Polycarbonate resin composition

Abstract

A polycarbonate resin composition containing 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 consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and a hydrogen atom, and a plurality of A in formula (1) are the same. B represents a divalent linking group consisting of 1 to 40 carbon atoms and a hydrogen atom. n is an integer of 2 to 100)

Description

Technical Field

[0001] This invention relates to polycarbonate resin compositions, and more specifically, to polycarbonate resin compositions exhibiting excellent heat resistance, long-term thermal stability, flexibility, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency. The invention also relates to thermoplastic resin compositions comprising the polycarbonate resin composition, and injection-molded and extruded articles thereof. Background Technology

[0002] Polycarbonate resin has excellent mechanical strength, electrical properties, and transparency, and is widely used as an engineering plastic in various fields such as electrical / electronic equipment and automobiles.

[0003] However, the current situation is that polycarbonate resins, like polyester-based thermoplastic elastomers and thermoplastic polyurethanes, are rarely used as elastomers. Further expansion of applications can be anticipated through the development of polycarbonate-based thermoplastic elastomers.

[0004] On the other hand, there are concerns about global warming caused by the depletion of oil resources and the increase in carbon dioxide emissions. Therefore, there is a demand for the development of plastics made from carbon-neutral plant-derived monomers. In this context, in recent years, polycarbonate resins made using isosorbide (hereinafter sometimes referred to as "ISB"), a plant-derived raw material, have been developed and are beginning to be used in automotive parts, optical applications, and glass replacement applications (see, for example, Patent Document 1 and Patent Document 2).

[0005] Traditional polycarbonate resins made from isosorbide have high elastic modulus, making them difficult to use as elastomers.

[0006] Patent Document 3 discloses a polycarbonate resin with excellent softness, hue, and thermal stability, made from a compound derived from plant-based raw materials, and a polycarbonate resin composition with excellent impact resistance and heat resistance obtained by using it as an impact resistance modifier. Specifically, Patent Document 3 proposes a copolymerized polycarbonate resin obtained using polytrimethylene ether glycol (hereinafter sometimes abbreviated as "PO3G") and isosorbide.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2004 / 111106

[0010] Patent Document 2: International Publication No. 2007 / 148604

[0011] Patent Document 3: Japanese Patent Application Publication No. 2021-91900 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] Although the copolymer polycarbonate resin in Patent Document 3 has excellent flexibility, its glass transition temperature is significantly reduced due to the copolymerization of polytrimethylene ether glycol, resulting in decreased heat resistance.

[0014] In order to use polycarbonate resin as a main component resin as an elastomer, not only is flexibility required, but also heat resistance and mechanical strength are also required, so it needs to be improved.

[0015] Under these circumstances, the object of the present invention is to provide a polycarbonate resin composition with excellent heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency.

[0016] Solution for solving the problem

[0017] The inventors have discovered that a polycarbonate resin composition comprising a carbonate structural unit derived from a specific aliphatic polyester polyol and a carbonate structural unit derived from a dihydroxy compound satisfying a specific requirement constitutes a polycarbonate resin composition that meets the above-mentioned objectives.

[0018] The present invention is based on the following [1] to

[57] .

[0019] [1] A polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) of formula (1) and a carbonate structural unit (Y1) derived from a dihydroxy compound (3) of formula (3).

[0020] [Chemical Formula 1]

[0021]

[0022] In formula (1), A represents a divalent linker without a ring structure consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom and hydrogen atom. The multiple A's in formula (1) are the same.

[0023] B represents a non-cyclic divalent linker consisting of 1 to 40 carbon and hydrogen atoms. (n is an integer from 2 to 100.)

[0024] [Chemical Formula 2]

[0025]

[0026] [2] The polycarbonate resin composition according to [1] has a melting point peak temperature when heated at a heating rate of 20°C / min using a differential calorimeter and the melting point peak temperature is measured.

[0027] [3] The polycarbonate resin composition according to [1] or [2], 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.

[0028] [4] According to the polycarbonate resin composition of [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.

[0029] [5] According to the polycarbonate resin composition of [4], wherein the content of the carbonate structural unit (X) in all 100% by mass of the polycarbonate 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.

[0030] [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) in all 100% by mass of the polycarbonate structural units of the polycarbonate resin composition is 90% by mass or more.

[0031] [7] The polycarbonate resin composition according to any one of [1] to [6], wherein the number average molecular weight of the aliphatic polyester polyol (1) represented by formula (1) is 400 or more and 10,000 or less.

[0032] [8] The polycarbonate resin composition according to any one of [1] to [7], wherein the aliphatic polyester polyol (1) is selected from one or more of the group consisting of the aliphatic polyester polyols shown in the following formula (2) and the following formulas (10) to (12).

[0033] [Chemical Formula 3]

[0034]

[0035] (In the above formula, n, o, p, q, r, and s are integers from 2 to 100. X is nonylene or 2-methyl-1,8-octylene.)

[0036] [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.

[0037]

[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 below 300°C.

[0038]

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

[10] , wherein the polycarbonate resin composition comprises the carbonate structural unit (X) and the carbonate structural unit (Y) in the form of a copolymerized polycarbonate resin.

[0039]

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

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

[0040]

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

[12] , wherein the viscosity-average molecular weight is 20,000 or more and 150,000 or less.

[0041]

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

[13] , wherein, when heated at a heating rate of 20°C / min using a differential calorimeter and the glass transition temperature is measured, the polycarbonate resin composition has a glass transition temperature of 30°C or less.

[0042]

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

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

[0043]

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

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

[0044]

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

[16] , wherein the tensile permanent deformation of the sample obtained by hot pressing of the polycarbonate resin composition is less than 30%.

[0045]

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

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

[0046]

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

[18] , wherein the viscosity-average molecular weight is retained at 80% or more after heating at 100°C for 100 hours using a hot air dryer.

[0047]

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

[19] , wherein the viscosity-average molecular weight is retained at 90% or more after treatment at a temperature of 80°C and a relative humidity of 96% for 168 hours.

[0048]

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

[20] , wherein a xenon lamp is used at an irradiation intensity of 60 W / m 2 The viscosity-average molecular weight was retained at over 90% after 100 hours of treatment.

[0049]

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

[21] , wherein the total light transmittance of the film with a thickness of 0.5 mm formed from the polycarbonate resin composition is 83% or more.

[0050]

[23] A thermoplastic resin composition comprising a 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.

[0051]

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

[22] or a thermoplastic resin composition according to

[23] .

[0052]

[25] An extruded article obtained by extruding a polycarbonate resin composition according to any one of [1] to

[22] or a thermoplastic resin composition according to

[23] .

[0053]

[26] The extruded article according to

[25] , wherein the extruded article is a sheet or film.

[0054]

[27] A membrane material used in a membrane structure building, obtained by using a polycarbonate resin composition according to any one of [1] to

[22] or a thermoplastic resin composition according to

[23] .

[0055]

[28] A vibration damping material for EV (Electric Vehicle): obtained by using a polycarbonate resin composition according to any one of [1] to

[22] or a thermoplastic resin composition according to

[23] .

[0056]

[29] A watch strap, obtained using a polycarbonate resin composition according to any one of [1] to

[22] or a thermoplastic resin composition according to

[23] .

[0057]

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

[22] or a thermoplastic resin composition according to

[23] .

[0058]

[31] A conduit fitting, obtained using a polycarbonate resin composition according to any one of [1] to

[22] or a thermoplastic resin composition according to

[23] .

[0059]

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

[22] or a thermoplastic resin composition according to

[23] .

[0060]

[33] A polycarbonate resin composition for use in any of the following groups selected from membrane materials used in membrane structure buildings, vibration damping materials for EVs, watch straps, camera grips, conduit fittings, and shoe midsoles.

[0061] The polycarbonate resin composition comprises a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) as shown in formula (1) below and a carbonate structural unit (Y2) derived from a dihydroxy compound (2) that satisfies condition I below.

[0062] The polycarbonate resin composition has a melting point peak temperature when heated using a differential operating calorimeter at a heating rate of 20°C / min and the melting point peak temperature is measured.

[0063] [Chemical Formula 4]

[0064]

[0065] (In formula (1), A represents a non-cyclic divalent linker consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and hydrogen atom. Multiple A's in formula (1) are the same. B represents a non-cyclic divalent linker consisting of 1 to 40 carbon atoms and hydrogen atoms. n is an integer from 2 to 100.)

[0066] <Requirement I>

[0067] The dihydroxy compound (2) is a dihydroxy compound that, when polymerized by transesterification with a carbonate source, has a melt volumetric flow rate (MVR) of 5–120 cm⁻¹ at 260 °C and a load of 2.16 kg. 3 When polycarbonate resin (2) is heated at a heating rate of 20°C / min using a differential calorimeter and the melting point peak temperature is measured, the polycarbonate resin (2) has a melting point peak temperature.

[0068]

[34] The polycarbonate resin composition according to

[33] , wherein the dihydroxy compound (2) is selected from any one or more of the dihydroxy compounds shown in the following formulas (3) to (7).

[0069] [Chemical Formula 5]

[0070]

[0071]

[35] The polycarbonate resin composition according to

[33] or

[34] wherein the viscosity-average molecular weight is retained at 80% or more after heating at 100°C for 100 hours using a hot air dryer.

[0072]

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

[33] to

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

[0073]

[37] According to the polycarbonate resin composition of

[36] , 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 (Y2) is 20% by mass or more and 75% by mass or less.

[0074]

[38] According to the polycarbonate resin composition of

[37] , 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 (Y2) is 20% by mass or more and 50% by mass or less.

[0075]

[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) in all 100% by mass of the polycarbonate structural units of the polycarbonate resin composition is 90% by mass or more.

[0076]

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

[33] to

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

[0077]

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

[33] to

[40] , wherein the aliphatic polyester polyol (1) is selected from one or more of the group consisting of the aliphatic polyester polyols shown in the following formula (2) and the following formulas (10) to (12).

[0078] [Chemical Formula 6]

[0079]

[0080] (In the above formula, n, o, p, q, r, and s are integers from 2 to 100. X is nonylene or 2-methyl-1,8-octylene.)

[0081]

[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.

[0082]

[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 below 300°C.

[0083]

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

[33] to

[43] , wherein the polycarbonate resin composition comprises the carbonate structural unit (X) and the carbonate structural unit (Y2) in a manner that copolymerizes the polycarbonate resin.

[0084]

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

[33] to

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

[0085]

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

[33] to

[45] , wherein the viscosity-average molecular weight is 20,000 or more and 150,000 or less.

[0086]

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

[33] to

[46] , wherein, when heated at a heating rate of 20°C / min using a differential calorimeter and the glass transition temperature is measured, the polycarbonate resin composition has a glass transition temperature of 30°C or less.

[0087]

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

[33] to

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

[0088]

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

[33] to

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

[0089]

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

[33] to

[49] , wherein the tensile permanent deformation of the sample obtained by hot pressing of the polycarbonate resin composition is less than 30%.

[0090]

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

[33] to

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

[0091]

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

[33] to

[51] , wherein the viscosity-average molecular weight is retained at 90% or more after treatment at a temperature of 80°C and a relative humidity of 96% for 168 hours.

[0092]

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

[33] to

[52] , wherein a xenon lamp is used at an irradiation intensity of 60 W / m 2 The viscosity-average molecular weight was retained at over 90% after 100 hours of treatment.

