Polycarbonate resin composition

Abstract

Provided is a polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) represented by formula (1) and a carbonate structural unit (Y1) derived from a dihydroxy compound (3) represented by formula (3). (In formula (1): A represents a divalent linking group comprising 1-15 carbon atoms, 0-1 oxygen atom, and hydrogen atoms and having no cyclic structure, wherein the A moieties in formula (1) are the same as each other; B represents a divalent linking group comprising 1-40 carbon atoms and hydrogen atoms and having no cyclic structure; and n is an integer of 2-100.)

Description

Polycarbonate resin composition

[0001] The present invention relates to a polycarbonate resin composition, more particularly to a polycarbonate resin composition excellent in heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency. The present invention also relates to a thermoplastic resin composition containing the polycarbonate resin composition, and an injection-molded or extrusion-molded article of the polycarbonate resin composition or the thermoplastic resin composition.

[0002] Polycarbonate resins have excellent mechanical strength, electrical properties, transparency, and other properties, and are widely used as engineering plastics in a variety of fields, including electrical and electronic equipment and the automotive industry. However, unlike polyester-based thermoplastic elastomers and thermoplastic polyurethanes, there are currently few polycarbonate resins used as elastomers. The development of polycarbonate-based thermoplastic elastomers may lead to further expansion of their applications.

[0003] On the other hand, there are concerns about global warming due to the depletion of petroleum resources and increased carbon dioxide emissions. For this reason, there is a demand for the development of plastics made from carbon-neutral plant-derived monomers. Under these circumstances, polycarbonate resins produced using the plant-derived raw material isosorbide (hereinafter sometimes referred to as "ISB") have been developed in recent years and have begun to be used for automotive parts, optical applications, and glass replacement applications (see, for example, Patent Documents 1 and 2). Conventional polycarbonate resins made from isosorbide have a high elastic modulus, making them difficult to use as elastomers.

[0004] Patent Document 3 discloses a polycarbonate resin that uses a compound produced from a plant-derived raw material and has excellent flexibility, color, and thermal stability, and a polycarbonate resin composition that uses the same as an impact modifier and has excellent impact resistance and heat resistance. Specifically, Patent Document 3 proposes a copolymer polycarbonate resin that uses polytrimethylene ether glycol (hereinafter sometimes abbreviated as "PO3G") and isosorbide.

[0005] International Publication No. 2004 / 111106 International Publication No. 2007 / 148604 Japanese Patent Application Laid-Open No. 2021-91900

[0006] Although the copolymer polycarbonate resin of Patent Document 3 has excellent flexibility, the copolymerization of polytrimethylene ether glycol significantly lowers the glass transition temperature and reduces heat resistance. In order to use a polycarbonate resin as an elastomer as a main component resin, it is necessary to achieve not only flexibility but also heat resistance and mechanical strength, and therefore improvements in these areas are necessary.

[0007] Under these circumstances, an object of the present invention is to provide a polycarbonate resin composition excellent in heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency.

[0008] The present inventors have found that a polycarbonate resin composition containing carbonate structural units derived from a specific aliphatic polyester polyol and carbonate structural units derived from a dihydroxy compound that satisfies specific requirements is a polycarbonate resin composition that meets the above-mentioned objectives.

[0009] The present invention relates to the following [1] to

[57] .

[0010] [1] A polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) represented by the following formula (1) and a carbonate structural unit (Y1) derived from a dihydroxy compound (3) represented by the following formula (3):

[0011]

[0012] (In formula (1), A represents a divalent linking group having no cyclic structure, which is composed of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and a hydrogen atom, and multiple As in formula (1) are the same. B represents a divalent linking group having no cyclic structure, which is composed of 1 to 40 carbon atoms and a hydrogen atom, and n is an integer from 2 to 100.)

[0013]

[0014] [2] The polycarbonate resin composition according to [1], wherein the polycarbonate resin composition has a peak melting point temperature when the peak melting point temperature is measured by heating at a temperature increase rate of 20°C / min using a differential scanning calorimeter.

[0015] [3] The polycarbonate resin composition according to [1] or [2], wherein the content of the carbonate structural unit (X) is 1% by mass or more and 99% by mass or less, and the content of the carbonate structural unit (Y1) is 1% by mass or more and 99% by mass or less, based on 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0016] [4] The polycarbonate resin composition according to [3], wherein the content of the carbonate structural unit (X) is 25% by mass or more and 80% by mass or less, and the content of the carbonate structural unit (Y1) is 20% by mass or more and 75% by mass or less, based on 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0017] [5] The polycarbonate resin composition according to [4], wherein the content of the carbonate structural unit (X) is 50% by mass or more and 80% by mass or less, and the content of the carbonate structural unit (Y1) is 20% by mass or more and 50% by mass or less, based on 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0018] [6] The polycarbonate resin composition according to any one of [1] to [5], wherein the sum of the content of the carbonate structural unit (X) and the content of the carbonate structural unit (Y1) is 90 mass% or more based on 100 mass% of all carbonate structural units in the polycarbonate resin composition.

[0019] [7] The polycarbonate resin composition according to any one of [1] to [6], wherein the aliphatic polyester polyol (1) represented by the formula (1) has a number average molecular weight of 400 or more and 10,000 or less.

[0020] [8] The polycarbonate resin composition according to any one of [1] to [7], wherein the aliphatic polyester polyol (1) is at least one selected from the group consisting of aliphatic polyester polyols represented by the following formula (2) and the following formulas (10) to (12):

[0021]

[0022] (In the above formula, n, o, p, q, r, and s are integers of 2 to 100. X is an n-nonylene group or a 2-methyl-1,8-octylene group.)

[0023] [9] The polycarbonate resin composition according to any one of [1] to [8], wherein the polycarbonate resin composition has the melting point peak temperature in the range of 100°C or higher.

[0024]

[10] The polycarbonate resin composition according to any one of [1] to [9], wherein the polycarbonate resin composition has the melting point peak temperature in the range of 300°C or less.

[0025]

[11] The polycarbonate resin composition according to any one of [1] to

[10] , which contains the carbonate structural unit (X) and the carbonate structural unit (Y) as a copolymer polycarbonate resin.

[0026]

[12] The polycarbonate resin composition according to any one of [1] to

[10] , which is a blend of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Y).

[0027]

[13] The polycarbonate resin composition according to any one of [1] to

[12] , having a viscosity average molecular weight of 20,000 or more and 150,000 or less.

[0028]

[14] The polycarbonate resin composition according to any one of [1] to

[13] , which has a glass transition temperature of 30°C or lower when measured using a differential scanning calorimeter by heating at a temperature increase rate of 20°C / min.

[0029]

[15] The polycarbonate resin composition according to any one of [1] to

[14] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a tensile modulus of 5 MPa or more and 1000 MPa or less.

[0030]

[16] The polycarbonate resin composition according to any one of [1] to

[15] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a tensile elongation at break of 100% or more.

[0031]

[17] The polycarbonate resin composition according to any one of [1] to

[16] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a tensile permanent set of 30% or less.

[0032]

[18] The polycarbonate resin composition according to any one of [1] to

[17] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a recovery rate of 70% or more.

[0033]

[19] The polycarbonate resin composition according to any one of [1] to

[18] , which has a viscosity average molecular weight retention of 80% or more after heating at 100°C for 100 hours using a hot air dryer.

[0034]

[20] The polycarbonate resin composition according to any one of [1] to

[19] , which has a viscosity average molecular weight retention of 90% or more after treatment for 168 hours under conditions of a temperature of 80°C and a relative humidity of 96%.

[0035]

[21] Irradiation intensity 60 W / m using a xenon lamp ２

[21] The polycarbonate resin composition according to any one of [1] to

[20] , wherein the retention of viscosity average molecular weight after treatment with HCl for 100 hours is 90% or more.

[0036]

[22] The polycarbonate resin composition according to any one of [1] to

[21] , wherein a film having a thickness of 0.5 mm made of the polycarbonate resin composition has a total light transmittance of 83% or more.

[0037]

[23] A thermoplastic resin composition comprising the polycarbonate resin composition according to any one of [1] to

[22] , wherein the content of the polycarbonate resin composition in 100% by mass of the thermoplastic resin composition is 1% by mass or more and 30% by mass or less.

[0038]

[24] An injection-molded article obtained by injection molding the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0039]

[25] An extrusion-molded product obtained by extrusion molding the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0040]

[26] The extrusion molded product according to

[25] , wherein the extrusion molded product is a sheet or a film.

[0041]

[27] A membrane material used for membrane structure buildings, obtained using the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0042]

[28] A vibration-damping material for EVs obtained using the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0043]

[29] A watch band obtained using the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0044]

[30] A camera grip obtained using the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0045]

[31] A catheter tube obtained using the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0046]

[32] A shoe midsole obtained using the polycarbonate resin composition according to any one of [1] to

[22] or the thermoplastic resin composition according to

[23] .

[0047]

[33] A polycarbonate resin composition used for any one application selected from the group consisting of membrane materials used in membrane structure buildings, vibration-damping materials for EVs, watch bands, camera grips, catheter tubes, and shoe midsoles, the polycarbonate resin composition comprising carbonate structural units (X) derived from an aliphatic polyester polyol (1) represented by the following formula (1) and carbonate structural units (Y2) derived from a dihydroxy compound (2) satisfying the following requirement I, and having a peak melting point temperature when measured by heating at a temperature increase rate of 20°C / min using a differential scanning calorimeter.

[0048]

[0049] (In formula (1), A represents a divalent linking group having no cyclic structure, consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and a hydrogen atom, and multiple As in formula (1) are the same. B represents a divalent linking group having no cyclic structure, consisting of 1 to 40 carbon atoms and a hydrogen atom, and n is an integer from 2 to 100.)

[0050] <Requirement I> The dihydroxy compound (2) has a melt volume flow rate (MVR) of 5 to 120 cm3 at 260°C under a load of 2.16 kg by a transesterification method with a carbonate source. ３ When the polycarbonate resin (2) is polymerized with the dihydroxy compound (A) at a temperature rise rate of 20°C / min and the melting point peak temperature is measured by using a differential scanning calorimeter, the polycarbonate resin (2) is a dihydroxy compound having a melting point peak temperature of 20°C / min. / 10 min.

[0051]

[34] The polycarbonate resin composition according to

[33] , wherein the dihydroxy compound (2) is at least one selected from the group consisting of dihydroxy compounds represented by the following formulas (3) to (7):

[0052]

[0053]

[35] The polycarbonate resin composition according to

[33] or

[34] , which has a viscosity average molecular weight retention of 80% or more after heating at 100°C for 100 hours using a hot air dryer.

[0054]

[36] The polycarbonate resin composition according to any one of

[33] to

[35] , wherein the content of the carbonate structural unit (X) is 1% by mass or more and 99% by mass or less, and the content of the carbonate structural unit (Y2) is 1% by mass or more and 99% by mass or less, based on 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0055]

[37] The polycarbonate resin composition according to

[36] , wherein the content of the carbonate structural unit (X) is 25% by mass or more and 80% by mass or less, and the content of the carbonate structural unit (Y2) is 20% by mass or more and 75% by mass or less, based on 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0056]

[38] The polycarbonate resin composition according to

[37] , wherein the content of the carbonate structural unit (X) is 50% by mass or more and 80% by mass or less, and the content of the carbonate structural unit (Y2) is 20% by mass or more and 50% by mass or less, based on 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0057]

[39] The polycarbonate resin composition according to any one of

[33] to

[38] , wherein the sum of the content of the carbonate structural unit (X) and the content of the carbonate structural unit (Y2) is 90 mass% or more based on 100 mass% of all carbonate structural units in the polycarbonate resin composition.

[0058]

[40] The polycarbonate resin composition according to any one of

[33] to

[39] , wherein the aliphatic polyester polyol (1) represented by the formula (1) has a number average molecular weight of 400 or more and 10,000 or less.

