaction temperature was 220°C.

[0066] (Example 3) 12.524 g (0.095 mol) of THFDM as a raw material diol monomer, 8.478 g (0.032 mol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter also referred to as "BPZ": manufactured by Honshu Chemical Industry Co., Ltd.), 27.079 g (0.126 mol) of DPC, and sodium bicarbonate (NaHCO3) as a catalyst. ３ , 15 × 10 for the total moles of THFDM and BPZ －６ The mol of the substance was accurately weighed into a 100 mL four-necked flask and dried under reduced pressure at room temperature and in a vacuum for 1 hour. After that, the reaction system was purged with nitrogen to create a nitrogen atmosphere.

[0067] A stirrer and distillation apparatus were attached to the four-necked flask described above, and the mixture was heated to 190°C under a nitrogen atmosphere (pressure: 101.3 kPa). After confirming the complete dissolution of the starting monomers, the pressure in the reactor was reduced to 20 kPa and stirred for 90 minutes. During this time, the start of distillation of the by-product phenol was confirmed. Next, the pressure was reduced to 13.3 kPa over 30 minutes, and then the temperature was raised to 200°C. After that, the pressure was reduced to 4.0 kPa over 20 minutes, and the temperature was raised to 220°C, after which the mixture was stirred for 10 minutes. After that, the pressure was adjusted to 1 kPa or less, and the mixture was stirred for a further 60 minutes to complete the reaction (final reaction temperature = 220°C). After the reaction was complete, nitrogen was introduced into the reactor to return to atmospheric pressure, and the resulting polycarbonate resin was removed.

[0068] (Example 4) The amounts of THFDM, BPZ, DPC, and sodium bicarbonate were as follows: THFDM 6.931 g (0.052 mol), BPZ 14.082 g (0.052 mol), DPC 22.472 g (0.105 mol), sodium bicarbonate (10 × 10 times the total mol of THFDM and BPZ) －６ A polycarbonate resin was obtained in the same manner as in Example 3, except that the amount was changed to mol.

[0069] (Example 5) Polycarbonate resin was obtained in the same manner as in Example 3, except that the amounts of THFDM, BPZ, and DPC were changed to 2.961 g (0.022 mol) of THFDM, 18.039 g (0.067 mol) of BPZ, and 19.200 g (0.090 mol) of DPC.

[0070] (Comparative Example 1) 620 mL of 9 w / w% sodium hydroxide aqueous solution was mixed with 300 mL of pure water. 100 g (0.44 mol) of bisphenol A (BPA) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 2.53 g (0.017 mol) of PTBP (p-tert-butylphenol), and 0.3 g of hydrosulfite were added and dissolved. 300 mL of methylene chloride was then added and stirred, and 60.7 g of phosgene was blown in over approximately 30 minutes while maintaining the temperature at 15-20°C.

[0071] After phosgene bubbling was complete, 100 mL of 9 w / w% aqueous sodium hydroxide solution and 100 mL of methylene chloride were added, and the reaction mixture was emulsified by vigorous stirring. Then, 0.5 mL of triethylamine was added as a polymerization catalyst, and polymerization was carried out by stirring at 20-30°C for about 40 minutes. After the polymerization reaction was complete, the resulting reaction mixture was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the washing solution (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was added dropwise to warm water maintained at 47°C, and the solvent was evaporated to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 105°C for 24 hours to obtain polycarbonate resin.

[0072] (Comparative Example 2) 530 mL of 9 w / w% sodium hydroxide aqueous solution was mixed with 200 mL of pure water, and 90 g (0.34 mol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter also referred to as "BPZ": manufactured by Honshu Chemical Industry Co., Ltd.), 1.65 g (0.011 mol) of PTBP (p-tert-butylphenol), and 0.3 g of hydrosulfite were dissolved therein. Then, 300 mL of methylene chloride was added and stirred, and while maintaining the temperature at 15-20°C, 46.5 g of phosgene was blown in over approximately 30 minutes.

[0073] After phosgene bubbling was complete, 100 mL of 9 w / w% aqueous sodium hydroxide solution and 100 mL of methylene chloride were added, and the reaction mixture was emulsified by vigorous stirring. Then, 0.5 mL of triethylamine was added as a polymerization catalyst, and polymerization was carried out by stirring at 20-30°C for about 40 minutes. After the polymerization reaction was complete, the resulting reaction mixture was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the washing solution (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was added dropwise to warm water maintained at 60°C, and the solvent was evaporated to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 105°C for 24 hours to obtain polycarbonate resin.

[0074] Table 1 below shows the composition and properties of the polycarbonate resins of the examples and comparative examples. Each property was measured by the following method. <Weight-average molecular weight (Mw) in polystyrene equivalent> A calibration curve was created using GPC (gel permeation chromatography) with chloroform as the developing solvent and standard polystyrene (Shodex STANDARD, SM-105) with a known molecular weight (molecular weight distribution = 1). The elution time and molecular weight value of each peak were plotted from the measured standard polystyrene, and an approximation using a cubic equation was performed to obtain a calibration curve. Then, based on the obtained calibration curve, the weight-average molecular weight (Mw) was calculated as a polystyrene equivalent value from the following formula. [Calculation formula] Mw = Σ(W ｉ ×M ｉ ) / Σ(W ｉ ) (In the above formula, i is the i-th division point when the molecular weight M is divided, W is the i-th division point.) ｉ The i-th weight is M ｉ represents the i-th molecular weight. Furthermore, the molecular weight M represents the molecular weight in polystyrene terms at the same elution time on the calibration curve.