[0093]

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

[33] to

[53] , wherein the total light transmittance of the 0.5 mm thick film formed from the polycarbonate resin composition is 83% or more.

[0094]

[55] A thermoplastic resin composition comprising a 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.

[0095]

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

[33] to

[54] or a thermoplastic resin composition according to

[54] .

[0096]

[57] An extruded article obtained by extruding a polycarbonate resin composition according to any one of

[33] to

[54] or a thermoplastic resin composition according to

[54] .

[0097]

[58] The extruded article according to

[57] , wherein the extruded article is a sheet or film.

[0098] Invention Effects

[0099] According to the present invention, a polycarbonate resin composition with excellent heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency can be provided.

[0100] The polycarbonate resin composition of the present invention has good heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, rubber properties (tensile permanent deformation, recovery speed), and transparency, and therefore can be widely used as a material for manufacturing components in the automotive, electrical and electronic, and other industrial fields.

[0101] In particular, 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 straps, camera handles, conduit fittings, and shoe midsoles due to its excellent rubber properties (tensile permanent deformation, recovery speed). Detailed Implementation

[0102] The present invention will now be described in detail with reference to embodiments and examples. However, the present invention is not to be construed as being limited to the embodiments and examples shown below.

[0103] In this specification, unless otherwise specified, “~” is used to mean the lower limit and upper limit values, including the values ​​listed before and after it.

[0104] [Polycarbonate resin composition]

[0105] The polycarbonate resin composition of the first embodiment of the present invention is a polycarbonate resin composition comprising a carbonate structural unit (X) (hereinafter, sometimes simply referred to as "carbonate structural unit (X)") derived from an aliphatic polyester polyol (1) shown in 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) shown in the following formula (3).

[0106] [Chemical Formula 1]

[0107]

[0108] In formula (1), A represents a divalent linker without a ring structure consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom and hydrogen atom. The multiple A's in formula (1) are the same.

[0109] B represents a non-cyclic divalent linker consisting of 1 to 40 carbon and hydrogen atoms. (n is an integer from 2 to 100.)

[0110] [Chemical Formula 2]

[0111]

[0112] The polycarbonate resin composition of the second embodiment of the present invention is a polycarbonate resin composition for use in membrane materials selected from membrane structure buildings, vibration damping materials for EVs, watch straps, camera handles, conduit fittings, and shoe midsoles. The polycarbonate resin composition comprises a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) as shown in the following formula (1) and a carbonate structural unit (Y2) derived from a dihydroxy compound (2) satisfying condition I below (hereinafter, sometimes simply referred to as "carbonate structural unit (Y2)"). The polycarbonate resin composition has a melting point peak temperature when heated using a differential operating calorimeter at a heating rate of 20°C / min and the melting point peak temperature is measured.

[0113] [Chemical Formula 4]

[0114]

[0115] (In formula (1), A represents a non-cyclic divalent linker consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and hydrogen atom. Multiple A's in formula (1) are the same. B represents a non-cyclic divalent linker consisting of 1 to 40 carbon atoms and hydrogen atoms. n is an integer from 2 to 100.)

[0116] <Requirement I>

[0117] The dihydroxy compound (2) is a dihydroxy compound that, when polymerized by transesterification with a carbonate source, has a melt volumetric flow rate (MVR) of 5–120 cm⁻¹ at 260 °C and a load of 2.16 kg. 3 When polycarbonate resin (2) is heated at a heating rate of 20°C / min using a differential calorimeter and the melting point peak temperature is measured, the polycarbonate resin (2) has a melting point peak temperature.

[0118] In this invention, "carbonate structural unit" refers to a structural unit with carbonate bonds that is introduced into polycarbonate resin by reacting raw material compounds such as aliphatic polyester polyol (1), dihydroxy compound (2), and dihydroxy compound (3) during the manufacturing process of polycarbonate resin (-OROC(=O)-: R is a group derived from the raw material compound).

[0119] Hereinafter, the polycarbonate resin composition of the first embodiment of the present invention will be referred to as "polycarbonate resin composition I", the polycarbonate resin composition of 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 "the polycarbonate resin composition of the present invention".

[0120] Furthermore, the carbonate structural unit (Y1) contained in the polycarbonate resin composition of the first embodiment of the present invention and the carbonate structural unit (Y2) contained in the polycarbonate resin composition of the second embodiment of the present invention are collectively referred to as "carbonate structural unit (Y)".

[0121] <Aliphatic Polyester Polyols (1)>

[0122] The aliphatic polyester polyol (1), which is the raw material for the carbonate structural unit (X), is an aliphatic dihydroxy compound as shown in the following formula (1).

[0123] [Chemical Formula 5]

[0124]

[0125] (In formula (1), A represents a non-cyclic divalent linker consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and hydrogen atom. Multiple A's in formula (1) are the same. B represents a non-cyclic divalent linker consisting of 1 to 40 carbon atoms and hydrogen atoms. n is an integer from 2 to 100.)

[0126] From a polymerizability point of view, A in formula (1) is preferably a straight-chain or branched alkylene group having 1 to 9 carbon atoms, more preferably a straight-chain or branched alkylene group having 1 to 6 carbon atoms. As a branch, a branched alkylene group having 1 to 9 carbon atoms and a methyl group is preferred, more preferably a branched alkylene group having 1 to 6 carbon atoms. Furthermore, B in formula (1) is preferably a straight-chain alkylene group having 1 to 10 carbon atoms.

[0127] From the viewpoint of ease of acquisition and polymerizability, the aliphatic polyester polyol (1) is preferably selected from any one or more of the aliphatic polyester polyols shown in the following formula (2) and the following formulas (10) to (12), among which the aliphatic polyester polyol shown in the following formula (2) is preferred.

[0128] [Chemical Formula 3]

[0129]

[0130] (In the above formula, n, o, p, q, r, and s are integers from 2 to 100. X is nonylene or 2-methyl-1,8-octylene.)

[0131] The aliphatic polyester polyol shown in formula (2) above is preferably a biomass-derived aliphatic polyester polyol synthesized by polycondensation of 3-methyl-1,5-pentanediol and sebacic acid produced from plant-derived raw materials.

[0132] The aliphatic polyester polyol shown in formula (12) above is preferably a biomass-derived aliphatic polyester polyol synthesized by polycondensation of 1,9-nonanediol and 2-methyl-1,8-pentanediol with sebacic acid produced from plant-derived raw materials.

[0133] Whether aliphatic polyester polyols are manufactured from plant-derived resources, for example, through radiocarbon dating (…). 14 Confirmation was made by measuring the concentration of C).

[0134] Ideally, the number average molecular weight of the aliphatic polyester polyol (1) is 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, n in formulas (1) and (2) above, o in formula (10) above, p and q in formula (11) above, and r and s in formula (12) above are preferably numbers that satisfy the number average molecular weight.

[0135] 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), namely 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, exhibiting heat resistance, softness, low-temperature mechanical strength, and rubber elasticity.

[0136] If the number average molecular weight of the aliphatic polyester polyol (1) is above the lower limit, it tends to easily form soft and hard segments, thus easily achieving heat resistance, softness, low-temperature mechanical strength, and rubber elasticity. If the number average molecular weight of the aliphatic polyester polyol (1) is below the upper limit, it has good compatibility with dihydroxy compound (3) or dihydroxy compound (2), and can prevent adverse situations such as deterioration of transparency and failure of polymerization due to poor compatibility.

[0137] It should be noted that there is no particular restriction on the ratio of p to q in the above formula (11). From the point of view of raw material availability, it is preferred that p:q = 1:0.2 to 1, and particularly preferred that p:q = 1:0.4 to 0.7.

[0138] Furthermore, from the same point of view, the ratio of r to s in the above formula (12) is preferably r:s=1:0.2~1, and particularly preferably r:s=1:0.4~0.7.

[0139] <Dihydroxy compound (3)>

[0140] The dihydroxy compound (3) that serves as the raw material for the carbonate structural unit (Y1) is the dihydroxy compound shown in the following formula (3), namely spirocyclic diol (hereinafter sometimes abbreviated as "SPG").

[0141] [Chemical Formula 2]

[0142]

[0143] <Dihydroxy compound (2)>

[0144] The dihydroxy compound (2), which serves as the raw material for the carbonate structural unit (Y2), satisfies the following requirement I.

[0145] <Requirement I>

[0146] The dihydroxy compound (2) is a dihydroxy compound with a melt volumetric flow rate (MVR) of 5–120 cm⁻¹ at 260 °C and 2.16 kg load, obtained by transesterification with a carbonate source. 3 When polycarbonate resin (2) is heated at a heating rate of 20°C / min using a differential calorimeter and the melting point peak temperature is measured, the polycarbonate resin (2) has a melting point peak temperature.

[0147] Specifically, in element I above, the method of polymerizing the dihydroxy compound (2) with a carbonate source via transesterification to produce polycarbonate resin (2) can be carried out in the same manner as the melt transesterification method in the method for producing the polycarbonate resin composition of the present invention described later. Examples of carbonate sources used in this process include those exemplified as carbonates in the melt transesterification method described later.

[0148] As described above, "having a melting point peak temperature" in polycarbonate resin (2) means that polycarbonate resin (2) "has crystallinity". Within the range of the specific MVR described above, as long as the dihydroxy compound (2) can produce a polycarbonate resin (2) with crystallinity, the polycarbonate resin composition of the present invention with a melting point peak temperature can be produced as described below, and a polycarbonate resin composition with excellent heat resistance, softness, low-temperature mechanical strength and rubber elasticity can be provided.

[0149] It should be noted that in the determination of melting point peak temperature using a differential calorimeter, for polycarbonate resin (2), the polycarbonate resin (2) obtained by polymerization by transesterification can be used as is for the determination of melting point peak temperature, or the polycarbonate resin (2) obtained by temporarily dissolving the polycarbonate resin in a solvent and then drying and removing the solvent can be used to determine the melting point peak temperature.

[0150] That is, immediately after manufacturing, the polycarbonate resin (2) can be a resin that is crystalline in itself, or it can be a resin that is crystalline by dissolving it in a solvent after manufacturing and drying the solvent to remove it.

[0151] As the solvent used at this time, any solvent that can dissolve polycarbonate resin (2) is acceptable. Examples of solvents used in the method of mixing polycarbonate resin (a) and polycarbonate resin (b) in solution state, which will be described later, are listed.

[0152] Furthermore, there are no particular restrictions on the concentration of polycarbonate resin (2) in the solution or the drying method at this time.

[0153] Typically, in order to remove the solvent from the resin solution after the polycarbonate resin (2) has been dissolved, the method of letting it stand for a certain period of time under normal pressure or slightly reduced pressure, or the method of heating to above the boiling point of the solvent used under normal pressure or slightly reduced pressure, is used.

[0154] The polycarbonate resin (2) that is crystalline immediately after manufacture (a polycarbonate resin (2) that has a melting point peak temperature when the polycarbonate resin (2) obtained by transesterification is supplied as is for the determination of melting point peak temperature) has higher crystallinity than a polycarbonate resin that is crystalline by dissolving it in a solvent after manufacture and then drying the solvent.

[0155] Here, the MVR of the polycarbonate resin (2) used for determining the melting point peak temperature is set to 5–120 cm. 3 The reasons for setting the time limit to 10 minutes are as follows.