[0059]

[41] The polycarbonate resin composition according to any one of

[33] to

[40] , wherein the aliphatic polyester polyol (1) is at least one selected from the group consisting of aliphatic polyester polyols represented by the following formula (2) and the following formulas (10) to (12):

[0060]

[0061] (In the above formula, n, o, p, q, r, and s are integers of 2 to 100. X is an n-nonylene group or a 2-methyl-1,8-octylene group.)

[0062]

[42] The polycarbonate resin composition according to any one of

[33] to

[41] , wherein the polycarbonate resin composition has the melting point peak temperature in the range of 100°C or higher.

[0063]

[43] The polycarbonate resin composition according to any one of

[33] to

[42] , wherein the polycarbonate resin composition has the melting point peak temperature in the range of 300°C or less.

[0064]

[44] The polycarbonate resin composition according to any one of

[33] to

[43] , which contains the carbonate structural unit (X) and the carbonate structural unit (Y2) as a copolymer polycarbonate resin.

[0065]

[45] The polycarbonate resin composition according to any one of

[33] to

[44] , which is a blend of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Y).

[0066]

[46] The polycarbonate resin composition according to any one of

[33] to

[45] , having a viscosity average molecular weight of 20,000 or more and 150,000 or less.

[0067]

[47] The polycarbonate resin composition according to any one of

[33] to

[46] , which has a glass transition temperature of 30°C or lower when measured using a differential scanning calorimeter by heating at a temperature increase rate of 20°C / min.

[0068]

[48] ​​The polycarbonate resin composition according to any one of

[33] to

[47] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a tensile modulus of 5 MPa or more and 1000 MPa or less.

[0069]

[49] The polycarbonate resin composition according to any one of

[33] to

[48] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a tensile elongation at break of 100% or more.

[0070]

[50] The polycarbonate resin composition according to any one of

[33] to

[49] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a tensile permanent set of 30% or less.

[0071]

[51] The polycarbonate resin composition according to any one of

[33] to

[50] , wherein a sample obtained by hot pressing the polycarbonate resin composition has a recovery rate of 70% or more.

[0072]

[52] The polycarbonate resin composition according to any one of

[33] to

[51] , which has a viscosity average molecular weight retention of 90% or more after treatment for 168 hours under conditions of a temperature of 80°C and a relative humidity of 96%.

[0073]

[53] Irradiation intensity 60 W / m using a xenon lamp ２

[53] The polycarbonate resin composition according to any one of

[33] to

[52] , wherein the retention of viscosity average molecular weight after treatment with HCl for 100 hours is 90% or more.

[0074]

[54] The polycarbonate resin composition according to any one of

[33] to

[53] , wherein a 0.5 mm thick film made of the polycarbonate resin composition has a total light transmittance of 83% or more.

[0075]

[55] A thermoplastic resin composition comprising the polycarbonate resin composition according to any one of

[33] to

[54] , wherein the content of the polycarbonate resin composition in 100% by mass of the thermoplastic resin composition is 1% by mass or more and 30% by mass or less.

[0076]

[56] An injection-molded article obtained by injection molding the polycarbonate resin composition according to any one of

[33] to

[54] or the thermoplastic resin composition according to

[54] .

[0077]

[57] An extrusion-molded product obtained by extrusion molding the polycarbonate resin composition according to any one of

[33] to

[54] or the thermoplastic resin composition according to

[54] .

[0078]

[58] The extrusion molded product according to

[57] , wherein the extrusion molded product is a sheet or a film.

[0079] According to the present invention, it is possible to provide a polycarbonate resin composition that is excellent in heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency. The polycarbonate resin composition of the present invention has good heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber physical properties (tensile set, recovery rate), and transparency, and therefore can be widely used as a material for manufacturing parts in automobiles, electrical and electronic materials, and other industrial fields. In particular, due to its excellent rubber physical properties (tensile set, recovery rate), the polycarbonate resin composition of the present invention is useful in applications such as membrane materials used in membrane structure buildings, vibration damping materials for EVs, watch bands, camera grips, catheter tubes, and shoe midsoles.

[0080] The present invention will be described in detail below with reference to embodiments and examples. The present invention should not be construed as being limited to the embodiments and examples shown below. In this specification, unless otherwise specified, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0081] [Polycarbonate Resin Composition] The polycarbonate resin composition according to the first embodiment of the present invention is a polycarbonate resin composition containing a carbonate structural unit (X) (hereinafter sometimes simply referred to as "carbonate structural unit (X)") derived from an aliphatic polyester polyol (1) represented by the following formula (1), and a carbonate structural unit (Y1) (hereinafter sometimes simply referred to as "carbonate structural unit (Y1)") derived from a dihydroxy compound (3) represented by the following formula (3).

[0082]

[0083] (In formula (1), A represents a divalent linking group having no cyclic structure, which is composed of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and a hydrogen atom, and multiple As in formula (1) are the same. B represents a divalent linking group having no cyclic structure, which is composed of 1 to 40 carbon atoms and a hydrogen atom, and n is an integer from 2 to 100.)

[0084]

[0085] A polycarbonate resin composition according to a second embodiment of the present invention is a polycarbonate resin composition used for any one application selected from the group consisting of membrane materials used in membrane structure buildings, vibration-damping materials for EVs, watch bands, camera grips, catheter tubes, and shoe midsoles, the polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) represented by the following formula (1) and a carbonate structural unit (Y2) (hereinafter, sometimes simply referred to as the "carbonate structural unit (Y2)") derived from a dihydroxy compound (2) satisfying the following requirement I, and having a peak melting point temperature when measured by heating at a temperature rise rate of 20°C / min using a differential scanning calorimeter.

[0086]

[0087] (In formula (1), A represents a divalent linking group having no cyclic structure, consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and a hydrogen atom, and multiple As in formula (1) are the same. B represents a divalent linking group having no cyclic structure, consisting of 1 to 40 carbon atoms and a hydrogen atom, and n is an integer from 2 to 100.)

[0088] <Requirement I> The dihydroxy compound (2) has a melt volume flow rate (MVR) of 5 to 120 cm3 at 260°C under a load of 2.16 kg by a transesterification method with a carbonate source. ３ When the polycarbonate resin (2) is polymerized with the dihydroxy compound (A) at a temperature rise rate of 20°C / min and the melting point peak temperature is measured by using a differential scanning calorimeter, the polycarbonate resin (2) is a dihydroxy compound having a melting point peak temperature of 20°C / min. / 10 min.

[0089] In the present invention, the term "carbonate structural unit" refers to a structural unit having a carbonate bond (-O-R-O-C(=O)-: R is a group derived from the raw material compound) that is introduced into a polycarbonate resin through a reaction between raw material compounds for the polycarbonate resin, such as an aliphatic polyester polyol (1), a dihydroxy compound (2), or a dihydroxy compound (3), during the production process of the polycarbonate resin.

[0090] Hereinafter, the polycarbonate resin composition according to the first embodiment of the present invention will be referred to as "polycarbonate resin composition I," the polycarbonate resin composition according to the second embodiment of the present invention will be referred to as "polycarbonate resin composition II," and polycarbonate resin composition I and polycarbonate resin composition II will be collectively referred to as "polycarbonate resin compositions of the present invention." Furthermore, the carbonate structural unit (Y1) contained in the polycarbonate resin composition according to the first embodiment of the present invention and the carbonate structural unit (Y2) contained in the polycarbonate resin composition according to the second embodiment of the present invention will be collectively referred to as "carbonate structural unit (Y)."

[0091] <Aliphatic Polyester Polyol (1)> The aliphatic polyester polyol (1) that serves as a raw material for the carbonate structural unit (X) is an aliphatic dihydroxy compound represented by the following formula (1).

[0092]

[0093] (In formula (1), A represents a divalent linking group having no cyclic structure, consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and a hydrogen atom, and multiple As in formula (1) are the same. B represents a divalent linking group having no cyclic structure, consisting of 1 to 40 carbon atoms and a hydrogen atom, and n is an integer from 2 to 100.)

[0094] From the viewpoint of polymerizability, A in the above formula (1) is preferably a linear or branched alkylene group having 1 to 9 carbon atoms, more preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and is preferably a branched alkylene group having 1 to 9 carbon atoms and having a methyl group as the branched chain, more preferably a branched alkylene group having 1 to 6 carbon atoms. Furthermore, B in formula (1) is preferably a linear alkylene group having 1 to 10 carbon atoms.

[0095] From the viewpoints of availability and polymerizability, the aliphatic polyester polyol (1) is preferably at least one selected from the group consisting of aliphatic polyester polyols represented by the following formula (2) and the following formulas (10) to (12), and among these, the aliphatic polyester polyol represented by the following formula (2) is preferred.

[0096]

[0097] (In the above formula, n, o, p, q, r, and s are integers of 2 to 100. X is an n-nonylene group or a 2-methyl-1,8-octylene group.)

[0098] The aliphatic polyester polyol represented by the formula (2) is preferably a biomass-derived aliphatic polyester polyol synthesized by condensing 3-methyl-1,5-pentanediol with sebacic acid produced from plant-derived raw materials. The aliphatic polyester polyol represented by the formula (12) is preferably a biomass-derived aliphatic polyester polyol synthesized by condensing 1,9-nonanediol and 2-methyl-1,8-octanediol with sebacic acid produced from plant-derived raw materials. Whether an aliphatic polyester polyol is produced from a plant-derived resource can be determined, for example, by radiocarbon ( １４ This can be confirmed by measuring the concentration of C).

[0099] The number average molecular weight of the aliphatic polyester polyol (1) is desirably 400 or more and 10,000 or less. The lower limit of the number average molecular weight of the aliphatic polyester polyol (1) is more preferably 900 or more, and even more preferably 1,500 or more. The upper limit of the number average molecular weight of the aliphatic polyester polyol is more preferably 8,000 or less, and even more preferably 6,500 or less. Therefore, it is preferable that n in the above formulas (1) and (2), o in the above formula (10), p and q in the above formula (11), and r and s in the above formula (12) are numbers that satisfy this number average molecular weight.

[0100] In the polycarbonate resin composition of the present invention, the carbonate structural unit (X) derived from the aliphatic polyester polyol (1) forms a soft segment, and the carbonate structural unit (Y), i.e., the carbonate structural unit (Y1) derived from the dihydroxy compound (3) or the carbonate structural unit (Y2) derived from the dihydroxy compound (2), forms a hard segment, thereby exhibiting heat resistance, flexibility, low-temperature mechanical strength, and rubbery elasticity. When the number-average molecular weight of the aliphatic polyester polyol (1) is equal to or greater than the lower limit, soft segments and hard segments are easily formed, and heat resistance, flexibility, low-temperature mechanical strength, and rubbery elasticity tend to be easily achieved. When the number-average molecular weight of the aliphatic polyester polyol (1) is equal to or less than the upper limit, compatibility with the dihydroxy compound (3) or the dihydroxy compound (2) is good, preventing problems such as poor transparency and poor polymerization due to poor compatibility.

[0101] Although there are no particular restrictions on the ratio of p to q in the formula (11), from the viewpoint of raw material availability, it is preferable that p:q = 1:0.2 to 1, particularly 1:0.4 to 0.7. From the same viewpoint, it is also preferable that the ratio of r to s in the formula (12) is r:s = 1:0.2 to 1, particularly 1:0.4 to 0.7.

[0102] <Dihydroxy Compound (3)> The dihydroxy compound (3) used as a raw material for the carbonate structural unit (Y1) is a dihydroxy compound represented by the following formula (3), that is, spiroglycol (hereinafter, sometimes abbreviated as "SPG").

[0103]

[0104] <Dihydroxy Compound (2)> The dihydroxy compound (2) used as a raw material for the carbonate structural unit (Y2) satisfies the following requirement I. <Requirement I> The dihydroxy compound (2) has a melt volume flow rate (MVR) of 5 to 120 cm3 at 260°C under a load of 2.16 kg by a transesterification method with a carbonate source. ３When the polycarbonate resin (2) is polymerized with the dihydroxy compound (A) at a temperature rise rate of 20°C / min and the melting point peak temperature is measured by using a differential scanning calorimeter, the polycarbonate resin (2) is a dihydroxy compound having a melting point peak temperature of 20°C / min. / 10 min.