[0075] [Measurement Conditions] • Apparatus: Tosoh Corporation High-Speed ​​GPC HLC-8320 GPC • Column: Tosoh Corporation GPC Column SuperMultiporeHZ-M (4.6 mm I.D. × 150 mm), 3 columns used in series • Flow Rate: 0.35 mL / min • Eluent: Chloroform • Sample Concentration: 0.2 w / v% • Detection Unit: Blythe Differential Refractometer (RI Detector)

[0076] <Number-average molecular weight (Mn) in polystyrene equivalent> Using the same method and measurement method as above for Mw, the number-average molecular weight (Mn) was calculated as a polystyrene equivalent value from the following formula. [Calculation formula] Mn = Σ(Mi) / Σ(i) (In the above formula, i represents the i-th division point when the molecular weight M is divided, and Mi represents the i-th molecular weight. The molecular weight M represents the molecular weight in polystyrene equivalent at the same elution time on the calibration curve.) Note that the molecular weights (Mn and Mw) listed in Table 2 are the molecular weights of the polycarbonate resin contained in the resin composition.

[0077] <Glass Transition Temperature (Tg)> The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) (Hitachi High-Tech Science, DSC-7000). Samples were prepared by weighing 7-12 mg test pieces into RDC aluminum pans (AI autosampler sample containers, φ6.8 H2.5 mm) and sealing them with an AI autosampler cover. Measurements were performed under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min). 10.0 mg of alumina was used as the reference cell standard. The sample temperature was adjusted to 30°C and then increased to 200°C at a rate of 10°C / min. Subsequently, the temperature was lowered to -50°C at a rate of 10°C / min. After that, the temperature was increased to 200°C at a rate of 10°C / min and measured.

[0078] <Oxygen Permeability> Hot-pressed films of the resins obtained in the examples and comparative examples were prepared and measured according to the method described in JIS K7126, and the oxygen permeability was converted to that at a thickness of 25 μm. The measurement conditions were as follows: • Apparatus: MOCON OX-TRAN 2 / 21 • Test temperature: 23°C • Humidity: 0% RH • Test pressure: 1 atm

[0079] <Water Vapor Transmission Rate> Hot-pressed films of the resins obtained in the examples and comparative examples were prepared and measured according to the method described in JIS K7129, and the water vapor transmission rate was converted to a value of 25 μm thickness. The measurement conditions were as follows: • Apparatus: MOCON PERMATRAN-w 3 / 34 • Test temperature: 40°C • Humidity: 90% RH

[0080] Table 1 shows that the polycarbonate resin used in the examples has advantages such as low oxygen permeability and low water vapor permeability.

[0081] While several embodiments of the present invention have been described, these embodiments are presented as examples only and are not intended to limit the scope of the invention. These novel embodiments can be carried out in a variety of other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents.

Claims

1. A polycarbonate resin comprising a structural unit (A) derived from a compound represented by the following general formula (1) and a structural unit (B) derived from a compound represented by the following general formula (2): [In the general formula (1), m and n each independently represent an integer of 0-5] [In the general formula (2), R ａ and R ｂ each independently represent an alkylene group having 1-8 carbon atoms which may have a substituent; x1 and x2 each independently represent an integer of 0-10; R １ to R ４ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, or each represents an alkyl group having 1-20 carbon atoms, an aryl group having 6-12 carbon atoms, an alkenyl group having 2-12 carbon atoms, an alkoxy group having 1-5 carbon atoms, or an aralkyl group having 7-17 carbon atoms which may each have a substituent; X represents a single bond, -O-, -S-, -SO-, -SO ２ -, -CO-, or a divalent group represented by any one of the following general formulas (3)-(8): (In the general formula (3), R ８ to R １７ each independently represent a hydrogen atom or an alkyl group having 1-3 carbon atoms which may have a substituent; in the general formulas (4)-(8), R １８ and R １９ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1-20 carbon atoms which may have a substituent, an alkoxy group having 1-5 carbon atoms which may have a substituent, an aryl group having 6-12 carbon atoms which may have a substituent, an aralkyl group having 7-17 carbon atoms which may have a substituent, or an alkenyl group having 2-15 carbon atoms which may have a substituent, where R １８ and R １９ may be linked to each other to form a carbocyclic ring having 3-20 carbon atoms or a heterocyclic ring having 1-20 carbon atoms which may each have a substituent; R ２０ represents an alkylene group having 1-9 carbon atoms which may have a substituent, c represents an integer of 1-20, and d represents an integer of 1-500)] 2. The polycarbonate resin according to claim 1, wherein the molar ratio [(A) / (B)] of the constituent unit (A) to the constituent unit (B) in the polycarbonate resin is 0.01 / 99.99 to 99.99 / 0.

01.

3. The polycarbonate resin according to claim 1 or 2, wherein m and n in the compound represented by the general formula (1) are both 1.

4. The polycarbonate resin according to any one of claims 1 to 3, wherein the compound represented by the general formula (2) is one or more selected from the group consisting of compounds represented by the following formulas (9) to (21).

5. The polycarbonate resin according to claim 4, wherein the compound represented by general formula (2) is the compound represented by formula (9) and / or the compound represented by formula (13).

6. The polycarbonate resin according to any one of claims 1 to 5, wherein the weight-average molecular weight (Mw) of the polycarbonate resin is 10,000 to 100,000.

7. The polycarbonate resin according to any one of claims 1 to 6, wherein the glass transition temperature (Tg) of the polycarbonate resin is 0 to 200°C.

8. The polycarbonate resin according to any one of claims 1 to 7, wherein the compound represented by the general formula (1) is a biomass-derived compound.

9. A resin composition comprising the polycarbonate resin according to any one of claims 1 to 8.

10. A molded article comprising the polycarbonate resin according to any one of claims 1 to 8.

11. Polycarbonate resin consisting of constituent units (A) derived from the compound represented by the following general formula (1): [In general formula (1), m and n are each independent integers between 0 and 5.]

Images