[0156] That is, when MVR is less than 5cm 3In polycarbonate resin with a t10min filtration rate, the increased branching may affect the crystallinity of polycarbonate resin (2), especially when the MVR exceeds 120cm20. 3 In polycarbonate resin with a molecular weight of 10 min, if the molecular weight is too low, the polycarbonate resin (2) may not become a polymer.

[0157] Therefore, in this invention, the MVR is set to 5–120 cm. 3 / 10min of polycarbonate resin (2) was used for the determination of melting point peak temperature.

[0158] There is no particular limitation on the melting point peak temperature of the polycarbonate resin (2), but for the same reason as the melting point peak temperature of the polycarbonate resin composition of the present invention described later, it is preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, preferably 300°C or lower, and more preferably 260°C or lower.

[0159] When the polycarbonate resin (2) has multiple melting point peak temperatures, it is preferable that at least one of the higher melting point peak temperatures is within the range described above.

[0160] The melting point peak temperature of polycarbonate resin (2) refers to the melting point peak temperature obtained by heating polycarbonate resin (2) at a heating rate of 20°C / min using a differential calorimeter, measuring the heat, and taking the temperature of the top of the melting peak. Specifically, it is determined by the method described in the following examples.

[0161] Furthermore, the MVR of the polycarbonate resin (2) was specifically determined by the method described in the examples described later.

[0162] As a dihydroxy compound (2), it is acceptable as long as the above requirement I is met, without any particular restrictions. As an example, dihydroxy compounds shown in the following formulas (3) to (7) can be listed.

[0163] That is, the following can be listed: spirocyclic diol (hereinafter, sometimes abbreviated as "SPG") as shown in formula (3), 4,4'-dihydroxydiphenyl ether (hereinafter, sometimes abbreviated as "DHDE") as shown in formula (4), bis(4-hydroxyphenylmethane) (=bisphenol F) (hereinafter, sometimes abbreviated as "BPF") as shown in formula (5), 4,4'-methylenebis(2,6-dimethylphenol) (hereinafter, sometimes abbreviated as "TmBPF") as shown in formula (6), and 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A) (hereinafter, sometimes abbreviated as "BPA") as shown in formula (7).

[0164] [Chemical Formula 5]

[0165]

[0166] The dihydroxy compounds shown in formulas (3) to (6) above are crystalline in themselves when used to make polycarbonate resin (2). The compound in formula (7) above is generally not crystalline in itself when used to make polycarbonate resin (2), but becomes crystalline by dissolving it in a solvent and drying it off. From the viewpoint of crystallinity, the dihydroxy compounds shown in formulas (3) to (6) above are more preferred. In particular, from the viewpoints of high crystallinity, heat resistance, softness, rubber elasticity, and transparency, the spirocyclic diol (SPG) shown in formula (3) above is especially preferred. Furthermore, from the viewpoints of heat resistance and softness, the 4,4'-dihydroxydiphenyl ether (DHDE) shown in formula (4) is preferred.

[0167] That is, the dihydroxy compound (2) of the present invention is preferably the spirocyclic diol shown in formula (3) or the 4,4'-dihydroxydiphenyl ether shown in formula (4).

[0168] <Containing morphologies of carbonate structural units (X) and (Y)>

[0169] There are no particular limitations on the morphology of the carbonate structural units (X) and carbonate structural units (Y) (carbonate structural unit (Y1) or carbonate structural unit (Y2)) in the polycarbonate resin composition of the present invention.

[0170] Typically, carbonate structural units (X) and carbonate structural units (Y) are contained in polycarbonate resin.

[0171] The polycarbonate resin composition of the present invention may be a mixture (blend) of polycarbonate resin containing a polycarbonate structural unit (X) and a polycarbonate resin containing a polycarbonate structural unit (Y), or may contain a copolymeric polycarbonate resin containing both a polycarbonate structural unit (X) and a polycarbonate structural unit (Y).

[0172] The polycarbonate resin composition of the present invention may be a mixture of a polycarbonate resin containing carbonate structural units (X) and / or carbonate structural units (Y) and a copolymer polycarbonate resin containing carbonate structural units (X) and carbonate structural units (Y).

[0173] The polycarbonate resin composition of the present invention may also comprise a polycarbonate resin that contains neither carbonate structural unit (X) nor carbonate structural unit (Y).

[0174] When the polycarbonate resin composition of the present invention contains carbonate structural units (X) and carbonate structural units (Y) in the form of a copolymer polycarbonate resin comprising carbonate structural units (X) and carbonate structural units (Y), the polycarbonate resin composition of the present invention is also referred to as "polycarbonate resin".

[0175] 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), it is generally referred to as a "polycarbonate resin composition". The same applies to the other containing forms described above.

[0176] In this invention, a case such as that consisting of a copolymer polycarbonate resin comprising carbonate structural units (X) and carbonate structural units (Y) is referred to as a "polycarbonate resin composition".

[0177] However, in the embodiments and comparative examples described later, a single copolymer polycarbonate resin is manufactured, and is therefore referred to as "polycarbonate resin" (the "polycarbonate resin" of the present invention).

[0178] <Content of each carbonate structural unit (X) and carbonate structural unit (Y)>

[0179] The content of carbonate structural unit (X) in 100% by mass of all carbonate structural units in the polycarbonate resin composition of the present invention (hereinafter, the content of carbonate structural units such as carbonate structural unit (X) and carbonate structural unit (Y) is expressed as a mass percentage 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 carbonate structural unit (Y) is preferably 1% by mass or more and 99% by mass or less.

[0180] By comprising 1% by mass and 99% by mass of carbonate structural units (X) and 1% by mass and 99% by mass of carbonate structural units (Y), the polycarbonate resin composition of the present invention can have good heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, rubber properties, and transparency.

[0181] From the viewpoint of flexibility and mechanical strength, the content of carbonate structural units (X) in the polycarbonate resin composition of the present invention is preferably 1% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass, particularly preferably 27% by mass or more, especially preferably 40% by mass or more, and most preferably 50% by mass or more. The content of carbonate structural units (Y) is preferably 99% by mass or less, more preferably 83% by mass or less, further preferably 75% by mass or less, particularly preferably 73% by mass or less, especially preferably 63% by mass or less, and most preferably 50% by mass or less.

[0182] From the viewpoint of heat resistance, the content of 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, especially preferably 60% by mass or less, and the content of 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, especially preferably 37% by mass or more.

[0183] The content ratio of carbonate structural units (X) and carbonate structural units (Y) in a polycarbonate resin composition can be determined by measuring the polycarbonate resin composition. 1 The result can be obtained using H-NMR.

[0184] From the viewpoint of more reliably obtaining the effects of heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, rubber properties, and transparency brought about by the presence of carbonate structural units (X) and carbonate structural units (Y), the sum of the content of carbonate structural unit (X) and the content of 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.

[0185] In the polycarbonate resin composition of the present invention, the aliphatic polyester polyol (1) constituting the carbonate structural unit (X) may be one type or two or more types. That is, it may contain carbonate structural units (X) derived from two or more aliphatic polyester polyols (1). Similarly, the carbonate structural unit (Y2) may also be one type or two or more types. That is, it may contain two or more carbonate structural units (Y2) derived from dihydroxy compound (2).

[0186] The contents of each carbonate structural unit (X) and (Y) in the polycarbonate resin composition of the present invention, and the proportions of other carbonate structural units described later, are as described above. This can be achieved by processing the polycarbonate resin composition...1 The result is obtained through analysis such as H-NMR determination. Details of this analytical method are shown in the examples section described later.

[0187] <Other carbonate structural units>

[0188] The polycarbonate resin composition of the present invention may also include, without prejudice to the purpose of the present invention, other carbonate structural units besides carbonate structural units (X) and carbonate structural units (Y) (carbonate structural unit (Y1) or carbonate structural unit (Y2)), namely carbonate structural units derived from aromatic or aliphatic dihydroxy compounds other than aliphatic polyester polyols (1) and dihydroxy compounds (2) or dihydroxy compounds (3).

[0189] Other carbonate structural units may also be included in the form of a copolymer polycarbonate resin with carbonate structural units (X) and / or carbonate structural units (Y), and the polycarbonate resin composed of other carbonate structural units may also be mixed with the polycarbonate resin containing carbonate structural units (X) and / or carbonate structural units (Y).

[0190] When the polycarbonate resin composition of the present invention contains other carbonate structural units, the content of other carbonate structural units in 100% by mass of all carbonate structural units of the polycarbonate resin composition is preferably 10% by mass or less, particularly preferably 5% by mass or less, and especially preferably 2% by mass or less.

[0191] By including other carbonate structural units in the polycarbonate resin composition, the energy source can sometimes be derived from these other carbonate structural units, resulting in improved effects such as reduced water absorption. However, if the content of these other units is excessive, it may impair the effects of the present invention, such as improved heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, rubber properties, and transparency, which are derived from the inclusion of carbonate structural units (X) and carbonate structural units (Y).

[0192] The polycarbonate resin composition of the present invention may contain only one type of other carbonate structural unit, or it may contain two or more types.

[0193] <Other Ingredients>

[0194] The polycarbonate resin composition of the present invention may, as needed, contain other components besides the polycarbonate resin comprising carbonate structural units (X) and / or carbonate structural units (Y), provided that it does not significantly impair the desired physical properties. Examples of other components include: polycarbonate resins not containing the aforementioned carbonate structural units (X) and carbonate structural units (Y), resins other than polycarbonate resins, various resin additives, etc.

[0195] Examples of resin additives include: heat stabilizers, antioxidants, release agents, lightfastness agents (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, dyes, and pigments.

[0196] These resin additives may contain one type, or two or more types in any combination and ratio.

[0197] Other resins that may be included in the polycarbonate resin composition of the present invention include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, propylene 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; and polymethacrylate resin.

[0198] Other resins may be contained in one type, or in any combination and ratio of two or more types.

[0199] When the polycarbonate resin composition of the present invention is incorporated as an additive such as an impact modifier into the thermoplastic resin composition of the present invention described later, the polycarbonate resin composition of the present invention preferably contains a total of 70% or more of carbonate structural units (X) and carbonate structural units (Y) (carbonate structural unit (Y1) or carbonate structural unit (Y2)) in 100% by mass of the polycarbonate resin composition.

[0200] <Properties of Polycarbonate Resin Compositions>

[0201] (Melting point peak temperature of polycarbonate resin composition)

[0202] When the polycarbonate resin composition I is heated at a heating rate of 20°C / min using a differential calorimeter and the melting point peak temperature is measured, the polycarbonate resin composition I preferably has a melting point peak temperature, i.e., it is crystalline.

[0203] Furthermore, when polycarbonate resin composition II is heated at a heating rate of 20°C / min using a differential calorimeter and the melting point peak temperature is measured, polycarbonate resin composition II exhibits a melting point peak temperature, indicating that it is crystalline.

[0204] As stated above, the phrase "having a melting point peak temperature" in the context of a polycarbonate resin composition refers to the polycarbonate resin composition's "crystallization." It should be noted that in the determination of the melting point peak temperature using a differential calorimeter, the polycarbonate resin composition is supplied as is for the determination, excluding cases where the melting point peak temperature is determined from a polycarbonate resin composition obtained by temporarily dissolving the polycarbonate resin in a solvent and then drying off the solvent.