[0105] In the above-mentioned requirement I, the method for producing the polycarbonate resin (2) by polymerizing the dihydroxy compound (2) and the carbonate source by the transesterification method can be specifically carried out in the same manner as the melt transesterification method in the production method of the polycarbonate resin composition of the present invention described below. The carbonate source used in this case can be any of the carbonate esters exemplified in the melt transesterification method described below.

[0106] The polycarbonate resin (2) “having a peak melting point temperature” as described above means that the polycarbonate resin (2) “has crystallinity.” If the dihydroxy compound (2) is capable of producing a crystalline polycarbonate resin (2) within the range that satisfies the above-mentioned specific MVR, it is possible to produce the polycarbonate resin composition of the present invention having a peak melting point temperature, as described below, and to provide a polycarbonate resin composition excellent in heat resistance, flexibility, low-temperature mechanical strength, and rubber elasticity.

[0107] In measuring the melting peak temperature using a differential scanning calorimeter, the polycarbonate resin (2) obtained by polymerization using a transesterification method may be directly subjected to the melting peak temperature measurement, or the melting peak temperature may be measured for the polycarbonate resin (2) obtained by dissolving the polycarbonate resin in a solvent and then drying and removing the solvent. That is, the polycarbonate resin (2) may be crystalline immediately after production, or may be crystalline by dissolving it in a solvent after production and then drying and removing the solvent to crystallize it. The solvent used in this case may be any solvent that can dissolve the polycarbonate resin (2), including solvents used in the method of mixing polycarbonate resin (a) and polycarbonate resin (b) in solution, as described below. There are no particular limitations on the concentration of polycarbonate resin (2) in the solution or the drying method. Usually, to remove the solvent from the resin solution after dissolving the polycarbonate resin (2), a method of leaving the resin solution to stand for a certain period of time under normal pressure or a slight reduced pressure, or a method of heating the resin solution to a temperature equal to or higher than the boiling point of the solvent used under normal pressure or a slight reduced pressure, is used. A polycarbonate resin (2) that is crystalline immediately after production (a polycarbonate resin (2) that has a peak melting point temperature when the polycarbonate resin (2) obtained by polymerizing the polycarbonate resin (2) by a transesterification method is directly subjected to measurement of the peak melting point temperature) has higher crystallinity and is therefore preferred than a polycarbonate resin that has become crystalline by dissolving the polycarbonate resin (2) in a solvent after production and then drying and removing the solvent.

[0108] Here, the MVR of the polycarbonate resin (2) used to measure the melting point peak temperature is 5 to 120 cm ３ The reason for setting the time to 10 min is as follows: ３ In the case of a polycarbonate resin having a molecular weight of less than 120 cm / 10 min, the amount of branching increases, which may affect the crystallinity of the polycarbonate resin (2). ３ In the case of a polycarbonate resin having an MVR of more than 10 min, the molecular weight is too low and the polycarbonate resin (2) may not be polymerized. ３The polycarbonate resin (2) is subjected to measurement of the melting point peak temperature.

[0109] The peak melting point temperature of the polycarbonate resin (2) is not particularly limited, but for the same reasons as those for the peak melting point temperature of the polycarbonate resin composition of the present invention described below, it is preferably 120° C. or higher, more preferably 130° C. or higher, and even more preferably 140° C. or higher, and is preferably 300° C. or lower, and more preferably 260° C. or lower. When the polycarbonate resin (2) has multiple peak melting point temperatures, it is preferable that at least the higher peak melting point temperature is within the above range.

[0110] The melting peak temperature of polycarbonate resin (2) is a melting peak temperature obtained by measuring the calorific value of polycarbonate resin (2) by heating it at a temperature increase rate of 20°C / min using a differential scanning calorimeter and taking the temperature at the apex of the melting peak, and is specifically measured by the method described in the Examples section below. The MVR of polycarbonate resin (2) is also specifically measured by the method described in the Examples section below.

[0111] The dihydroxy compound (2) is not particularly limited as long as it satisfies the above-mentioned requirement I, and examples thereof include dihydroxy compounds represented by the following formulas (3) to (7): spiroglycol represented by the following formula (3) (hereinafter, may be abbreviated as "SPG"), 4,4'-dihydroxydiphenyl ether represented by the following formula (4) (hereinafter, may be abbreviated as "DHDE"), bis(4-hydroxyphenylmethane (=bisphenol F) (hereinafter, may be abbreviated as "BPF") represented by the following formula (5), 4,4'-methylenebis(2,6-dimethylphenol) (hereinafter, may be abbreviated as "TmBPF") represented by the following formula (6), and 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A) (hereinafter, may be abbreviated as "BPA") represented by the following formula (7).

[0112]

[0113] The dihydroxy compounds represented by the above formulas (3) to (6) themselves exhibit crystallinity when made into polycarbonate resin (2). The compound represented by the above formula (7) does not usually exhibit crystallinity when made into polycarbonate resin (2), but becomes crystalline when dissolved in a solvent and the solvent is dried and removed. From the viewpoint of crystallinity, the dihydroxy compounds represented by the above formulas (3) to (6) are more preferred. In particular, spiro glycol (SPG) represented by the above formula (3) has high crystallinity and is particularly preferred from the viewpoints of heat resistance, flexibility, rubber elasticity, and transparency. Furthermore, 4,4'-dihydroxydiphenyl ether (DHDE) represented by formula (4) is preferred from the viewpoints of heat resistance and flexibility. That is, the dihydroxy compound (2) according to the present invention is preferably spiro glycol represented by formula (3) or 4,4'-dihydroxydiphenyl ether represented by formula (4).

[0114] <Containment Form of Carbonate Structural Unit (X) and Carbonate Structural Unit (Y)> There are no particular limitations on the containment form of the carbonate structural unit (X) and the carbonate structural unit (Y) (carbonate structural unit (Y1) or carbonate structural unit (Y2)) in the polycarbonate resin composition of the present invention. Usually, the carbonate structural unit (X) and the carbonate structural unit (Y) are contained in the polycarbonate resin.

[0115] The polycarbonate resin composition of the present invention may be a polycarbonate resin mixture (blend) of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Y), or may contain a copolymer-type polycarbonate resin containing both the carbonate structural unit (X) and the carbonate structural unit (Y).

[0116] The polycarbonate resin composition of the present invention may be a mixture of a polycarbonate resin containing the carbonate structural unit (X) and / or the carbonate structural unit (Y) and a copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Y).

[0117] The polycarbonate resin composition of the present invention may further contain a polycarbonate resin that does not contain the carbonate structural unit (X) or the carbonate structural unit (Y).

[0118] When the polycarbonate resin composition of the present invention contains the carbonate structural unit (X) and the carbonate structural unit (Y) as a copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Y), the polycarbonate resin composition of the present invention is referred to as a "polycarbonate resin."

[0119] When the polycarbonate resin composition of the present invention is a mixture of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Y), it is usually referred to as a "polycarbonate resin composition." The same applies to the above-mentioned other containing forms.

[0120] In the present invention, the term "polycarbonate resin composition" includes cases where a single copolymer polycarbonate resin contains the carbonate structural unit (X) and the carbonate structural unit (Y). However, in the examples and comparative examples described below, a single copolymer polycarbonate resin is produced, and therefore it is referred to as a "polycarbonate resin" (the "polycarbonate resin" of the present invention).

[0121] <Contents of Each Carbonate Structural Unit (X) and Carbonate Structural Unit (Y)> The content of the carbonate structural unit (X) in 100% by mass of all carbonate structural units in the polycarbonate resin composition of the present invention (hereinafter, the contents of carbonate structural units such as the carbonate structural unit (X) and the carbonate structural unit (Y) are all expressed as mass percentages relative to 100% by mass of all carbonate structural units in the polycarbonate resin composition) is preferably 1% by mass or more and 99% by mass or less, and the content of the carbonate structural unit (Y) is preferably 1% by mass or more and 99% by mass or less. By containing 1% by mass or more and 99% by mass or less of the carbonate structural unit (X) and 1% by mass or more and 99% by mass or less of the carbonate structural unit (Y), the polycarbonate resin composition of the present invention can have good heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber physical properties, and transparency.

[0122] From the viewpoints of flexibility and mechanical strength, the content of the carbonate structural unit (X) in the polycarbonate resin composition of the present invention is preferably 1% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, particularly preferably 27% by mass or more, especially preferably 40% by mass or more, and most preferably 50% by mass or more, and the content of the carbonate structural unit (Y) is preferably 99% by mass or less, more preferably 83% by mass or less, even more preferably 75% by mass or less, especially preferably 73% by mass or less, especially preferably 63% by mass or less, and most preferably 50% by mass or less. From the viewpoint of heat resistance, the content of the carbonate structural unit (X) is preferably 99% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, particularly preferably 73% by mass or less, and especially preferably 60% by mass or less, and the content of the carbonate structural unit (Y) is preferably 1% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, particularly preferably 27% by mass or more, and especially preferably 37% by mass or more. The content of the carbonate structural unit (X) and the content of the carbonate structural unit (Y) in the polycarbonate resin composition are determined by the following formula: １ It can be determined by measuring H-NMR.

[0123] From the viewpoint of more reliably obtaining the effects of heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber physical properties, and transparency due to the inclusion of the carbonate structural unit (X) and the carbonate structural unit (Y), the sum of the content of the carbonate structural unit (X) and the content of the carbonate structural unit (Y) in 100% by mass of all carbonate structural units in the polycarbonate resin composition of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98 to 100% by mass.

[0124] The polycarbonate resin composition of the present invention may use only one type of aliphatic polyester polyol (1) constituting the carbonate structural unit (X), or may use two or more types. That is, the composition may contain carbonate structural units (X) derived from two or more types of aliphatic polyester polyol (1). The polycarbonate resin composition may also contain only one type of carbonate structural unit (Y2), or may contain two or more types. That is, the composition may contain carbonate structural units (Y2) derived from two or more types of dihydroxy compounds (2).

[0125] The content of each carbonate structural unit (X) and (Y) in the polycarbonate resin composition of the present invention and the content ratio of other carbonate structural units described below are determined as described above for the polycarbonate resin composition. １ This can be determined by analysis such as H-NMR measurement, etc. Details of this analysis method will be described in the Examples section below.

[0126] <Other Carbonate Structural Units> The polycarbonate resin composition of the present invention may contain other carbonate structural units besides the carbonate structural unit (X) and the carbonate structural unit (Y) (the carbonate structural unit (Y1) or the carbonate structural unit (Y2)), i.e., carbonate structural units derived from an aromatic or aliphatic dihydroxy compound other than the aliphatic polyester polyol (1) and the dihydroxy compound (2) or the dihydroxy compound (3), within the scope of the present invention.

[0127] Other carbonate structural units may also be contained as copolymer polycarbonate resins with the carbonate structural unit (X) and / or the carbonate structural unit (Y), and polycarbonate resins comprising other carbonate structural units may be mixed with polycarbonate resins containing the carbonate structural unit (X) and / or the carbonate structural unit (Y).

[0128] When the polycarbonate resin composition of the present invention contains other carbonate structural units, the content of the other carbonate structural units in 100% by mass of all carbonate structural units in the polycarbonate resin composition is preferably 10% by mass or less, particularly 5% by mass or less, and especially 2% by mass or less. When the polycarbonate resin composition contains other carbonate structural units, it may be possible to obtain improving effects such as a decrease in water absorption due to the other carbonate structural units, but if the content is too high, the effects of the present invention, such as improvements in heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber physical properties, and transparency, which are achieved by containing the carbonate structural units (X) and (Y), may be impaired.

[0129] The polycarbonate resin composition of the present invention may contain only one type of other carbonate structural unit, or may contain two or more types.

[0130] <Other Components> The polycarbonate resin composition of the present invention may contain other components in addition to the polycarbonate resin containing the carbonate structural unit (X) and / or the carbonate structural unit (Y), as necessary, as long as the desired physical properties are not significantly impaired. Examples of the other components include polycarbonate resins that do not contain the carbonate structural unit (X) and the carbonate structural unit (Y), resins other than polycarbonate resins, various resin additives, etc.

[0131] Examples of resin additives include heat stabilizers, antioxidants, mold release agents, light stabilizers (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, dyes, pigments, etc. These resin additives may be contained alone or in any combination and ratio of two or more.

[0132] Examples of other resins that can be contained in the polycarbonate resin composition of the present invention include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; styrene-based resins such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polymethacrylate resin, etc. One type of other resin may be contained, or two or more types may be contained in any combination and ratio.

[0133] When the polycarbonate resin composition of the present invention is blended as an additive such as an impact modifier into the thermoplastic resin composition of the present invention described below, the polycarbonate resin composition of the present invention preferably contains the carbonate structural unit (X) and the carbonate structural unit (Y) (the carbonate structural unit (Y1) or the carbonate structural unit (Y2)) in a total amount of 70 mass% or more per 100 mass% of the polycarbonate resin composition.

[0134] <Characteristics of Polycarbonate Resin Composition> (Peak Melting Point Temperature of Polycarbonate Resin Composition) When the peak melting point temperature is measured by heating at a temperature rise rate of 20°C / min using a differential scanning calorimeter, the polycarbonate resin composition I preferably has a peak melting point temperature, i.e., has crystallinity. When the peak melting point temperature is measured by heating at a temperature rise rate of 20°C / min using a differential scanning calorimeter, the polycarbonate resin composition II preferably has a peak melting point temperature, i.e., has crystallinity.

[0135] The polycarbonate resin composition "having a peak melting point temperature" as described above means that the polycarbonate resin composition "has crystallinity." It should be noted that, in measuring the peak melting point temperature using a differential scanning calorimeter, the polycarbonate resin composition is subjected to the measurement of the peak melting point temperature as is, and does not include the case where the peak melting point temperature is measured on a polycarbonate resin composition obtained by dissolving a polycarbonate resin in a solvent and then removing the solvent by drying. When the polycarbonate resin composition of the present invention has a peak melting point temperature as measured using a differential scanning calorimeter, good rubber elasticity is obtained due to pseudo-crosslinking, and a polycarbonate resin composition having excellent heat resistance, flexibility, low-temperature mechanical strength, and rubber physical properties can be provided.

[0136] The melting peak temperature of the polycarbonate resin composition I when it has a melting peak temperature, or the melting peak temperature of the polycarbonate resin composition II, is not particularly limited. However, the melting peak temperature, which is determined by heating the polycarbonate resin composition of the present invention at a heating rate of 20°C / min using a differential scanning calorimeter, measuring the calorific value, and taking the temperature at the apex of the melting peak, is preferably 100°C or higher, more preferably 120°C or higher, even more preferably 130°C or higher, and particularly preferably 140°C or higher. A melting peak temperature above the above-mentioned lower limit is preferred because of excellent heat resistance. From the viewpoint of moldability, the upper limit of the melting peak temperature of the polycarbonate resin composition of the present invention is preferably 300°C or lower, more preferably 260°C or lower, and even more preferably 240°C or lower. When the polycarbonate resin composition of the present invention has multiple melting peak temperatures, it is preferred that at least the higher melting peak temperature be within the above-mentioned range. The melting point peak temperature of the polycarbonate resin composition of the present invention is specifically measured by the method described in the Examples section below.

[0137] (Molecular Weight of Polycarbonate Resin Composition) The molecular weight of the polycarbonate resin composition of the present invention is preferably 20,000 or more and 150,000 or less, in terms of viscosity average molecular weight (Mv) calculated from the solution viscosity. If the viscosity average molecular weight (Mv) is equal to or more than the above lower limit, the mechanical properties of the polycarbonate resin composition of the present invention are good, which is preferable. If the viscosity average molecular weight (Mv) is equal to or less than the above upper limit, the flowability and moldability of the polycarbonate resin composition of the present invention tend to be good, which is preferable. From this viewpoint, the viscosity average molecular weight (Mv) of the polycarbonate resin composition of the present invention is more preferably 25,000 or more, even more preferably 30,000 or more, and more preferably 120,000 or less, even more preferably 100,000 or less.

[0138] The viscosity average molecular weight (Mv) of the polycarbonate resin composition of the present invention can be determined by measuring the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at 20°C using an Ubbelohde viscometer in methylene chloride or chloroform as a solvent, and then calculating the viscosity average molecular weight (Mv) using the Schnell viscosity formula, i.e., η = 1.23 × 10 －４ Mv０．８３ The intrinsic viscosity (limiting viscosity) [η] is a value calculated from the specific viscosity [ηsp] measured at each solution concentration [C] (g / dL) using the following formula:

[0139]

[0140] (Glass Transition Temperature of Polycarbonate Resin Composition) There are no particular restrictions on the glass transition temperature of the polycarbonate resin composition of the present invention, but the polycarbonate resin composition of the present invention preferably has a glass transition temperature of 30°C or lower, more preferably 25°C or lower, and even more preferably 10°C or lower, as determined by measuring the calorific value while heating at a temperature rise rate of 20°C / min using a differential scanning calorimeter. If the glass transition temperature is equal to or lower than the above upper limit, the composition will exhibit excellent low-temperature mechanical strength and rubber elasticity. There is no particular restriction on the lower limit of the glass transition temperature of the polycarbonate resin composition of the present invention, but it is usually −100°C or higher. When the polycarbonate resin composition of the present invention has multiple glass transition temperatures, it is preferred that at least the lower glass transition temperature be within the above range.

[0141] (Tensile Modulus of Polycarbonate Resin Composition) The polycarbonate resin composition of the present invention preferably has a tensile modulus of 5 MPa or more, particularly 20 MPa or more, and especially 40 MPa or more, as measured by the method described in the Examples section below, from the viewpoint of shape retention. On the other hand, from the viewpoint of flexibility, this tensile modulus is preferably 1000 MPa or less, particularly 300 MPa or less, and especially 150 MPa or less.

[0142] (Tensile Breaking Elongation of Polycarbonate Resin Composition) From the viewpoint of mechanical strength, it is preferable that the polycarbonate resin composition of the present invention has a tensile breaking elongation of 100% or more, particularly 150% or more, and particularly 400% or more, as measured by the method described in the Examples section below. From the viewpoint of mechanical strength, the larger the tensile breaking elongation, the better, but from the viewpoint of shape retention, the upper limit is usually 1200% or less.

[0143] (Permanent Tensile Set of Polycarbonate Resin Composition) From the viewpoint of rubber elasticity, the polycarbonate resin composition of the present invention preferably has a permanent tensile set of 30% or less, particularly 25% or less, and especially 15% or less, as measured by the method described in the Examples section below. From the viewpoint of rubber elasticity, the smaller the permanent tensile set, the better, but the lower limit is usually 1% or more.

[0144] (Restoration Rate of Polycarbonate Resin Composition) From the viewpoint of rubber elasticity, the polycarbonate resin composition of the present invention preferably has a restoration rate of 70% or more, particularly 80% or more, and particularly 90% or more, as measured by the method described in the Examples section below. From the viewpoint of rubber elasticity, the higher the restoration rate, the better, but the upper limit is usually 99% or less.

[0145] (Retention of Viscosity Average Molecular Weight of Polycarbonate Resin Composition) From the viewpoint of long-term thermal stability, the retention of viscosity average molecular weight (Mv) of the polycarbonate resin composition of the present invention after heating at 100°C for 100 hours using a hot air dryer, as measured by the method described in the Examples section below (hereinafter, this may be referred to as "long-term thermal stability Mv retention"), is preferably 80% or more, particularly 90% or more, and especially 95% or more. From the viewpoint of long-term thermal stability, the higher the long-term thermal stability Mv retention, the better, but the upper limit is usually 105% or less.

[0146] From the viewpoint of hydrolysis resistance, the polycarbonate resin composition of the present invention preferably has a viscosity average molecular weight (Mv) retention rate after treatment for 168 hours under conditions of a temperature of 80°C and a relative humidity of 96%, as measured by the method described in the Examples section below (hereinafter, this may be referred to as "hydrolysis-resistant Mv retention rate") of 90% or more, particularly 92% or more, and especially 94% or more. From the viewpoint of hydrolysis resistance, the higher the hydrolysis-resistant Mv retention rate, the better, but the upper limit is usually 105% or less.

[0147] The polycarbonate resin composition of the present invention was measured using a xenon lamp at an irradiation intensity of 60 W / m by the method described in the Examples section below. ２From the viewpoint of light resistance and weather resistance, it is preferable that the viscosity average molecular weight (Mv) retention rate after treatment with 100 hours (hereinafter, this may be referred to as "lightfast Mv retention rate") is 90% or more, particularly 95% or more, and especially 97% or more. From the viewpoint of light resistance and weather resistance, the higher the lightfast Mv retention rate, the better, but the upper limit is usually 105% or less.

[0148] (Total Light Transmittance of Polycarbonate Resin Composition) From the viewpoint of transparency, it is preferable that the total light transmittance of a 0.5 mm-thick film of the polycarbonate resin composition of the present invention, measured by the method described later in the Examples section, is 83% or more, particularly 84% or more, and especially 88% or more. From the viewpoint of transparency, the higher the total light transmittance, the better, but the upper limit is usually 95% or less.

[0149] (Biomass Degree of Polycarbonate Resin Composition) The biomass degree of the polycarbonate resin composition of the present invention is defined as the mass ratio of carbonate structural units synthesized from plant-derived resources to the carbonate structural units contained in the polycarbonate resin composition of the present invention. In the examples described below, the biomass degree of each polycarbonate resin was calculated according to this definition. From the viewpoint of the Sustainable Development Goals (SDGs) advocated by the United Nations, the polycarbonate resin composition of the present invention preferably has a higher biomass degree, preferably 10% by mass or more, and more preferably 25% by mass or more. On the other hand, since the carbonate source is basically petroleum-derived, the upper limit is usually 98% by mass or less.

[0150] [Method for producing polycarbonate resin composition] <Method for producing polycarbonate resin> The polycarbonate resin constituting the polycarbonate resin composition of the present invention can be produced by a conventionally known polymerization method, and the polymerization method is not particularly limited. Examples of the polymerization method include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, and solid-phase transesterification of a prepolymer. Among these, the melt transesterification and interfacial polymerization methods are preferred, and the melt transesterification method is more preferred. Below, particularly preferred methods among these methods will be specifically described.

[0151] (Melt transesterification method) In the melt transesterification method, for example, a transesterification reaction is carried out between a carbonate ester and a raw material dihydroxy compound.

[0152] By using a raw material dihydroxy compound containing an aliphatic polyester polyol (1) and a dihydroxy compound (3) or a dihydroxy compound (2), a copolymer polycarbonate resin containing a carbonate structural unit (X) and a carbonate structural unit (Y) (carbonate structural unit (Y1) or a carbonate structural unit (Y2)) can be produced. By using one of these dihydroxy compounds, a polycarbonate resin containing the carbonate structural unit (X) or the carbonate structural unit (Y) can be produced. When producing a polycarbonate resin containing the above-mentioned other carbonate structural unit, it is sufficient to use an aliphatic polyester polyol (1) and one or more dihydroxy compounds other than the dihydroxy compound (3) or the dihydroxy compound (2).

[0153] The carbonate ester may be, for example, a compound represented by the following formula (8), and examples thereof include aryl carbonates, dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0154]

[0155] In the above formula (8), R １１ and R １２ each independently represents an alkyl group, an aryl group, or an arylalkyl group having 1 to 30 carbon atoms, which may have a substituent. １１ and R １２ However, when the group is an alkyl group or an arylalkyl group, it is called a dialkyl carbonate, and when the group is an aryl group, it is called a diaryl carbonate. １１ and R １２are preferably aryl groups which may have a substituent, and more preferably diaryl carbonate represented by the following formula (9).

[0156]

[0157] In the above formula (9), R １３ and R １４ are each independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. p and q are each independently an integer of 0 to 5.