[0205] The polycarbonate resin composition of the present invention has a melting point peak temperature as determined by differential calorimetry, and can obtain good rubber elasticity through quasi-crosslinking. It provides a polycarbonate resin composition with excellent heat resistance, softness, low-temperature mechanical strength and rubber properties.

[0206] There are no particular limitations on the melting point peak temperature of polycarbonate resin composition I or polycarbonate resin composition II, but the melting point peak temperature determined by heating the polycarbonate resin composition of the present invention at a heating rate of 20°C / min using a differential calorimeter, measuring the heat, and taking the temperature of the peak of the melting point 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. If the melting point peak temperature is above the above lower limit, the heat resistance is excellent and preferred. Regarding the upper limit of the melting point peak temperature of the polycarbonate resin composition of the present invention, from the viewpoint of moldability, it is preferably 300°C or lower, more preferably 260°C or lower, and even more preferably 240°C or lower.

[0207] When the polycarbonate resin composition of the present invention has multiple melting point peak temperatures, it is preferable that at least one of the higher melting point peak temperatures is within the above-mentioned range.

[0208] Specifically, the melting point peak temperature of the polycarbonate resin composition of the present invention is determined by the method described in the following examples.

[0209] (Molecular weight of the polycarbonate resin composition)

[0210] The molecular weight of the polycarbonate resin composition of the present invention, expressed as a viscosity-average molecular weight (Mv) calculated from solution viscosity, is preferably 20,000 or more and 150,000 or less. If the viscosity-average molecular weight (Mv) is above the lower limit mentioned above, the mechanical properties of the polycarbonate resin composition of the present invention become good, and therefore this is preferred. If the viscosity-average molecular weight (Mv) is below the upper limit mentioned above, there is a tendency for the flowability and moldability of the polycarbonate resin composition of the present invention to become good, and therefore this is preferred.

[0211] From this perspective, the viscosity-average molecular weight (Mv) of the polycarbonate resin composition of the present invention is more preferably 25,000 or more, further preferably 30,000 or more, more preferably 120,000 or less, and even more preferably 100,000 or less.

[0212] The viscosity-average molecular weight (Mv) of the polycarbonate resin composition of the present invention refers to the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at 20°C, obtained using dichloromethane and chloroform as solvents and an Ubbelohde viscometer, according to Schnell's viscosity formula, i.e., η = 1.23 × 10⁻⁶. -4 Mv 0.83 The calculated value. In addition, the intrinsic viscosity (limiting viscosity) [η] refers to the intrinsic viscosity [ηsp] measured at each solution concentration [C] (g / dL) and calculated according to the following formula.

[0213] [Formula 1]

[0214]

[0215] (Glass transition temperature of polycarbonate resin composition)

[0216] The glass transition temperature of the polycarbonate resin composition of the present invention is not particularly limited, but the glass transition temperature determined by heating the polycarbonate resin composition of the present invention using a differential calorimeter at a heating rate of 20°C / min and measuring the heat is preferably 30°C or less, more preferably 25°C or less, and even more preferably 10°C or less. If the glass transition temperature is below the above-mentioned upper limit, the low-temperature mechanical strength and rubber elasticity are excellent. There is no particular limitation on the lower limit of the glass transition temperature of the polycarbonate resin composition of the present invention, but it is generally -100°C or more.

[0217] When the polycarbonate resin composition of the present invention has multiple glass transition temperatures, it is preferable that at least one of the lower glass transition temperatures is within the above-mentioned range.

[0218] (Tensive modulus of polycarbonate resin composition)

[0219] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of shape retention, the tensile modulus measured by the method described in the examples below is preferably 5 MPa or more, particularly preferably 20 MPa or more, and especially preferably 40 MPa or more. On the other hand, from the viewpoint of flexibility, this tensile modulus is preferably 1000 MPa or less, particularly preferably 300 MPa or less, and especially preferably 150 MPa or less.

[0220] (Tension elongation at break of polycarbonate resin composition)

[0221] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of mechanical strength, the elongation at break measured by the method described in the examples below is preferably 100% or more, particularly preferably 150% or more, and especially preferably 400% or more. From the viewpoint of mechanical strength, a higher elongation at break is more preferred, but from the viewpoint of shape retention, its upper limit is generally 1200% or less.

[0222] (Tension permanent deformation of polycarbonate resin composition)

[0223] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of rubber elasticity, the tensile permanent deformation measured by the method described in the examples below is preferably 30% or less, particularly preferably 25% or less, and especially preferably 15% or less. From the viewpoint of rubber elasticity, the smaller the tensile permanent deformation, the more preferred, but generally its lower limit is 1% or more.

[0224] (Recovery rate of polycarbonate resin composition)

[0225] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of rubber elasticity, the recovery rate measured by the method described in the following examples is preferably 70% or more, particularly preferably 80% or more, and especially preferably 90% or more. From the viewpoint of rubber elasticity, the higher the recovery rate, the more preferred, but generally its upper limit is 99% or less.

[0226] (Retention rate of viscosity-average molecular weight of polycarbonate resin composition)

[0227] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of long-term thermal stability, the retention rate of viscosity-average molecular weight (Mv) after heating at 100°C for 100 hours using a hot air dryer, as determined by the method described in the examples below (hereinafter, sometimes referred to as "long-term thermal stability Mv retention rate") is preferably 80% or more, particularly preferably 90% or more, and especially preferably 95% or more. From the viewpoint of long-term thermal stability, a higher long-term thermal stability Mv retention rate is preferred, but generally its upper limit is 105% or less.

[0228] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of hydrolysis resistance, the retention rate of viscosity-average molecular weight (Mv) after treatment at 80°C and 96% relative humidity for 168 hours, as determined by the method described in the examples below (hereinafter sometimes referred to as "hydrolysis resistance Mv retention rate"), is preferably 90% or more, particularly preferably 92% or more, and especially preferably 94% or more. From the viewpoint of hydrolysis resistance, a higher hydrolysis resistance Mv retention rate is preferred, but generally its upper limit is 105% or less.

[0229] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of lightfastness and weather resistance, the results measured by the method described in the following examples, using a xenon lamp with an irradiation intensity of 60 W / m, are as follows. 2 The retention rate of viscosity-average molecular weight (Mv) after 100 hours of treatment (hereinafter sometimes referred to as "lightfastness Mv retention rate") is preferably 90% or more, particularly preferably 95% or more, and especially preferably 97% or more. From the viewpoint of lightfastness and weather resistance, a higher lightfastness Mv retention rate is preferred, but its upper limit is usually 105% or less.

[0230] (Total light transmittance of the polycarbonate resin composition)

[0231] Regarding the polycarbonate resin composition of the present invention, from the viewpoint of transparency, the total light transmittance of a 0.5 mm thick film, measured by the method described in the examples below, is preferably 83% or more, particularly preferably 84% or more, and especially preferably 88% or more. From the viewpoint of transparency, the higher the total light transmittance, the more preferred, but generally its upper limit is 95% or less.

[0232] (Biomaterial quality of polycarbonate resin composition)

[0233] 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 among the carbonate structural units contained in the polycarbonate resin composition of the present invention. In the embodiments described later, the biomass degree of each polycarbonate resin is also calculated according to this definition.

[0234] From the perspective of the Sustainable Development Goals (SDGs) advocated by the United Nations, the higher the biomass content of the polycarbonate resin composition of the present invention, the more preferred it is, preferably 10% by mass or more, and more preferably 25% by mass or more. On the other hand, from the viewpoint that the carbonate source is basically derived from petroleum, its upper limit is generally 98% by mass or less.

[0235] [Method for manufacturing polycarbonate resin composition]

[0236] <Manufacturing Method of Polycarbonate Resin>

[0237] The polycarbonate resin constituting the polycarbonate resin composition of the present invention can be manufactured by conventionally known polymerization methods, which are not particularly limited. Examples of polymerization methods include: interfacial polymerization, melt transesterification, pyridine polymerization, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among these, melt transesterification and interfacial polymerization are preferred, and melt transesterification is more preferred. Hereinafter, particularly preferred methods will be specifically described.

[0238] (Melted transesterification method)

[0239] In the melt transesterification process, for example, a transesterification reaction is carried out between a carbonate and a dihydroxy compound from the feedstock.

[0240] By using a substance comprising an aliphatic polyester polyol (1) and a dihydroxy compound (3) or a dihydroxy compound (2) as a raw material dihydroxy compound, a copolymer polycarbonate resin comprising carbonate structural units (X) and carbonate structural units (Y) (carbonate structural unit (Y1) or carbonate structural unit (Y2)) can be manufactured. By using one of these dihydroxy compounds, a polycarbonate resin comprising carbonate structural units (X) or carbonate structural units (Y) can be manufactured.

[0241] In the case of manufacturing a polycarbonate resin containing the other carbonate structural units mentioned above, one or more dihydroxy compounds other than aliphatic polyester polyol (1) and dihydroxy compound (3) or dihydroxy compound (2) may be used.

[0242] As a carbonate, any compound shown in formula (8) below can be used, such as aryl carbonates, dialkyl carbonates, dihydroxy compounds, monohydroxy compounds, cyclic carbonates, etc.

[0243] [Chemical Formula 8]

[0244]

[0245] In the above formula (8), R 11 and R 12 Each of the following can be independently represented as an alkyl, aryl, or aralkyl group having 1 to 30 carbon atoms, optionally with a substituent.

[0246] Below, in R 11 and R 12 When the alkyl or aralkyl group is used, it is sometimes called a dialkyl carbonate ester. 11 and R 12 When it is aryl, it is sometimes called diaryl carbonate.

[0247] From the perspective of reactivity with dihydroxy compounds, R 11 and R 12 Preferably, all are aryl groups that optionally have substituents, and more preferably are diaryl carbonate esters represented by the following formula (9).

[0248] [Chemical Formula 9]

[0249]

[0250] In the above formula (9), R13 and R 14 Each group can be independently represented by a halogen atom, a nitro group, a cyano group, an alkyl group with 1 to 20 carbon atoms, an alkoxycarbonyl group with 1 to 20 carbon atoms, a cycloalkyl group with 4 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms. p and q can independently represent integers from 0 to 5.

[0251] Such carbonates specifically include: dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-tert-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(methylsalicylic acid phenyl) carbonate, xylene carbonate, and other optional diaryl carbonates having substituents. Among these, diphenyl carbonate is preferred.

[0252] These carbonates can be used alone or in combination of two or more.

[0253] Alternatively, the carbonate, preferably in amounts of 50 mol% or less, more preferably 30 mol% or less, can be replaced with a dicarboxylic acid or a dicarboxylic acid ester. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When such a dicarboxylic acid or dicarboxylic acid ester is used, a polyester carbonate can be obtained.

[0254] The ratio of the raw material dihydroxy compound to the carbonate is arbitrary as long as the desired polycarbonate resin is obtained. Preferably, the carbonate is used in a slightly smaller amount or a slightly larger amount than the raw material dihydroxy compound during polymerization. That is, the carbonate is preferably 0.95 to 1.30 times (mol ratio) of the dihydroxy compound, more preferably 0.98 to 1.20 times (mol ratio).

[0255] If the molar ratio is too small, the resulting polycarbonate resin will have more terminal OH groups, and the resin's thermal stability will tend to deteriorate. If the molar ratio is too large, the transesterification reaction rate will decrease, and sometimes the production of polycarbonate resin with the desired molecular weight will become difficult; the residual amount of carbonate in the resin will increase, sometimes causing odor during molding and when the molded product is made.