[0158] Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate; diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"); bis(4-methylphenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-fluorophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(2,4-difluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, bis(2-nitrophenyl)carbonate, bis(methylsalicylphenyl)carbonate, and diaryl carbonates which may have a substituent such as ditolyl carbonate. Of these, diphenyl carbonate is preferred. These carbonate esters may be used alone or in combination of two or more.

[0159] The carbonate ester may be substituted with a dicarboxylic acid or a dicarboxylic acid ester, preferably in an amount of 50 mol % or less, more preferably 30 mol % or less. Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate, etc. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

[0160] The ratio of the starting dihydroxy compound to the carbonate ester may be any ratio as long as the desired polycarbonate resin is obtained. When polymerizing these carbonate esters with dihydroxy compounds, it is preferable to use a slightly smaller or slightly larger amount of carbonate ester than the starting dihydroxy compound. That is, the amount of carbonate ester is preferably 0.95 to 1.30 times (molar ratio), more preferably 0.98 to 1.20 times (molar ratio), relative to the amount of dihydroxy compound. If this molar ratio is too small, the resulting polycarbonate resin will have more terminal OH groups, which tends to deteriorate the thermal stability of the resin. If this molar ratio is too large, the transesterification reaction rate will decrease, making it difficult to produce a polycarbonate resin having the desired molecular weight, or the amount of carbonate ester remaining in the resin will increase, which may cause an odor during molding or when the molded product is formed.

[0161] When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination as an auxiliary. One type of transesterification catalyst may be used, or two or more types may be used in any combination and ratio.

[0162] In the melt transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 300°C. The pressure during the reaction is not particularly limited, but is usually a reduced pressure of 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be carried out under the above conditions while removing by-products.

[0163] In the presence of an alkali catalyst, the polycarbonate resin composition of the present invention is significantly affected by thermal history and oxidation, leading to deterioration of the color. Therefore, the reaction temperature is preferably 300° C. or lower. In addition, to prevent oxygen leakage from the equipment due to excessive pressure reduction, it is preferable to select reduced pressure conditions with a lower limit of about 0.05 mmHg.

[0164] The reaction can be carried out in either a batch or continuous manner. When the reaction is carried out in a batch manner, the order of mixing the reaction substrates (reaction raw materials), catalyst, additives, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set.

[0165] In the melt transesterification method, a catalyst deactivator may be used as needed. As the catalyst deactivator, any compound that neutralizes the transesterification catalyst can be used. Examples thereof include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc. One catalyst deactivator may be used, or two or more catalyst deactivators may be used in any combination and ratio.

[0166] The amount of the catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, relative to the transesterification catalyst, and usually 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less. The amount of the catalyst deactivator used is usually 1 ppm or more and 1000 ppm or less, preferably 500 ppm or less, relative to the polycarbonate resin.

[0167] <Method for Producing Polycarbonate Resin Composition> When the polycarbonate resin composition of the present invention is a mixture of a polycarbonate resin containing a carbonate structural unit (X) and a polycarbonate resin containing a carbonate structural unit (Y), or a mixture of a polycarbonate resin containing the carbonate structural unit (X) and / or the carbonate structural unit (Y) and a copolymer polycarbonate resin containing the carbonate structural unit (X) and the carbonate structural unit (Y), or when the polycarbonate resin composition of the present invention contains two or more polycarbonate resins, such as a mixture containing a polycarbonate resin containing neither the carbonate structural unit (X) nor the carbonate structural unit (Y), there are no particular limitations on the method for producing the polycarbonate resin composition of the present invention by mixing a plurality of polycarbonate resins, for example, two polycarbonate resins, polycarbonate resin (a) and polycarbonate resin (b). Examples of the method include the following methods 1) to 4). 1) A method of melt-kneading polycarbonate resin (a) and polycarbonate resin (b); 2) A method of melt-kneading molten polycarbonate resin (a) and molten polycarbonate resin (b); 3) A method of mixing polycarbonate resin (a) and polycarbonate resin (b) in a solution state; 4) A method of dry-blending polycarbonate resin (a) and polycarbonate resin (b). Each method will be described below.

[0168] 1) A method of melt-kneading polycarbonate resin (a) and polycarbonate resin (b): Pellets or powder particles of polycarbonate resin (a) and pellets or powder particles of polycarbonate resin (b) are melt-kneaded using a mixing device such as a kneader, a twin-screw extruder, a single-screw extruder, etc. Pellets or powder particles of polycarbonate resin (a) and pellets or powder particles of polycarbonate resin (b) may be mixed in advance in a solid state and then kneaded, or one of them may be melted first in the mixing device, and the other polycarbonate resin may be added thereto and kneaded.

[0169] The temperature during kneading is not particularly limited, but is preferably 200°C or higher, more preferably 210°C or higher, and even more preferably 220°C or higher. Also, 320°C or lower is preferred, and 300°C or lower is particularly preferred. If the kneading temperature is low, the polycarbonate resin (a) and the polycarbonate resin (b) are not mixed completely, which is undesirable as this may result in variations in hardness and impact resistance when a molded product is produced. If the kneading temperature is too high, the color tone of the polycarbonate resin composition may deteriorate, which is undesirable.

[0170] 2) A method of melt-kneading a molten polycarbonate resin (a) and a molten polycarbonate resin (b): The molten polycarbonate resin (a) and the molten polycarbonate resin (b) are mixed using a mixing device such as a stirring tank, a static mixer, a kneader, a twin-screw extruder, a single-screw extruder, etc. In this case, if the polycarbonate resin is obtained by, for example, a melt polymerization method, it may be introduced into the mixing device in a molten state without being cooled or solidified.

[0171] 3) Method of mixing polycarbonate resin (a) and polycarbonate resin (b) in a solution state: In this method, polycarbonate resin (a) and polycarbonate resin (b) are dissolved in an appropriate solvent to form a solution, mixed in the solution state, and then isolated as a polycarbonate resin composition.

[0172] Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and n-heptane; chlorinated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, and 1,2-dichloroethylene; aromatic hydrocarbons such as benzene, toluene, and xylene; and substituted aromatic hydrocarbons such as nitrobenzene and acetophenone. Among these, chlorinated hydrocarbons such as dichloromethane or chlorobenzene are preferably used. These solvents can be used alone or in mixtures with other solvents.

[0173] Examples of the mixing device include a stirring tank, a static mixer, etc. The mixing temperature is not particularly limited as long as the polycarbonate resin (a) and the polycarbonate resin (b) are dissolved, and the mixing is usually carried out at a temperature equal to or lower than the boiling point of the solvent used.

[0174] 4) Method of dry blending polycarbonate resin (a) and polycarbonate resin (b): This method involves dry blending pellets or powder of polycarbonate resin (a) with pellets or powder of polycarbonate resin (b) using a tumbler, a super mixer, a Henschel mixer, a Nauta mixer, or the like.

[0175] Among the above methods 1) to 4), methods 1) and 2) in which the polycarbonate resin (a) and the polycarbonate resin (b) are melt-kneaded, and method 4) in which the polycarbonate resin (a) and the polycarbonate resin (b) are dry-blended are preferred.

[0176] In producing the polycarbonate resin composition, in any of the above methods, pigments, dyes, mold release agents, heat stabilizers, etc. may be added as appropriate within the range that does not impair the object of the present invention.

[0177] [Thermoplastic resin composition] The thermoplastic resin composition of the present invention is a thermoplastic resin composition containing the polycarbonate resin composition of the present invention described above. The content of the polycarbonate resin composition of the present invention in 100% by mass of the thermoplastic resin composition of the present invention is usually 1% by mass or more and 30% by mass or less, and preferably 5% by mass or more and 25% by mass or less, from the viewpoints of heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber elasticity, and moldability.

[0178] Examples of the thermoplastic resin other than the polycarbonate resin composition of the present invention contained in the thermoplastic resin composition of the present invention include the other resins that can be contained in the polycarbonate resin composition of the present invention described above. The thermoplastic resin composition of the present invention can also contain the additives that can be contained in the polycarbonate resin composition of the present invention.

[0179] The polycarbonate resin composition of the present invention, having excellent heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, and rubber elasticity, can be blended with a thermoplastic resin composition and used as a physical property modifier such as an impact modifier. As described above, when the polycarbonate resin composition of the present invention is used as an additive such as an impact modifier for a thermoplastic resin composition, the polycarbonate resin composition of the present invention preferably contains 70% by mass or more in total of the carbonate structural unit (X) and the carbonate structural unit (Y) (the carbonate structural unit (Y1) or the carbonate structural unit (Y2)) per 100% by mass of the polycarbonate resin composition.

[0180] [Molded Articles] To produce molded articles from the polycarbonate resin composition or thermoplastic resin composition of the present invention, a conventional extruder or injection molding machine is used.

[0181] The molding temperature when molding the polycarbonate resin composition or thermoplastic resin composition of the present invention is preferably 200°C or higher, more preferably 210°C or higher, and even more preferably 220°C or higher. It is also preferably 320°C or lower, more preferably 300°C or lower. If the molding temperature is too low, the melt viscosity increases, the flowability decreases, and moldability may decrease. If the molding temperature is too high, the polycarbonate resin composition or thermoplastic resin composition may become discolored, which may deteriorate the color tone of the resulting molded product, which is undesirable. Furthermore, polycarbonate resin compositions containing structural units derived from aliphatic dihydroxy compounds, such as carbonate structural units (X), may decompose at high temperatures.

[0182] When injection molding or extrusion molding is carried out, pigments, dyes, mold release agents, heat stabilizers, etc. may be added to the polycarbonate resin composition or thermoplastic resin composition of the present invention as appropriate within the range that does not impair the object of the present invention.

[0183] <Injection Molded Article> To produce an injection molded article from the polycarbonate resin composition or thermoplastic resin composition of the present invention, a conventional injection molding machine is used.

[0184] When an injection molding machine or the like is used, the mold temperature is preferably 120°C or lower, more preferably 90°C or lower. Also, it is preferably 20°C or higher, more preferably 30°C or higher. If the mold temperature is too high, the cooling time during molding must be extended, which may lengthen the production cycle of molded articles and reduce productivity. If the mold temperature is too low, the melt viscosity of the polycarbonate resin composition or thermoplastic resin composition may become too high, making it impossible to obtain a uniform molded article, and problems such as unevenness on the surface of the molded article may occur, which is undesirable.

[0185] <Extrusion Molded Articles> To produce extrusion molded articles from the polycarbonate resin composition or thermoplastic resin composition of the present invention, a conventional extrusion molding machine is used. The extrusion molding machine is generally equipped with a T-die, a round die, or the like, and extrusion molded articles of various shapes can be obtained. Examples of extrusion molded articles include sheets, films, plates, tubes, pipes, and the like. Among these, sheets and films are preferred.

[0186] The extrusion molded article of the polycarbonate resin composition or thermoplastic resin composition of the present invention may be laminated on one or both sides of the extrusion molded article with a hard coat layer to improve adhesion, paintability, and printability, or may be heat-laminated on one or both sides of the extrusion molded article with a film for improving weather resistance and / or scratch resistance. Furthermore, the surface may be subjected to a graining process or a semi-transparent or opaque process.

[0187] [Uses] Molded articles of the polycarbonate resin composition or thermoplastic resin composition of the present invention have excellent heat resistance, long-term thermal stability, light resistance, flexibility, mechanical strength, low-temperature mechanical strength, and rubber physical properties, and therefore can be used in various fields such as buildings, vehicles, electrical and electronic devices, machinery, and the like.

[0188] In particular, because of the excellent rubber properties (tensile permanent set, recovery rate) possessed by the polycarbonate resin composition of the present invention, the polycarbonate resin composition or thermoplastic resin composition of the present invention is useful in applications such as membrane materials used in membrane structure buildings, vibration damping materials for EVs, watch bands, camera grips, catheter tubes, shoe midsoles, etc. Therefore, polycarbonate resin composition II is used for any of vibration damping materials for EVs, watch bands, camera grips, catheter tubes, and shoe midsoles.

[0189] [Required Properties for Each Application] <Membrane Materials Used in Membrane Structure Buildings> Membrane materials used in membrane structure buildings are particularly required to have weather resistance, light resistance, heat resistance, long-term heat resistance, hydrolysis resistance, and transparency, and a high biomass content is desirable from the perspective of the SDGs. For this reason, the polycarbonate resin composition of the present invention applied to membrane materials used in membrane structure buildings preferably has the following properties among the properties of the polycarbonate resin compositions described above. Melting point peak temperature: From the perspective of heat resistance, it is preferably 120°C or higher, particularly 140°C or higher, and especially 160°C or higher. Long-term thermal stability Mv retention: From the perspective of long-term thermal stability, it is preferably 90% or higher, particularly 95% or higher, and especially 97% or higher. Hydrolysis resistance Mv retention: From the perspective of hydrolysis resistance, it is preferably 90% or higher, particularly 93% or higher, and especially 95% or higher. Light resistance Mv retention: From the perspective of weather resistance and light resistance, it is preferably 90% or higher, particularly 95% or higher, and especially 97% or higher. Biomass content: From the viewpoint of the SDGs, it is preferably 10% by mass or more, particularly preferably 20% by mass or more, and particularly preferably 25% by mass or more.

[0190] <EV Vibration Damping Material> Vibration damping materials for EVs are required to have heat resistance and long-term heat resistance, and from the perspective of the SDGs, a high biomass content is desirable. For this reason, the polycarbonate resin composition of the present invention used in EV vibration damping materials preferably has the following properties among the properties of the polycarbonate resin compositions described above. Melting point peak temperature: from the perspective of heat resistance, it is preferably 150°C or higher, particularly 160°C or higher, and especially 190°C or higher. Long-term thermal stability Mv retention: from the perspective of long-term thermal stability, it is preferably 95% or higher, particularly 97% or higher, and especially 98% or higher. Biomass content: from the perspective of the SDGs, it is preferably 10% by mass or higher, particularly 20% by mass or higher, and especially 25% by mass or higher.

[0191] <Watch band> Watch bands are required to have weather resistance, light resistance, and hydrolysis resistance, and from the perspective of the SDGs, a high biomass content is desirable. For this reason, the polycarbonate resin composition of the present invention used for watch bands preferably has the following properties in particular, among the properties of the polycarbonate resin compositions described above. Hydrolysis resistance Mv retention: From the perspective of hydrolysis resistance, it is preferably 90% or more, particularly 93% or more, and especially 95% or more. Light resistance Mv retention: From the perspective of weather resistance and light resistance, it is preferably 90% or more, particularly 95% or more, and especially 97% or more. Biomass content: From the perspective of the SDGs, it is preferably 10% by mass or more, particularly 20% by mass or more, and especially 25% by mass or more.

[0192] <Camera Grip> Camera grips are required to have weather resistance, light resistance, and hydrolysis resistance, and from the perspective of the SDGs, a high biomass content is desirable. For this reason, the polycarbonate resin composition of the present invention used in camera grips preferably has the following properties among the properties of the polycarbonate resin compositions described above. Hydrolysis resistance Mv retention: From the perspective of hydrolysis resistance, it is preferably 90% or more, particularly 93% or more, and especially 95% or more. Light resistance Mv retention: From the perspective of weather resistance and light resistance, it is preferably 90% or more, particularly 95% or more, and especially 97% or more. Biomass content: From the perspective of the SDGs, it is preferably 10% by mass or more, particularly 20% by mass or more, and especially 25% by mass or more.

[0193] <Catheter Tube> Catheter tubes are required to be biocompatible (hydrolysis resistance), and from the viewpoint of the SDGs, a high biomass content is desirable. For this reason, the polycarbonate resin composition of the present invention used for catheter tubes preferably has the following properties among the properties of the polycarbonate resin compositions described above. Hydrolysis-resistant Mv retention: From the viewpoint of hydrolysis resistance, it is preferably 90% or more, particularly 93% or more, and especially 95% by mass or more. Biomass content: From the viewpoint of the SDGs, it is preferably 10% by mass or more, particularly 20% by mass or more, and especially 25% by mass or more.

[0194] <Shoe Midsole> Shoe midsoles are required to have high resilience (rubber elasticity), and from the viewpoint of the SDGs, a high biomass content is desirable. For this reason, the polycarbonate resin composition of the present invention used in shoe midsoles preferably has the following properties among the properties of the polycarbonate resin compositions described above. Tensile set: from the viewpoint of rubber elasticity, it is preferably 30% or less, particularly 20% or less, and especially 12% or less. Recovery rate: from the viewpoint of rubber elasticity, it is 70% or more, particularly 85% or more, and especially 92% or more. Biomass content: from the viewpoint of the SDGs, it is preferably 10% by mass or more, particularly 20% by mass or more, and especially 25% by mass or more.

[0195] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to the following examples.

[0196] The physical properties of the polycarbonate resins obtained in the following Examples and Comparative Examples were evaluated by the following methods.

[0197] (1) Viscosity Average Molecular Weight (Mv) A polycarbonate resin was dissolved in methylene chloride (concentration: 6.0 g / L), and the intrinsic viscosity (intrinsic viscosity) [η] (unit: dL / g) at 20°C was determined using an Ubbelohde viscosity tube (manufactured by Moritomo Rika Kogyo Co., Ltd.), and the viscosity average molecular weight (Mv) was calculated using Schnell's viscosity formula (formula below). In Example 2, the resin was dissolved in chloroform due to its poor solubility in methylene chloride, and the measurement was performed. η = 1.23 × 10 －４ Mv ０．８３

[0198] (2) Glass transition temperature (Tg) and melting peak temperature (Tm) were measured using a differential scanning calorimeter (DSC6220 manufactured by SII). The obtained polycarbonate resin was used as a measurement sample without drying. An aluminum sample pan containing approximately 10 mg of the measurement sample was heated from 30°C to 300°C at a temperature increase rate of 20°C / min with a nitrogen gas flow rate of 50 mL / min, and then cooled to -120°C at a temperature decrease rate of 40°C / min. Thereafter, the temperature was increased again to 300°C at a temperature increase rate of 20°C / min. The differential scanning calorimetry curve obtained in the second temperature increase was analyzed as the measurement curve. Analysis of the glass transition temperature (Tg) and melting peak temperature (Tm) was performed in accordance with JIS K7121-1987. The extrapolated glass transition onset temperature was determined as the temperature at the intersection of a straight line extending the low-temperature baseline toward the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change in the glass transition is maximum. This extrapolated glass transition temperature was taken as the glass transition temperature (Tg). The melting peak temperature (Tm) was taken as the apex of the melting peak temperature. When the glass transition temperature (Tg) could not be clearly confirmed or when the melting peak temperature (Tm) did not exist, it was recorded as "n.d."

[0199] (3) Long-term thermal stability 1.0 g of the obtained polycarbonate resin pellets was placed on an aluminum dish, placed in a WFO-400 constant temperature air blower dryer (manufactured by Tokai Rikakikai Co., Ltd.), and heated at 100°C for 100 hours. After heating for 100 hours, the viscosity average molecular weight (Mv) was measured using the method described above, and the percentage (%) of the viscosity average molecular weight relative to the viscosity average molecular weight before heating was calculated. In Tables 2A, 2B, 3A, and 3B below, this is referred to as "100°C / 100h heating test Mv retention."

[0200] (4) Hydrolysis Resistance Using a small injection molding machine C, Mobile (manufactured by Shinko Selvic Co., Ltd.), polycarbonate resin plates measuring 2 mm thick, 25 mm long, and 25 mm wide were molded under conditions of a cylinder temperature of 230°C and a mold temperature of 40°C to obtain test specimens. The viscosity average molecular weight (Mv) of the test specimens before treatment was measured using the method described above. The obtained test specimens were treated for 168 hours using a constant temperature and humidity chamber PR-1KTH (manufactured by Espec Corporation) under conditions of an internal temperature of 80°C and an internal relative humidity of 96%. After 168 hours of treatment, the viscosity average molecular weight (Mv) of the test specimens was measured using the method described above, and the ratio (%) of the viscosity average molecular weight to the viscosity average molecular weight of the test specimen before treatment was calculated. In Tables 2A, 2B, 3A, and 3B below, this is referred to as "80°C, 90%, 168-h test Mv retention rate."

[0201] (5) Light resistance 1.0 g of the obtained polycarbonate resin pellets was placed on an aluminum dish and placed in a small light irradiation test device EYE SUN-CUBE Xenon (manufactured by Iwasaki Electric Co., Ltd.). The test was conducted at an irradiation intensity of 60 W / m ２ After the 100-hour treatment, the viscosity-average molecular weight (Mv) was measured by the method described above, and the ratio (%) of the viscosity-average molecular weight before treatment was calculated. ２ ・100h・Xe lamp test Mv retention rate"

[0202] (6) Tensile Modulus and Elongation at Break The obtained polycarbonate resin was dried at 70-80°C for 3 hours or more, and approximately 3 g of the resin was pressed in a heat press using a 0.5 mm thick, 70 mm long, and 70 mm wide SUS spacer at a heat press temperature of 200-240°C, preheated for 1-3 minutes, and pressurized at 1-5 MPa for 1 minute. The spacer was then removed and cooled at room temperature to produce a 0.5 mm thick pressed piece. This pressed piece was cut with scissors into strips of 0.5 mm thick, 70 mm long, and 10 mm wide to obtain a test sample. The following tensile test was performed using test samples that had been hot pressed for 24 hours or more. The obtained test samples were subjected to a tensile test using an AUTOGRAPH AGS-X tabletop precision universal testing machine (Shimadzu Corporation) at an initial chuck distance of 45 mm and a tensile speed of 50 mm / min, and the tensile modulus and elongation at break were measured. The lower the tensile modulus, the better the flexibility, and the higher the elongation at break, the better the mechanical strength.

[0203] (7) Test Piece Bending Test Pressed pieces that had been left for 24 hours or more after the above-mentioned heat pressing were used. The pressed pieces obtained by heat pressing were folded in a mountain fold and a valley fold alternately five times each, for a total of 10 folds. If there was no break after a total of 10 mountain folds and valley folds, it was rated "A." If breaks or cuts occurred between two and ten total folds, it was rated "B." If breaks or cuts occurred after the first mountain fold, it was rated "C." If it was rated A or B, it was determined that the mechanical strength was high.

[0204] (8) Tensile Set and Recovery Rate: A rectangular test sample was prepared from the obtained polycarbonate resin in the same manner as for the tensile modulus and elongation at break. The test sample was used after 24 hours or more had passed since the above-mentioned hot pressing. The obtained test sample was stretched using a tabletop precision universal testing machine, AUTOGRAPH AGS-X (manufactured by Shimadzu Corporation), with an initial chuck distance (gauge distance) of 45 mm and a pulling speed of 50 mm / min. The stretching was stopped when the sample reached approximately 100% (approximately 45 mm) and held for 10 minutes. The gauge distance during the stretching was also measured. The test sample was then shrunk to the initial gauge distance, and removed. The gauge distance of the test sample immediately after removal (within 30 seconds) and 30 minutes after removal were measured. Using these measured values, the stretched length (A), the restored length (C) immediately after removal (within 30 seconds), and the restored length (B) 30 minutes after removal were calculated, and the tensile permanent set and the recovery rate were determined using the following formula: The calculation methods for the stretched length (A), the restored length immediately after removal (C), and the restored length 30 minutes after removal (B), and the calculation formulas for the tensile permanent set and the recovery rate are as follows: Stretched length (A): The difference between the gauge length at 100% elongation and the initial distance between the zippers.Restored length immediately after removal (within 30 seconds) (C): The difference between the gauge length at 100% elongation and the gauge length immediately after removal (within 30 seconds).Restored length 30 minutes after removal (B): The difference between the gauge length at 100% elongation and the gauge length 30 minutes after removal.Tensile set (%) = {((A) - (B)) / (A)} x 100(%).A smaller tensile set means better rubber elasticity and is therefore preferred.Restore rate = {(C) / (B)} x 100(%).A larger restore rate means better rubber elasticity and is therefore preferred.