[0256] When manufacturing polycarbonate resins via melt transesterification, a transesterification catalyst is typically used. The transesterification catalyst is not particularly limited, and conventionally known transesterification catalysts can be used. For example, alkali metal compounds and / or alkaline earth metal compounds are preferred. Furthermore, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds can be used as adjuncts.

[0257] One type of transesterification catalyst can be used, or two or more can be used in any combination and ratio.

[0258] In the melt transesterification process, the reaction temperature is not particularly limited, and is usually between 100 and 300°C.

[0259] There is no particular limit to the pressure during the reaction, but it is usually a reduced pressure of less than 2 mmHg.

[0260] In practice, the melt polycondensation reaction can be carried out while removing byproducts under the conditions described.

[0261] The polycarbonate resin composition of the present invention is significantly affected by thermal history and oxidation in the presence of an alkaline catalyst, leading to deterioration of its color. Therefore, the reaction temperature is preferably set to below 300°C. Furthermore, to prevent oxygen leakage from the equipment due to excessive decompression, it is preferable to select a decompression condition with a lower limit of approximately 0.05 mmHg.

[0262] The reaction can be carried out using either batch or continuous methods. In the case of batch reaction, the order in which the reaction matrix (reaction raw materials), catalyst, additives, etc., are mixed is arbitrary, as long as the desired polycarbonate resin is obtained; any appropriate order can be set.

[0263] In the melt transesterification process, catalyst deactivators can also be used as needed. Compounds that neutralize the transesterification catalyst can be used as catalyst deactivators. Examples include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc.

[0264] Catalyst deactivators can be used in one form or in any combination and ratio of two or more.

[0265] The amount of catalyst deactivator used is not particularly limited, but it is generally 0.5 equivalents or more relative to the transesterification catalyst, preferably 1 equivalent or more, more preferably 3 equivalents or more, generally 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less.

[0266] The amount of catalyst deactivator used relative to polycarbonate resin is typically above 1 ppm and below 1000 ppm, preferably below 500 ppm.

[0267] <Method for manufacturing polycarbonate resin composition>

[0268] In the case where 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 a carbonate structural unit (X) and / or a carbonate structural unit (Y) and a copolymer polycarbonate resin containing a carbonate structural unit (X) and a carbonate structural unit (Y), and further, in the case where the polycarbonate resin composition contains two or more polycarbonate resins, such as a mixture containing a polycarbonate resin that does not contain either a carbonate structural unit (X) or a carbonate structural unit (Y), there are no particular limitations on the method of mixing multiple polycarbonate resins, such as polycarbonate resin (a) and polycarbonate resin (b), to manufacture the polycarbonate resin composition of the present invention, and methods 1) to 4) below can be listed.

[0269] 1) A method for melt-blending polycarbonate resin (a) and polycarbonate resin (b);

[0270] 2) A method for melt-blending polycarbonate resin (a) and polycarbonate resin (b) in a molten state;

[0271] 3) A method for mixing polycarbonate resin (a) and polycarbonate resin (b) in a solution state;

[0272] 4) A method for dry-blending polycarbonate resin (a) and polycarbonate resin (b);

[0273] The methods are explained below.

[0274] 1) A method for melt-blending polycarbonate resin (a) and polycarbonate resin (b);

[0275] For example, mixing devices such as kneaders, twin-screw extruders, and single-screw extruders are used to melt-blend polycarbonate resin (a) granules or powders with polycarbonate resin (b). The polycarbonate resin (a) granules or powders and polycarbonate resin (b) granules or powders can be pre-mixed in a solid state and then blended, or either one can be melted first using the aforementioned mixing device, and the other polycarbonate resin can be added and blended.

[0276] The mixing temperature is not particularly specified, but is preferably 200°C or higher, more preferably 210°C or higher, and even more preferably 220°C or higher. Furthermore, it is preferably 320°C or lower, and particularly preferably 300°C or lower. If the mixing temperature is too low, the polycarbonate resin (a) and polycarbonate resin (b) will not be completely mixed, and uneven hardness and impact resistance may occur when manufacturing molded articles, which is undesirable. If the mixing temperature is too high, the color of the polycarbonate resin composition may deteriorate, which is also undesirable.

[0277] 2) A method for melt-blending molten polycarbonate resin (a) with molten polycarbonate resin (b);

[0278] For example, mixing devices such as mixing tanks, static mixers, kneaders, twin-screw extruders, and single-screw extruders are used to mix molten polycarbonate resin (a) with molten polycarbonate resin (b). In this case, if the polycarbonate resin is obtained by melt polymerization, for example, it can be introduced into the above-mentioned mixing device in a molten state without cooling and solidification.

[0279] 3) A method for mixing polycarbonate resin (a) and polycarbonate resin (b) in a solution state;

[0280] The method is as follows: polycarbonate resin (a) and polycarbonate resin (b) are dissolved in a suitable solvent to form a solution, mixed in the solution state, and then separated into a polycarbonate resin composition.

[0281] 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 preferred, for example. These solvents can be used alone or in mixtures with other solvents.

[0282] Examples of mixing devices include stirred tanks and static mixers. As for the mixing temperature, there are no special requirements as long as the conditions for dissolving polycarbonate resin (a) and polycarbonate resin (b) are met; generally, it is carried out below the boiling point of the solvent used.

[0283] 4) A method of dry-blending polycarbonate resin (a) and polycarbonate resin (b);

[0284] The method is as follows: using a drum mixer, super mixer, Henschel mixer, Nota mixer, etc., to dry mix the granules or powder of polycarbonate resin (a) with the granules or powder of polycarbonate resin (b).

[0285] Of the methods described in 1) to 4), methods 1) and 2) which involve melt-blending polycarbonate resin (a) and polycarbonate resin (b) are preferred, as are methods 4) which involve dry-blending polycarbonate resin (a) and polycarbonate resin (b).

[0286] When manufacturing the polycarbonate resin composition, pigments, dyes, release agents, heat stabilizers, etc., may be appropriately added in any of the above methods without prejudice to the purpose of the present invention.

[0287] [Thermoplastic resin composition]

[0288] The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising the polycarbonate resin composition of the present invention described above.

[0289] From the viewpoints of heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, rubber elasticity, and moldability, 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 generally 1% by mass or more and 30% by mass or less, preferably 5% by mass or more and 25% by mass or less.

[0290] Other thermoplastic resins besides the polycarbonate resin composition of the present invention included in the thermoplastic resin composition of the present invention can be listed as examples of resins that the aforementioned polycarbonate resin composition of the present invention may contain. The thermoplastic resin composition of the present invention may contain the aforementioned additives that the polycarbonate resin composition of the present invention may contain.

[0291] The polycarbonate resin composition of the present invention, due to its excellent heat resistance, long-term thermal stability, softness, mechanical strength, low-temperature mechanical strength, and rubber elasticity, can be used in thermoplastic resin compositions as a physical property modifier such as an impact resistance modifier.

[0292] When the polycarbonate resin composition of the present invention is used as an additive such as an impact modifier for a thermoplastic resin composition as described above, the polycarbonate resin composition of the present invention preferably contains a total of 70% or more of carbonate structural units (X) and carbonate structural units (Y) (carbonate structural unit (Y1) or carbonate structural unit (Y2)) in 100% by mass of the polycarbonate resin composition.

[0293] [Molded product]

[0294] When manufacturing molded articles from the polycarbonate resin composition or thermoplastic resin composition of the present invention, a conventional extrusion molding machine or injection molding machine is used.

[0295] The molding temperature for 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. Furthermore, it is preferably 320°C or lower, more preferably 300°C or lower.

[0296] If the molding temperature is too low, the following may occur: the melt viscosity increases, the fluidity decreases, and the moldability decreases. If the molding temperature is too high, the polycarbonate resin composition or thermoplastic resin composition may sometimes become discolored, and the color of the resulting molded article will also deteriorate, which is undesirable. In addition, polycarbonate resin compositions containing structural units derived from aliphatic dihydroxy compounds, such as carbonate structural units (X), sometimes decompose at high temperatures.

[0297] When performing injection molding or extrusion molding, pigments, dyes, release agents, heat stabilizers, etc., may be appropriately added to the polycarbonate resin composition or thermoplastic resin composition of the present invention without prejudice to the purpose of the present invention.

[0298] <Injection Molded Products>

[0299] When manufacturing injection molded articles from the polycarbonate resin composition or thermoplastic resin composition of the present invention, a conventional injection molding machine is used.

[0300] When using an injection molding machine or similar device, the mold temperature is preferably 120°C or lower, more preferably 90°C or lower. Furthermore, it is preferably 20°C or higher, more preferably 30°C or higher.

[0301] If the mold temperature is too high, the cooling time during molding needs to be extended, which can sometimes lengthen the manufacturing cycle of the molded product and reduce productivity. If the mold temperature is too low, the melt viscosity of the polycarbonate resin composition or thermoplastic resin composition will be too high, which may prevent the production of uniform molded products and cause problems such as unevenness on the surface of the molded products, which is not preferable.

[0302] <Extruded Products>

[0303] When manufacturing extruded articles from the polycarbonate resin composition or thermoplastic resin composition of the present invention, a conventional extrusion molding machine is used. This extrusion molding machine is typically equipped with a T-die, a round die, etc., and can produce extruded articles of various shapes. Examples of extruded articles include: sheets, films, plates, tubes, pipes, etc. Among these, sheets or films are preferred.

[0304] For extruded articles of the polycarbonate resin composition or thermoplastic resin composition of the present invention, in order to improve adhesion, coatability, and printability, a hard coating may be laminated on one or both sides of the extruded article, or a weather-resistant and / or scratch-resistant improvement film may be hot-laminated on one or both sides of the extruded article. Furthermore, surface embossing, translucent processing, and opaque processing may also be performed.

[0305] [use]

[0306] The 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, softness, mechanical strength, low-temperature mechanical strength and rubber properties, and therefore can be used in buildings, vehicles, electrical / electronic equipment, machinery and other various fields.

[0307] In particular, considering the excellent rubber properties (tensile permanent deformation, recovery speed) of the polycarbonate resin composition of the present invention, the polycarbonate resin composition or thermoplastic resin composition of the present invention is useful in membrane materials used in membrane structure buildings, vibration damping materials for EVs, watch straps, camera handles, as well as conduit fittings, shoe midsoles and other applications.

[0308] Therefore, polycarbonate resin composition II can be used in any of the following applications: vibration damping materials for EVs, watch straps, camera grips, conduit fittings, and shoe midsoles.

[0309] [Required characteristics for various applications]

[0310] Membrane materials used in membrane structure buildings

[0311] Regarding the membrane materials used in membrane structure buildings, special requirements are placed on weather resistance, light resistance, heat resistance, long-term heat resistance, hydrolysis resistance, and transparency. Furthermore, from the perspective of SDGs, high biomass content is expected.

[0312] Therefore, the polycarbonate resin composition of the present invention, which is used in membrane materials for membrane structures, is particularly preferably to have the properties described below among the aforementioned properties of polycarbonate resin compositions.

[0313] Melting point peak temperature: From the point of view of heat resistance, it is preferably above 120°C, particularly preferably above 140°C, and especially preferably above 160°C.

[0314] Long-term thermal stability Mv retention rate: From the viewpoint of long-term thermal stability, it is preferably 90% or more, particularly preferably 95% or more, and especially preferably 97% or more.

[0315] Hydrolysis resistance Mv retention rate: From the perspective of hydrolysis resistance, it is preferably 90% or more, particularly preferably 93% or more, and especially preferably 95% or more.

[0316] Light resistance Mv retention rate: From the perspectives of weather resistance and light resistance, it is preferably 90% or more, particularly preferably 95% or more, and especially preferably 97% or more.

[0317] Biomass content: From the perspective of SDGs, it is preferably 10% by mass or more, particularly preferably 20% by mass or more, and especially preferably 25% by mass or more.

[0318] <Vibration damping material for EV>

[0319] Regarding the vibration damping material for EV, heat resistance and long-term heat resistance are required, and from the perspective of SDGs, a high biomass content is desired.

[0320] Therefore, the polycarbonate resin composition of the present invention applied to the vibration damping material for EV is also particularly preferably to have the following characteristics among the characteristics of the above-mentioned polycarbonate resin composition.

[0321] Melting point peak temperature: From the perspective of heat resistance, it is preferably 150 °C or more, particularly preferably 160 °C or more, and especially preferably 190 °C or more.

[0322] Long-term thermal stability Mv retention rate: From the perspective of long-term thermal stability, it is preferably 95% or more, particularly preferably 97% or more, and especially preferably 98% or more. <00\00695>

[0323] Biomass content: From the perspective of SDGs, it is preferably 10% by mass or more, particularly preferably 20% by mass or more, and especially preferably 25% by mass or more.

[0324] <Watch band>

[0325] Regarding the watch band, weather resistance, light resistance, and hydrolysis resistance are required, and from the perspective of SDGs, a high biomass content is desired.

[0326] Therefore, the polycarbonate resin composition of the present invention applied to the watch band is also particularly preferably to have the following characteristics among the characteristics of the above-mentioned polycarbonate resin composition.

[0327] Hydrolysis resistance Mv retention rate: From the perspective of hydrolysis resistance, it is preferably 90% or more, particularly preferably 93% or more, and especially preferably 95% or more.

[0328] Light resistance Mv retention rate: From the perspectives of weather resistance and light resistance, it is preferably 90% or more, particularly preferably 95% or more, and especially preferably 97% or more.

[0329] Biomass content: From the viewpoint of SDGs, it is preferably 10% by mass or more, particularly preferably 20% by mass or more, and especially preferably 25% by mass or more.

[0330] <Camera Handle>

[0331] Regarding the camera grip, it requires weather resistance, light resistance, and hydrolysis resistance, and from the perspective of SDGs, a high biomass content is expected.

[0332] Therefore, the polycarbonate resin composition of the present invention applied to a camera handle is particularly preferably to have the properties described below among the aforementioned properties of polycarbonate resin compositions.

[0333] Hydrolysis resistance Mv retention rate: From the point of view of hydrolysis resistance, it is preferably 90% or more, particularly preferably 93% or more, and especially preferably 95% or more.

[0334] Lightfastness Mv retention rate: From the point of view of weather resistance and lightfastness, it is preferably 90% or more, particularly preferably 95% or more, and especially preferably 97% or more.

[0335] Biomass content: From the viewpoint of SDGs, it is preferably 10% by mass or more, particularly preferably 20% by mass or more, and especially preferably 25% by mass or more.

[0336] <Conduit Fittings>

[0337] Regarding tubing and fittings, biocompatibility (hydrolysis resistance) is required, and from the perspective of SDGs, high biomass density is desirable.

[0338] Therefore, the polycarbonate resin composition of the present invention applied to conduit fittings is particularly preferably to have the properties described below among the aforementioned properties of the polycarbonate resin composition.

[0339] Hydrolysis resistance Mv retention rate: From the point of view of hydrolysis resistance, it is preferably 90% or more, particularly preferably 93% or more, and especially preferably 95% or more by mass.

[0340] Biomass content: From the viewpoint of SDGs, it is preferably 10% by mass or more, particularly preferably 20% by mass or more, and especially preferably 25% by mass or more.

[0341] <Shoe Midsole>

[0342] Regarding the shoe midsole, high resilience (rubber elasticity) is required, and from the perspective of SDGs, high biomass content is expected.

[0343] Therefore, the polycarbonate resin composition of the present invention applied to the midsole of a shoe is particularly preferably to have the properties described below among the aforementioned properties of the polycarbonate resin composition.

[0344] Tensile permanent deformation: From the viewpoint of rubber elasticity, it is preferably 30% or less, particularly preferably 20% or less, and especially preferably 12% or less.

[0345] Recovery speed: From the perspective of rubber elasticity, it is above 70%, especially above 85%, and particularly above 92%.

[0346] Biomass content: From the viewpoint of SDGs, it is preferably 10% by mass or more, particularly preferably 20% by mass or more, and especially preferably 25% by mass or more.

[0347] Example

[0348] The present invention will be further described in detail below based on embodiments. It should be noted that the present invention is not limited to the following embodiments.

[0349] The physical properties of the polycarbonate resins obtained in the following examples and comparative examples were evaluated by the methods described below.

[0350] (1) Viscosity-average molecular weight (Mv)

[0351] Polycarbonate resin was dissolved in dichloromethane (concentration 6.0 g / L), and the intrinsic viscosity (limiting viscosity) [η] (unit dL / g) at 20°C was determined using an Ubbelohde viscometer (manufactured by Moritomo Rika Co., Ltd.). The viscosity-average molecular weight (Mv) was calculated according to the Schnell viscosity formula (the formula below). Furthermore, regarding Example 2, due to its poor solubility in dichloromethane, the determination was performed by dissolving it in chloroform.

[0352] η = 1.23 × 10 -4 Mv 0.83

[0353] (2) Glass transition temperature (Tg) / Melting point peak temperature (Tm)

[0354] The determination was performed using a differential operating calorimeter (SII DSC6220). The obtained polycarbonate resin was used as the test sample without drying. An aluminum sample dish containing approximately 10 mg of the test sample was heated from 30 °C to 300 °C at a heating rate of 20 °C / min with nitrogen at a flow rate of 50 mL / min, and then cooled to -120 °C at a cooling rate of 40 °C / min. The sample was then heated again to 300 °C at a heating rate of 20 °C / min.

[0355] The differential scanning calorimetry (DSC) curve obtained during the second heating was used as the measurement curve for analysis. The glass transition temperature (Tg) and melting point peak temperature (Tm) were analyzed according to JIS K7121-1987.

[0356] The temperature at which the line obtained by extending the baseline from the low-temperature side to the high-temperature side intersects the tangent line drawn from the point where the gradient of the curve in the stepwise transition section of the glass transition is maximum is the extrapolated glass transition initiation temperature. This extrapolated glass transition temperature is set as the glass transition temperature (Tg). Furthermore, the melting point peak temperature (Tm) is set as the peak of the melting point peak temperature.

[0357] If the glass transition temperature (Tg) cannot be clearly determined and there is no melting point peak temperature (Tm), it is set to "nd".

[0358] (3) Long-term thermal stability

[0359] 1.0 g of the obtained polycarbonate resin particles were placed on an aluminum tray and placed in a WFO-400 constant temperature desiccator (manufactured by Tokai Rika & Instrument Co., Ltd.) and heated at 100°C for 100 hours. After heating for 100 hours, the viscosity-average molecular weight (Mv) was determined using the method described above, and the percentage (%) relative to the viscosity-average molecular weight before heating was calculated.

[0360] Tables 2A, 2B, 3A, and 3B below record “Mv retention rate of heating test at 100℃ for 100h”.

[0361] (4) Hydrolysis resistance

[0362] Using a small injection molding machine C, Mobile (manufactured by Shinco Sellbic Co., Ltd.), polycarbonate resin sheets with a thickness of 2 mm, a length of 25 mm, and a width of 25 mm were formed at a barrel temperature of 230°C and a mold temperature of 40°C to obtain test pieces. The viscosity-average molecular weight (Mv) of the test pieces before treatment was determined using the above method. The obtained test pieces were treated for 168 hours using a constant temperature and humidity bath PR-1KTH (manufactured by ESPEC Co., Ltd.) at a bath temperature of 80°C and a relative humidity of 96%. After 168 hours of treatment, the viscosity-average molecular weight (Mv) of the test pieces was determined using the above method, and the percentage (%) relative to the viscosity-average molecular weight of the test pieces before treatment was calculated.

[0363] Tables 2A, 2B, 3A, and 3B below record “Mv retention rate tested at 80℃ for 90% for 168h”.

[0364] (5) Light resistance

[0365] 1.0 g of the obtained polycarbonate resin particles were placed on an aluminum disk and placed in a small light irradiation test apparatus, EYESUN-CUBE Xenon (manufactured by Iwasaki Electric Co., Ltd.), under an irradiation intensity of 60 W / m. 2Under the specified conditions, the mixture was treated for 100 hours. After 100 hours of treatment, the viscosity-average molecular weight (Mv) was determined using the method described above, and the percentage (%) relative to the viscosity-average molecular weight before treatment was calculated.

[0366] In Tables 2A, 2B, 3A, and 3B below, it is recorded as "60W / m". 2 • 100h • Xe lamp test Mv retention rate.

[0367] (6) Tensile modulus / elongation at break

[0368] The obtained polycarbonate resin was dried at 70–80°C for at least 3 hours. Approximately 3g of SUS spacer material with a thickness of 0.5mm, a length of 70mm, and a width of 70mm was used. The material was then pressed for 1 minute at a hot press temperature of 200–240°C with preheating for 1–3 minutes and a pressure of 1–5MPa. The press, along with the spacer material, was then removed and cooled at room temperature to produce a 0.5mm thick sheet. This sheet was then cut into strips with a thickness of 0.5mm, a length of 70mm, and a width of 10mm to obtain strip-shaped test samples.

[0369] The subsequent tensile tests used test samples that had been hot-pressed for more than 24 hours.

[0370] The obtained test samples were subjected to tensile tests using a benchtop precision universal testing machine AUTOGRAPH AGS-X (manufactured by Shimadzu Corporation) with an initial chuck distance of 45 mm and a tensile speed of 50 mm / min. The tensile modulus and elongation at break were determined.

[0371] A lower tensile modulus indicates better flexibility. A higher elongation at break indicates better mechanical strength.

[0372] (7) Test piece bending test

[0373] After hot pressing as described above, the tablets are compressed for more than 24 hours.

[0374] The sheet obtained by hot pressing is alternately folded 5 times in a convex shape and 5 times in a concave shape, forming a total of 10 creases. If there is no breakage during the 10 folds, it is marked as "A". If a breakage or cut occurs during the 2nd to 10th folds, it is marked as "B". If a breakage or cut occurs during the first convex fold, it is marked as "C".

[0375] If the answer is A or B, it is judged to have high mechanical strength.

[0376] (8) Tensile permanent deformation / recovery speed

[0377] From the obtained polycarbonate resin, strip-shaped test specimens were prepared using the same method as for tensile modulus and elongation at break. The test specimens were then subjected to hot pressing as described above for at least 24 hours.

[0378] The obtained test samples were subjected to tensile testing using a benchtop precision universal testing machine, AUTOGRAPH AGS-X (manufactured by Shimadzu Corporation), with an initial chuck-to-mark distance (to-mark distance) of 45 mm and a tensile speed of 50 mm / min. The tensile speed was stopped when the sample was approximately 100% elongated (approximately 45 mm) and held for 10 minutes. The distance between the marks during the holding period was also measured.