[0205] (9) Total Light Transmittance A 0.5 mm thick heat-pressed film was prepared from the obtained polycarbonate resin in the same manner as for the tensile modulus and elongation at break. The test sample was left for at least 24 hours after the heat pressing. The polycarbonate resin film was measured twice using a spectral colorimeter / haze meter (Nippon Denshoku Co., Ltd. COH7700) in accordance with ISO 13468-1, and the average value was calculated.

[0206] [Raw Materials] The compounds used in the following Examples, Reference Examples, and Comparative Examples are abbreviated as follows. The compounds used were manufactured by the following manufacturers. Of the following compounds, plant-derived raw materials were used for P-2050, P-4050, P-6050, O-4050, O-5050, PO3G, and ISB.

[0207] <Dihydroxy Compounds> P-2050: aliphatic polyester polyol represented by the formula (2), number average molecular weight 1965 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol), biomass degree 59 mass% P-4050: aliphatic polyester polyol represented by the formula (2), number average molecular weight 4110 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol), biomass degree 62 mass% P-6050: aliphatic polyester polyol represented by the formula (2), number average molecular weight 5844 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol), biomass degree 62 mass% P-6010: aliphatic polyester polyol represented by the formula (10), number average molecular weight 5724 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol) O-2010: aliphatic polyester polyol represented by the formula (11), number average molecular weight 2004 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol) O-4050: Aliphatic polyester polyol represented by the formula (12), number average molecular weight 4022 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol), biomass degree 51% by mass. O-5050: Aliphatic polyester polyol represented by the formula (12), number average molecular weight 4921 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol), biomass degree 51% by mass. PO3G500: Polytrimethylene ether glycol, number average molecular weight 562 (manufactured by ALLESSA, trade name: VELVETOL), biomass degree 100% by mass. PO3G1000: Polytrimethylene ether glycol, number average molecular weight 1042 (manufactured by ALLESSA, trade name: VELVETOL), biomass degree 100% by mass. SPG: Spiroglycol (manufactured by Mitsubishi Gas Chemical Company, Inc.). ISB: Isosorbide (manufactured by Roquette Fleuret), biomass degree 100% by mass. DHDE: 4,4'-dihydroxydiphenyl ether (manufactured by CHEMFISH) BPA: 2,2-bis(4-hydroxyphenyl)propane (manufactured by Mitsubishi Chemical Corporation)

[0208] <Carbonate ester> DPC: diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

[0209] <Polymerization catalyst> Calcium acetate monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0210] [Measurement of Glass Transition Temperature, Melting Peak Temperature, and Melt Volume Flow Rate (MVR) of Polycarbonate Resin Comprising Dihydroxy Compound (2)] Using only the compounds shown in Table 1 as dihydroxy compounds, polycarbonate resins (corresponding to polycarbonate resin (2)) containing 100% by mass of carbonate structural units (Y2) were produced by the polymerization method described below, and the glass transition temperature and melting peak temperature were measured. The measurement method was the same as described above, except that the temperature was lowered to 50°C instead of -120°C at a temperature drop rate of 40°C / min, and the results are shown in Table 1. Furthermore, in accordance with ISO 1133, a polycarbonate resin sample was dried at 100°C for 4 hours and the melt volume flow rate (MVR) per unit time (unit: cm) was measured using a melt indexer F-F01 (manufactured by Toyo Seiki Seisakusho, Ltd.) at 260°C and a load of 2.16 kg. ３ / 10 min)

[0211]

[0212] It can be seen from Table 1 that all of the compounds used as dihydroxy compound (2) in the examples have a melting point peak temperature.

[0213] [Polymerization Method Using SPG as Dihydroxy Compound] A raw material mixture was prepared by adding 116.71 g (approximately 0.383 mol) of SPG, 83.37 g (approximately 0.389 mol) of DPC, and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst to a 570 mL glass reactor equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device so that the calcium acetate monohydrate was present in an amount of 100 μmol per 1 mol of the total dihydroxy compounds.

[0214] Next, the pressure inside the glass reactor was reduced to 1.3 to 4.0 kPa (10 to 30 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated five times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Thereafter, the stirrer was rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute over 40 minutes, while distilling off phenol, which was a by-product of the oligomerization reaction of the dihydroxy compound and DPC occurring inside the reactor.

[0215] Next, the pressure inside the reactor was maintained at 13.3 kPa, and a transesterification reaction was carried out for 45 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 285°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute over 40 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was then reduced to 60 Pa (approximately 0.4 Torr), and a polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power.

[0216] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter.

[0217] [Polymerization Method Using DHDE as Dihydroxy Compound] A raw material mixture was prepared by adding 116.71 g (approximately 0.577 mol) of DHDE, 123.64 g (approximately 0.577 mol) of DPC, and a 0.4 mass% aqueous solution of cesium carbonate as a catalyst to a 570 mL glass reactor equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device so that the amount of cesium carbonate was 5 μmol per 1 mol of the total dihydroxy compounds.

[0218] Next, the pressure inside the glass reactor was reduced to 1.3 to 4.0 kPa (10 to 30 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated five times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Thereafter, the stirrer was rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute over 40 minutes, while distilling off phenol, which was a by-product of the oligomerization reaction of the dihydroxy compound and DPC occurring inside the reactor.

[0219] Next, the pressure inside the reactor was maintained at 13.3 kPa, and a transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute over 40 minutes, and the distilled phenol was removed from the system. The temperature outside the reactor was then raised to 280°C, and the absolute pressure inside the reactor was reduced to 60 Pa (approximately 0.4 Torr), and a polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power.

[0220] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter.

[0221] [Measurement of the content ratio of carbonate structural unit] The content ratios of the carbonate structural unit (X), the carbonate structural unit (Y1), and the carbonate structural unit (Y2) in the polycarbonate resins produced in the following Examples, Reference Examples, and Comparative Examples were measured as follows: １ It can be calculated from the value measured by H-NMR, but it can also be determined from the amount of the raw material dihydroxy compound charged during the production of the polycarbonate resin.

[0222] Reference Example 1 A raw material mixture was prepared by adding 60.00 g (approximately 0.0305 mol) of P-2050, 40.00 g (approximately 0.131 mol) of SPG, 34.87 g (approximately 0.163 mol) of DPC, and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst to a glass reactor having an internal volume of 570 mL and equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device. The amount of calcium acetate monohydrate was 150 μmol per 1 mol of the total dihydroxy compounds.

[0223] Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Thereafter, the stirrer was rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute pressure over 40 minutes, while distilling off phenol, which was a by-product of the oligomerization reaction of the dihydroxy compound and DPC occurring inside the reactor.

[0224] Next, the pressure inside the reactor was maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute over 40 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was then reduced to 30 Pa (approximately 0.2 Torr), and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power.

[0225] The reactor was then pressurized with nitrogen to an absolute pressure of 101.3 kPa, and then the gauge pressure was increased to 0.2 MPa. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strands were pelletized using a rotary cutter. This polycarbonate resin contained 58.3% by mass of carbonate structural units (X) and 41.7% by mass of carbonate structural units (Y), and had a biomass content of 34% by mass.

[0226] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0227] Example 1 A polycarbonate resin was produced by the same method as in Reference Example 1, except that a raw material mixture was prepared by adding 35.00 g (approximately 0.0085 mol) of P-4050, 65.00 g (approximately 0.214 mol), 47.81 g (approximately 0.223 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, so that the calcium acetate monohydrate was 200 μmol per 1 mol of total dihydroxy compounds. The resulting polycarbonate resin contained 33.3 mass% of carbonate structural units (X) and 66.7 mass% of carbonate structural units (Y), and had a biomass content of 21 mass%.

[0228] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0229] Example 2 A polycarbonate resin was produced by the same method as in Reference Example 1, except that a raw material mixture was prepared using 60.00 g (approximately 0.0103 mol) of P-6050, 40.00 g (approximately 0.131 mol), 30.50 g (approximately 0.142 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, with the calcium acetate monohydrate added at 150 μmol per mol of total dihydroxy compounds. The resulting polycarbonate resin contained 58.1 mass% of carbonate structural units (X) and 41.9 mass% of carbonate structural units (Y), and had a biomass content of 36 mass%.

[0230] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0231] [Example 3] P-6050 70.00 g (approximately 0.0120 mol), SPG 30.00 g (approximately 0.0986 mol), DPC 23.80 g (approximately 0.111 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, calcium acetate monohydrate was added so that the total dihydroxy compound was 200 μmol per 1 mol of the raw material mixture was prepared, and the reactor external temperature was raised to 240 ° C. instead of 250 ° C. The polycarbonate resin was produced by the method described in Reference Example 1. The obtained polycarbonate resin contains 68.3 mass% of carbonate structural units (X) and 31.7 mass% of carbonate structural units (Y), and the biomass content is 42 mass%.

[0232] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0233] Example 4 A polycarbonate resin was produced by the same method as in Reference Example 1, except that a raw material mixture was prepared using 56.02 g (approximately 0.0096 mol) of P-6050, 60.69 g (approximately 0.199 mol), 44.99 g (approximately 0.210 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, with the calcium acetate monohydrate added at 150 μmol per 1 mol of total dihydroxy compounds. The resulting polycarbonate resin contained 46.1 mass% of carbonate structural units (X) and 53.9 mass% of carbonate structural units (Y), and had a biomass content of 28 mass%.

[0234] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0235] [Example 5] P-6010 70.03 g (approximately 0.0122 mol), SPG 46.68 g (approximately 0.153 mol), DPC 36.01 g (approximately 0.168 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, calcium acetate monohydrate was added so that the total dihydroxy compound per 1 mol was 100 μmol to prepare a raw material mixture, and the reactor external temperature after heating from 220 ° C. was changed from 250 ° C. to 240 ° C., except that the production of a polycarbonate resin was carried out by the method described in Reference Example 1. The obtained polycarbonate resin contains 58.1 mass% of carbonate structural units (X) and 41.9 mass% of carbonate structural units (Y), and the biomass degree is 0 mass%.

[0236] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0237] [Example 6] O-2010 70.03 g (approximately 0.0349 mol), SPG 46.68 g (approximately 0.153 mol), DPC 40.54 g (approximately 0.189 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, calcium acetate monohydrate was added so that the total dihydroxy compound per 1 mol was 150 μmol to prepare a raw material mixture, and the reactor external temperature after heating from 220 ° C. was changed from 250 ° C. to 240 ° C., except that the production of a polycarbonate resin was carried out by the method described in Reference Example 1. The obtained polycarbonate resin contains 58.3 mass% of carbonate structural units (X) and 41.7 mass% of carbonate structural units (Y), and the biomass degree is 0 mass%.

[0238] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0239] [Example 7] O-4050 70.03 g (approximately 0.0174 mol), SPG 46.68 g (approximately 0.153 mol), DPC 36.77 g (approximately 0.172 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, calcium acetate monohydrate was added so that the total dihydroxy compound per 1 mol was 150 μmol to prepare a raw material mixture, and the reactor external temperature after heating from 220 ° C. was changed from 250 ° C. to 240 ° C., except that the production of a polycarbonate resin was carried out by the method described in Reference Example 1. The obtained polycarbonate resin contains 58.2 mass% of carbonate structural units (X) and 41.8 mass% of carbonate structural units (Y), and the biomass degree is 29 mass%.

[0240] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0241] [Example 8] O-5050 70.03 g (approximately 0.0142 mol), SPG 46.68 g (approximately 0.153 mol), DPC 36.08 g (approximately 0.168 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, calcium acetate monohydrate was added so that the total dihydroxy compound per 1 mol was 150 μmol to prepare a raw material mixture, and the reactor external temperature after heating from 220 ° C. was changed from 250 ° C. to 240 ° C., except that the production of a polycarbonate resin was carried out by the method described in Reference Example 1. The obtained polycarbonate resin contains 58.1 mass% of carbonate structural units (X) and 41.9 mass% of carbonate structural units (Y), and the biomass degree is 29 mass%.