[0379] Then, shrink it to the initial distance between the markings, take out the test sample, and measure the distance between the markings of the test sample immediately after taking it out (within 30 seconds) and 30 minutes after taking it out.

[0380] Using these measurements, calculate the elongation length (A), the recovery length immediately after removal (within 30 seconds) (C), and the recovery length 30 minutes after removal (B). Calculate the permanent tensile deformation and recovery speed using the following formula.

[0381] It should be noted that the calculation methods for elongation length (A), recovery length immediately after removal (C), and recovery length 30 minutes after removal (B), as well as the calculation formulas for tensile permanent deformation and recovery speed, are as follows.

[0382] Elongation (A): The difference between the distance between the marks when elongated to 100% and the initial distance between the chucks.

[0383] Recovery length (C) immediately after removal (within 30 seconds): The difference between the distance between the marks when they are 100% elongated and the distance between the marks immediately after removal (within 30 seconds).

[0384] Recovery length after 30 minutes (B): The difference between the distance between the markers when the line is 100% elongated and the distance between the markers after 30 minutes.

[0385] Permanent tensile deformation (%) = {((A) - (B)) / (A)} × 100 (%)

[0386] The smaller the tensile permanent deformation, the better the rubber's elasticity, and therefore the better it is.

[0387] Recovery rate = {(C) / (B)} × 100 (%)

[0388] A faster recovery speed means better rubber elasticity, making it a better choice.

[0389] (9) Total transmittance

[0390] A 0.5 mm thick hot-pressed film was prepared from the obtained polycarbonate resin using the same method as for tensile modulus and elongation at break. Test samples were then subjected to hot pressing for at least 24 hours. The polycarbonate resin film was measured twice using a spectrophotometer / haze meter (Nippon Denshoku Co., Ltd. COH7700) according to ISO 13468-1, and the average value was calculated.

[0391] [raw materials]

[0392] The compounds used in the following examples, reference examples, and comparative examples are referred to by the following abbreviations. Furthermore, the compounds used are products of the manufacturers listed below.

[0393] It should be noted that among the following compounds, P-2050, P-4050, P-6050, O-4050, O-5050, PO3G, and ISB use plant-derived raw materials.

[0394] <Dihydroxy compounds>

[0395] P-2050: The aliphatic polyester polyol represented by formula (2) has a number average molecular weight of 1965 (manufactured by KURARAY Company, trade name: KURARAY Polyol) and a biomass content of 59% by mass.

[0396] P-4050: The aliphatic polyester polyol represented by formula (2) has a number average molecular weight of 4110 (manufactured by KURARAY Company, trade name: KURARAY Polyol) and a biomass content of 62 by mass.

[0397] P-6050: The aliphatic polyester polyol represented by formula (2) has a number average molecular weight of 5844 (manufactured by KURARAY Company, trade name: KURARAY Polyol) and a biomass content of 62 by mass.

[0398] P-6010: The aliphatic polyester polyol represented by formula (10), with a number average molecular weight of 5724 (manufactured by KURARAY, trade name: KURARAY Polyol).

[0399] O-2010: The aliphatic polyester polyol represented by formula (11) has a number average molecular weight of 2004 (manufactured by KURARAY, trade name: KURARAY Polyol).

[0400] O-4050: The aliphatic polyester polyol represented by formula (12) has a number average molecular weight of 4022 (manufactured by KURARAY, trade name: KURARAY Polyol) and a biomass content of 51% by mass.

[0401] O-5050: The aliphatic polyester polyol represented by formula (12) has a number average molecular weight of 4921 (manufactured by KURARAY Company, trade name: KURARAY Polyol) and a biomass content of 51 by mass.

[0402] PO3G500: Polytrimethylene ether glycol, number average molecular weight 562 (manufactured by ALLESSA, trade name: VELVETOL), biomass content 100% by mass.

[0403] PO3G1000: Polytrimethylene ether glycol, number average molecular weight 1042 (manufactured by ALLESSA, trade name: VELVETOL), biomass content 100% by mass.

[0404] SPG: Spirocyclohexanediol (manufactured by MITSUBISHI GAS CHEMICAL).

[0405] ISB: Isosorbide (Roquette Frères), biomass 100% by mass.

[0406] DHDE: 4,4'-Dihydroxydiphenyl ether (manufactured by CHEMFISH).

[0407] BPA: 2,2-bis(4-hydroxyphenyl)propane (manufactured by MITSUBISHI CHEMICAL).

[0408] <carbonate>

[0409] DPC: Diphenyl carbonate (manufactured by MITSUBISHI CHEMICAL).

[0410] <Polymerization Catalyst>

[0411] Calcium acetate monohydrate (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.)

[0412] [Determination of glass transition temperature, melting point peak temperature, and melt volumetric flow rate (MVR) of polycarbonate resin formed from dihydroxy compound (2)]

[0413] As dihydroxy compounds, only the compounds shown in Table 1 were used to manufacture polycarbonate resins (equivalent to polycarbonate resin (2)) with 100% by mass of carbonate structural unit (Y2) using the polymerization method described later, and their glass transition temperature and melting point peak temperature were determined. Except that the temperature was lowered to 50°C at a cooling rate of 40°C / min instead of -120°C, the determination method was the same as described above, and the results are shown in Table 1. In addition, according to ISO 1133, the melt volume flow rate (MVR) per unit time (unit: cm) of polycarbonate resin samples dried at 100°C for 4 hours was determined at 260°C and under a load of 2.16 kg using a melt indexer F-F01 (manufactured by Toyo Seiki Co., Ltd.). 3 / 10min)

[0414] [Table 1]

[0415]

[0416] As shown in Table 1, all compounds used as dihydroxy compounds (2) in the examples have melting point peak temperatures.

[0417] [Polymerization method using SPG as a dihydroxy compound]

[0418] In a 570 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device, 116.71 g (approximately 0.383 mol) of SPG, 83.37 g (approximately 0.389 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst were added, such that each 1 mol of calcium acetate monohydrate relative to all dihydroxy compounds was 100 μmol, thus preparing a raw material mixture.

[0419] Next, the pressure inside the glass reactor was reduced to 1.3–4.0 kPa (10–30 Torr). Then, the pressure was repeatedly restored to atmospheric pressure five times using nitrogen to purge the reactor's interior. After nitrogen purging, the external temperature of the reactor was set to 220°C, and the internal temperature was gradually increased to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. Next, while distilling away the phenol byproduct from the oligomerization reaction of the dihydroxy compound with DPC inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over 40 minutes.

[0420] Next, the pressure inside the reactor was maintained at 13.3 kPa, and phenol was further distilled off while a transesterification reaction was carried out for 45 minutes. Afterward, the external temperature of the reactor was raised to 285°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) using an absolute pressure gauge over 40 minutes to remove the distilled phenol from the system. Then, the absolute pressure inside the reactor was reduced to 60 Pa (approximately 0.4 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the reactor agitator reached the pre-set stirring power.

[0421] Next, the reactor is pressurized to 101.3 kPa using an absolute pressure gauge with nitrogen, and then pressurized to 0.2 MPa using a gauge pressure gauge. Polycarbonate resin is then extracted from the bottom of the reactor in a strand-like manner. After obtaining the strand-like polycarbonate resin, it is granulated using a rotary cutter.

[0422] [Polymerization method using DHDE as a dihydroxy compound]

[0423] In a 570 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device, 116.71 g (approximately 0.577 mol) of DHDE, 123.64 g (approximately 0.577 mol) of DPC, and a 0.4% by mass aqueous solution of cesium carbonate as a catalyst were added, such that 1 mol of cesium carbonate relative to all dihydroxy compounds was 5 μmol, thus preparing a raw material mixture.

[0424] Next, the pressure inside the glass reactor was reduced to 1.3–4.0 kPa (10–30 Torr). Then, the pressure was repeatedly restored to atmospheric pressure five times using nitrogen to purge the reactor's interior. After nitrogen purging, the external temperature of the reactor was set to 220°C, and the internal temperature was gradually increased to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. Next, while distilling away the phenol byproduct from the oligomerization reaction of the dihydroxy compound with DPC inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over 40 minutes.

[0425] Next, the pressure inside the reactor was maintained at 13.3 kPa, and phenol was further distilled off while an 80-minute transesterification reaction was carried out. Afterward, the external temperature of the reactor was raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes using an absolute pressure gauge, removing the distilled phenol from the system. Then, the external temperature of the reactor was raised to 280°C, and the absolute pressure inside the reactor was reduced to 60 Pa (approximately 0.4 Torr) to carry out a polycondensation reaction. The polycondensation reaction was terminated when the reactor agitator reached the pre-set stirring power.

[0426] Next, the reactor is pressurized to 101.3 kPa using nitrogen with an absolute pressure gauge, and then pressurized to 0.2 MPa using a gauge pressure gauge. Polycarbonate resin is then extracted from the bottom of the reactor in a strand-like manner. After obtaining the strand-like polycarbonate resin, it is granulated using a rotary cutter.

[0427] [Determination of the proportion of carbonate structural units]

[0428] The proportions of carbonate structural units (X), carbonate structural units (Y1), and carbonate structural units (Y2) in the polycarbonate resins manufactured in the following examples, reference examples, and comparative examples can be determined according to... 1 The value can be calculated from the H-NMR measurement, but it can also be determined based on the amount of dihydroxy compounds added during the manufacture of polycarbonate resin.

[0429] [Reference Example 1]

[0430] In a 570 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device, 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% by mass aqueous solution of calcium acetate monohydrate as a catalyst were added, such that each 1 mol of calcium acetate monohydrate relative to all dihydroxy compounds was 150 μmol, thus preparing a raw material mixture.

[0431] Next, the pressure inside the glass reactor was reduced to 50 Pa (0.38 Torr). Then, the pressure was repeatedly restored to atmospheric pressure three times using nitrogen to purge the reactor's interior with nitrogen. After nitrogen purging, the external temperature of the reactor was set to 220°C, and the internal temperature was gradually increased to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. Then, while distilling away the phenol byproduct from the oligomerization reaction of the dihydroxy compound with DPC inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over 40 minutes.

[0432] Next, the pressure inside the reactor was maintained at 13.3 kPa, and phenol was further distilled off while an 80-minute transesterification reaction was carried out. Afterward, the external temperature of the reactor was raised to 250°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) using an absolute pressure gauge over 40 minutes, removing the distilled phenol from the system. Then, the absolute pressure inside the reactor was reduced to 30 Pa (approximately 0.2 Torr) to allow for polycondensation. The polycondensation reaction was terminated when the reactor agitator reached the pre-set stirring power.

[0433] Next, the reactor is pressurized to 101.3 kPa using nitrogen with an absolute pressure gauge, and then pressurized to 0.2 MPa using a gauge pressure gauge. Polycarbonate resin is then extracted from the bottom of the reactor in a strand-like manner. After obtaining the strand-like polycarbonate resin, it is granulated using a rotary cutter.

[0434] The polycarbonate resin contains 58.3% by mass of carbonate structural units (X) and 41.7% by mass of carbonate structural units (Y), with a biomass content of 34% by mass.

[0435] The polycarbonate resin obtained in this way was evaluated as described above.