[0242] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0243] Comparative Example 1 A raw material mixture was prepared by adding 55.84 g (approximately 0.109 mol) of PO3G500, 60.87 g (approximately 0.417 mol) of ISB, 113.62 g (approximately 0.530 mol) of DPC, and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst to a glass reactor having an internal volume of 570 mL and equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device.

[0244] Next, the pressure inside the glass reactor was reduced to 1.3 to 4.0 kPa (10 to 30 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated five times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 210°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Thereafter, the stirrer was rotated at 100 rpm. After stirring for 30 minutes, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute over 90 minutes while distilling off phenol, which was a by-product of the oligomerization reaction of the dihydroxy compound and DPC occurring inside the reactor.

[0245] Next, the pressure inside the reactor was maintained at 13.3 kPa, and a transesterification reaction was carried out for 45 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 220°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 133 Pa (1 Torr) absolute over 20 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was then reduced to 50 Pa (approximately 0.4 Torr), and a polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power.

[0246] The reactor was then pressurized with nitrogen to an absolute pressure of 101.3 kPa, and then the gauge pressure was increased to 0.2 MPa. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strands were pelletized using a rotary cutter. This polycarbonate resin contained neither the carbonate structural unit (X) nor the carbonate structural unit (Y), and had a biomass content of 89% by mass.

[0247] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0248] Comparative Example 2 A raw material mixture was prepared by adding 76.11 g (approximately 0.073 mol) of PO3G1000, 44.15 g (approximately 0.302 mol), 80.29 g (approximately 0.375 mol) of DPC, and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, so that the calcium acetate monohydrate concentration was 40 μmol per mol of total dihydroxy compounds, and a polycarbonate resin was produced in the same manner as in Comparative Example 1, except that the external temperature of the reactor was raised to 230° C. instead of 220° C. The obtained polycarbonate resin contained neither the carbonate structural unit (X) nor the carbonate structural unit (Y), and had a biomass degree of 92 mass%.

[0249] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0250] [Example 9 of Polycarbonate Resin Composition II] O-5050 70.03 g (approximately 0.0142 mol), BPA 46.68 g (approximately 0.205 mol), DPC 47.32 g (approximately 0.221 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, calcium acetate monohydrate was added so that the total dihydroxy compound was 150 μmol per 1 mol of the raw material mixture was prepared, and the reactor external temperature after heating from 220 ° C. was changed from 250 ° C. to 240 ° C., except that the production of a polycarbonate resin was carried out in the manner described in Reference Example 1. The obtained polycarbonate resin contained 57.5 mass% of carbonate structural units (X) and 42.5 mass% of carbonate structural units (Y), and had a biomass content of 29 mass%.

[0251] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0252] [Example 10 of Polycarbonate Resin Composition II] A polycarbonate resin was produced in the same manner as in Reference Example 1, except that a raw material mixture was prepared using 70.03 g (approximately 0.0142 mol) of O-5050, 46.68 g (approximately 0.231 mol), 53.55 g (approximately 0.250 mol), and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst, with the calcium acetate monohydrate added at 150 μmol per mol of total dihydroxy compounds. The resulting polycarbonate resin contained 57.2 mass% of carbonate structural units (X) and 42.8 mass% of carbonate structural units (Y), and had a biomass content of 29 mass%.

[0253] The polycarbonate resin thus obtained was subjected to the above-mentioned evaluations.

[0254] The evaluation results of Examples and Comparative Examples of Polycarbonate Resin Composition I according to the first embodiment of the present invention are summarized in Tables 2A and 2B, along with the content ratio of the carbonate structural unit (X) and the carbonate structural unit (Y1) in each polycarbonate resin. The evaluation results of Examples and Comparative Examples of Polycarbonate Resin Composition II according to the second embodiment of the present invention are summarized in Tables 3A and 3B, along with the content ratio of the carbonate structural unit (X) and the carbonate structural unit (Y2) in each polycarbonate resin. In Tables 2A, 2B, 3A, and 3B below, "-" in the evaluation result column indicates that the evaluation was not performed.

[0255]

[0256]

[0257]

[0258]

[0259] Tables 2A and 2B show that polycarbonate resin composition I of the present invention is excellent in heat resistance, long-term thermal stability, light resistance, flexibility, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency. In contrast, the polycarbonate resin compositions of Comparative Examples 1 and 2, which do not contain the carbonate structural unit (X) or the carbonate structural unit (Y1), are inferior in at least two of the following: heat resistance, long-term thermal stability, light resistance, flexibility, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency.

[0260] It can be seen from Tables 3A and 3B that the polycarbonate resin composition II of the present invention is excellent in heat resistance, long-term thermal stability, light resistance, flexibility, mechanical strength, low-temperature mechanical strength, and rubber elasticity. In contrast, the polycarbonate resin compositions of Comparative Examples 1 and 2, which do not contain the carbonate structural unit (X) or the carbonate structural unit (Y2), are inferior in at least two of the following: heat resistance, long-term thermal stability, light resistance, flexibility, mechanical strength, low-temperature mechanical strength, and rubber elasticity.

[0261] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2024-010350, filed on January 26, 2024, and is incorporated by reference in its entirety.

Claims

1. A polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) represented by the following formula (1) and a carbonate structural unit (Y1) derived from a dihydroxy compound (3) represented by the following formula (3). (In formula (1), A represents a divalent linking group having no cyclic structure, composed of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and hydrogen atoms, and a plurality of A's in formula (1) are the same. B represents a divalent linking group having no cyclic structure, composed of 1 to 40 carbon atoms and hydrogen atoms. n is an integer of 2 to 100.) 2. The polycarbonate resin composition according to claim 1, having a melting point peak temperature when heated at a temperature rising rate of 20 ° C / min using a differential scanning calorimeter to measure the melting point peak temperature.

3. The polycarbonate resin composition according to claim 1, wherein the content of the carbonate structural unit (X) in 100% by mass of all carbonate structural units of the polycarbonate resin composition is 1% by mass or more and 99% by mass or less, and the content of the carbonate structural unit (Y1) is 1% by mass or more and 99% by mass or less.

4. The polycarbonate resin composition according to claim 3, wherein the content of the carbonate structural unit (X) in 100% by mass of all carbonate structural units of the polycarbonate resin composition is 25% by mass or more and 80% by mass or less, and the content of the carbonate structural unit (Y1) is 20% by mass or more and 75% by mass or less.

5. The polycarbonate resin composition according to claim 4, wherein the content of the carbonate structural unit (X) in 100% by mass of all carbonate structural units of the polycarbonate resin composition is 50% by mass or more and 80% by mass or less, and the content of the carbonate structural unit (Y1) is 20% by mass or more and 50% by mass or less.

6. The polycarbonate resin composition according to claim 1, wherein the sum of the content of the carbonate structural unit (X) and the content of the carbonate structural unit (Y1) in 100% by mass of all carbonate structural units of the polycarbonate resin composition is 90% by mass or more.

7. The polycarbonate resin composition according to claim 1, wherein the number average molecular weight of the aliphatic polyester polyol (1) represented by the formula (1) is 400 or more and 10,000 or less.

8. The polyester polyol (1) is at least one selected from the group of aliphatic polyester polyols represented by the following formula (2) and the following formulas (10) to (12), the polycarbonate resin composition according to claim 1. (In the above formula, n, o, p, q, r, s are integers from 2 to 100. X is an n-nonylene group or a 2-methyl-1,8-octylene group.) 9. The polycarbonate resin composition according to claim 1, having the melting point peak temperature in the range of 100 ° C or higher.

10. The polycarbonate resin composition according to claim 1, having the melting point peak temperature in the range of 300 ° C or lower.

11. The polycarbonate resin composition according to claim 1, containing the carbonate structural unit (X) and the carbonate structural unit (Y) as a copolymerized polycarbonate resin.

12. The polycarbonate resin composition according to claim 1, which is a blend of a polycarbonate resin containing the carbonate structural unit (X) and a polycarbonate resin containing the carbonate structural unit (Y).

13. The polycarbonate resin composition according to claim 1, having a viscosity-average molecular weight of 20,000 or more and 150,000 or less.

14. The polycarbonate resin composition according to claim 1, having a glass transition temperature of 30°C or less when measured by heating at a heating rate of 20°C / min using a differential scanning calorimeter.

15. The polycarbonate resin composition according to claim 1, wherein the tensile elastic modulus of a sample obtained by hot pressing the polycarbonate resin composition is 5 MPa or more and 1000 MPa or less.

16. The polycarbonate resin composition according to claim 1, wherein the tensile elongation at break of a sample obtained by hot pressing the polycarbonate resin composition is 100% or more.

17. The polycarbonate resin composition according to claim 1, wherein the tensile permanent strain of a sample obtained by hot pressing the polycarbonate resin composition is 30% or less.

18. The polycarbonate resin composition according to claim 1, wherein the recovery rate of a sample obtained by hot pressing the polycarbonate resin composition is 70% or more.

19. The polycarbonate resin composition according to claim 1, having a retention rate of viscosity-average molecular weight of 80% or more after heating at 100°C for 100 hours using a hot air dryer.

20. The polycarbonate resin composition according to claim 1, having a retention rate of viscosity-average molecular weight of 90% or more after treatment for 168 hours under the conditions of a temperature of 80°C and a relative humidity of 96%.

21. The retention rate of the viscosity-average molecular weight after treatment for 100 hours at an irradiation intensity of 60 W / m ２ is 90% or more, and the polycarbonate resin composition according to claim 1.

22. The polycarbonate resin composition according to claim 1, wherein the total light transmittance of a 0.5 mm-thick film made of the polycarbonate resin composition is 83% or more.

23. A thermoplastic resin composition containing the polycarbonate resin composition according to claim 1, wherein the content of the polycarbonate resin composition in 100% by mass of the thermoplastic resin composition is 1% by mass or more and 30% by mass or less.

24. An injection molded article obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

25. An extruded product obtained by extrusion molding the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

26. The extruded product according to claim 25, wherein the extruded product is a sheet or a film.

27. A film material for a membrane structure building, obtained by using the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

28. A vibration damping material for an EV, obtained by using the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

29. A watch band, obtained by using the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

30. A camera grip, obtained by using the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

31. A catheter tube, obtained by using the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

32. A shoe midsole, obtained by using the polycarbonate resin composition according to any one of claims 1 to 22 or the thermoplastic resin composition according to claim 23.

33. A polycarbonate resin composition used for any one application selected from the group consisting of a film material used for a membrane structure building, a vibration damping material for an EV, a watch band, a camera grip, a catheter tube, and a shoe midsole, wherein the polycarbonate resin composition contains a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) represented by the following formula (1) and a carbonate structural unit (Y2) derived from a dihydroxy compound (2) that satisfies the following requirement I, and when measured using a differential scanning calorimeter at a heating rate of 20 °C / min to measure the melting point peak temperature, it is a polycarbonate resin composition having a melting point peak temperature. (In formula (1), A represents a divalent linking group having no cyclic structure, consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and hydrogen atoms, and a plurality of A's in formula (1) are the same. B represents a divalent linking group having no cyclic structure, consisting of 1 to 40 carbon atoms and hydrogen atoms. n is an integer from 2 to 100.) <Requirement I> When the dihydroxy compound (2) is polymerized with a polycarbonate resin (2) having a melt volume flow rate (MVR) of 5 to 120 cm ３ / 10 min at 260 °C and a load of 2.16 kg by a transesterification method with a carbonate source, the polycarbonate resin (2) is a dihydroxy compound having a melting point peak temperature when measured using a differential scanning calorimeter at a heating rate of 20 °C / min to measure the melting point peak temperature.

34. The polycarbonate resin composition according to claim 33, wherein the dihydroxy compound (2) is at least one selected from the group of dihydroxy compounds represented by the following formulas (3) to (7).

35. The polycarbonate resin composition according to claim 33, wherein the retention rate of the viscosity average molecular weight after heating at 100 °C for 100 hours using a hot air dryer is 80% or more.

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