[0436] [Example 1]

[0437] A raw material mixture was prepared by adding 35.00 g (about 0.0085 mol) of P-4050, 65.00 g (about 0.214 mol) of SPG, 47.81 g (about 0.223 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that the calcium acetate monohydrate is 200 μmol per mol relative to all dihydroxy compounds. Otherwise, the polycarbonate resin was manufactured using the method described in Reference Example 1.

[0438] The obtained polycarbonate resin contains 33.3% by mass of carbonate structural units (X) and 66.7% by mass of carbonate structural units (Y), with a biomass content of 21% by mass.

[0439] The polycarbonate resin obtained in this way was evaluated as described above.

[0440] [Example 2]

[0441] A raw material mixture was prepared by adding 60.00 g (about 0.0103 mol) of P-6050, 40.00 g (about 0.131 mol) of SPG, 30.50 g (about 0.142 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that the calcium acetate monohydrate is 150 μmol per mol of all dihydroxy compounds. Otherwise, the polycarbonate resin was manufactured using the method described in Reference Example 1.

[0442] The obtained polycarbonate resin contains 58.1% by mass of carbonate structural units (X) and 41.9% by mass of carbonate structural units (Y), with a biomass content of 36% by mass.

[0443] The polycarbonate resin obtained in this way was evaluated as described above.

[0444] [Example 3]

[0445] Add 70.00 g (about 0.0120 mol) of P-6050, 30.00 g (about 0.0986 mol) of SPG, 23.80 g (about 0.111 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that each 1 mol of calcium acetate monohydrate is 200 μmol relative to all dihydroxy compounds, to prepare a raw material mixture. Raise the external temperature of the reactor to 240°C instead of 250°C, and otherwise carry out the manufacture of polycarbonate resin using the method described in Reference Example 1.

[0446] The obtained polycarbonate resin contains 68.3% by mass of carbonate structural units (X) and 31.7% by mass of carbonate structural units (Y), with a biomass content of 42 by mass.

[0447] The polycarbonate resin obtained in this way was evaluated as described above.

[0448] [Example 4]

[0449] A raw material mixture was prepared by adding 56.02 g (about 0.0096 mol) of P-6050, 60.69 g (about 0.199 mol) of SPG, 44.99 g (about 0.210 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that the calcium acetate monohydrate is 150 μmol per mol relative to all dihydroxy compounds. Otherwise, the polycarbonate resin was manufactured using the method described in Reference Example 1.

[0450] The obtained polycarbonate resin contains 46.1% by mass of carbonate structural units (X) and 53.9% by mass of carbonate structural units (Y), with a biomass content of 28% by mass.

[0451] The polycarbonate resin obtained in this way was evaluated as described above.

[0452] [Example 5]

[0453] Add 70.03 g (approximately 0.0122 mol) of P-6010, 46.68 g (approximately 0.153 mol) of SPG, 36.01 g (approximately 0.168 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that each 1 mol of calcium acetate monohydrate is 100 μmol relative to all dihydroxy compounds, to prepare a raw material mixture. Change the external temperature of the reactor from 250°C to 240°C after heating from 220°C. Otherwise, carry out the manufacture of polycarbonate resin using the method described in Reference Example 1.

[0454] The obtained polycarbonate resin contains 58.1% by mass of carbonate structural units (X) and 41.9% by mass of carbonate structural units (Y), with a biomass degree of 0 by mass.

[0455] The polycarbonate resin obtained in this way was evaluated as described above.

[0456] [Example 6]

[0457] Add 70.03 g (approximately 0.0349 mol) of O-2010, 46.68 g (approximately 0.153 mol) of SPG, 40.54 g (approximately 0.189 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that each 1 mol of calcium acetate monohydrate is 150 μmol relative to all dihydroxy compounds, to prepare a raw material mixture. Change the external temperature of the reactor from 250°C to 240°C after heating from 220°C. Otherwise, carry out the manufacture of polycarbonate resin using the method described in Reference Example 1.

[0458] The obtained polycarbonate resin contains 58.3% by mass of carbonate structural units (X) and 41.7% by mass of carbonate structural units (Y), with a biomass degree of 0 by mass.

[0459] The polycarbonate resin obtained in this way was evaluated as described above.

[0460] [Example 7]

[0461] Add 70.03 g (approximately 0.0174 mol) of P-4050, 46.68 g (approximately 0.153 mol) of SPG, 36.77 g (approximately 0.172 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that each 1 mol of calcium acetate monohydrate is 150 μmol relative to all dihydroxy compounds, to prepare a raw material mixture. Change the external temperature of the reactor from 250°C to 240°C after heating from 220°C. Otherwise, carry out the manufacture of polycarbonate resin using the method described in Reference Example 1.

[0462] The obtained polycarbonate resin contains 58.2% by mass of carbonate structural units (X) and 41.8% by mass of carbonate structural units (Y), with a biomass content of 29% by mass.

[0463] The polycarbonate resin obtained in this way was evaluated as described above.

[0464] [Example 8]

[0465] Add 70.03 g (approximately 0.0142 mol) of O-5050, 46.68 g (approximately 0.153 mol) of SPG, 36.08 g (approximately 0.168 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that each 1 mol of calcium acetate monohydrate is 150 μmol relative to all dihydroxy compounds, to prepare a raw material mixture. Change the external temperature of the reactor from 250°C to 240°C after heating from 220°C. Otherwise, carry out the manufacture of polycarbonate resin using the method described in Reference Example 1.

[0466] The obtained polycarbonate resin contains 58.1% by mass of carbonate structural units (X) and 41.9% by mass of carbonate structural units (Y), with a biomass content of 29% by mass.

[0467] The polycarbonate resin obtained in this way was evaluated as described above.

[0468] [Comparative Example 1]

[0469] In a 570 mL glass reactor equipped with a reactor stirrer, reactor heating device, and reactor pressure adjustment device, 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% by mass aqueous solution of calcium acetate monohydrate as a catalyst were added, so that the calcium acetate monohydrate was 140 μmol per mol of all dihydroxy compounds, thus preparing a raw material mixture.

[0470] Next, the pressure inside the glass reactor was reduced to 1.3–4.0 kPa (10–30 Torr). Then, the pressure was repeatedly restored to atmospheric pressure five times using nitrogen to purge the reactor's interior with nitrogen. After nitrogen purging, the external temperature of the reactor was set to 210°C, and the internal temperature was gradually increased to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. After stirring for 30 minutes, while distilling away the phenol byproduct from the oligomerization reaction of the dihydroxy compound with DPC inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) using an absolute pressure gauge over 90 minutes.

[0471] Next, the pressure inside the reactor was maintained at 13.3 kPa, and phenol was further distilled off while a transesterification reaction was carried out for 45 minutes. Afterward, the external temperature of the reactor was raised to 220°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 133 Pa (1 Torr) using an absolute pressure gauge over 20 minutes, removing the distilled-off phenol from the system. Then, the absolute pressure inside the reactor was reduced to approximately 50 Pa (approximately 0.4 Torr) to allow for polycondensation. The polycondensation reaction was terminated when the reactor agitator reached the pre-set stirring power.

[0472] Next, the reactor is pressurized to 101.3 kPa using nitrogen with an absolute pressure gauge, and then pressurized to 0.2 MPa using a gauge pressure gauge. Polycarbonate resin is then extracted from the bottom of the reactor in a strand-like manner. After obtaining the strand-like polycarbonate resin, it is granulated using a rotary cutter.

[0473] The polycarbonate resin contains neither carbonate structural units (X) nor carbonate structural units (Y), and has a biomass content of 89% by mass.

[0474] The polycarbonate resin obtained in this way was evaluated as described above.

[0475] [Comparative Example 2]

[0476] A raw material mixture was prepared by adding 76.11 g (approximately 0.073 mol) of PO3G1000, 44.15 g (approximately 0.302 mol) of ISB, 80.29 g (approximately 0.375 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that each 1 mol of calcium acetate monohydrate is 40 μmol relative to all dihydroxy compounds. The external temperature of the reactor was raised to 230°C instead of 220°C. Otherwise, the polycarbonate resin was manufactured using the method described in Comparative Example 1.

[0477] The resulting polycarbonate resin contains neither carbonate structural units (X) nor carbonate structural units (Y), and has a biomass content of 92 by mass.

[0478] The polycarbonate resin obtained in this way was evaluated as described above.

[0479] [Example 9 of polycarbonate resin composition II]

[0480] Add 70.03 g (approximately 0.0142 mol) of O-5050, 46.68 g (approximately 0.205 mol) of BPA, 47.32 g (approximately 0.221 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that each 1 mol of calcium acetate monohydrate is 150 μmol relative to all dihydroxy compounds, to prepare a raw material mixture. Change the external temperature of the reactor from 250°C to 240°C after heating from 220°C. Otherwise, carry out the manufacture of polycarbonate resin using the method described in Reference Example 1.

[0481] The obtained polycarbonate resin contains 57.5% by mass of carbonate structural units (X) and 42.5% by mass of carbonate structural units (Y), with a biomass content of 29% by mass.

[0482] The polycarbonate resin obtained in this way was evaluated as described above.

[0483] [Example 10 of polycarbonate resin composition II]

[0484] A raw material mixture was prepared by adding 70.03 g (about 0.0142 mol) of O-5050, 46.68 g (about 0.231 mol) of DHDE, 53.55 g (about 0.250 mol) of DPC, and a 3.0% by mass aqueous solution of calcium acetate monohydrate as a catalyst, such that the calcium acetate monohydrate is 150 μmol per mol of all dihydroxy compounds. Otherwise, the polycarbonate resin was manufactured using the method described in Reference Example 1.

[0485] The obtained polycarbonate resin contains 57.2% by mass of carbonate structural units (X) and 42.8% by mass of carbonate structural units (Y), with a biomass content of 29% by mass.

[0486] The polycarbonate resin obtained in this way was evaluated as described above.

[0487] The evaluation results of the examples and comparative examples of the polycarbonate resin composition I of the first embodiment of the present invention, together with the content ratio of carbonate structural units (X) and carbonate structural units (Y1) of each polycarbonate resin, are summarized in Tables 2A and 2B.

[0488] The evaluation results of the examples and comparative examples of the polycarbonate resin composition II of the second embodiment of the present invention, together with the content ratio of carbonate structural units (X) and carbonate structural units (Y2) of each polycarbonate resin, are summarized in Tables 3A and 3B.

[0489] It should be noted that in Tables 2A, 2B, 3A, and 3B below, a column for the evaluation result marked with "-" indicates that the evaluation was not performed.

[0490] [Table 2A]

[0491]

[0492] [Table 2B]

[0493]

[0494] [Table 3A]

[0495]

[0496] [Table 3B]

[0497]

[0498] As can be seen from Tables 2A and 2B, the polycarbonate resin composition I of the present invention exhibits excellent heat resistance, long-term thermal stability, light resistance, softness, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency.

[0499] In contrast, the polycarbonate resin compositions of Comparative Example 1 and Comparative Example 2, which do not contain either carbonate structural unit (X) or carbonate structural unit (Y1), are worse than in any two of the following: heat resistance, long-term thermal stability, light resistance, softness, mechanical strength, low-temperature mechanical strength, rubber elasticity, and transparency.

[0500] As can be seen from Tables 3A and 3B, the polycarbonate resin composition II of the present invention exhibits excellent heat resistance, long-term thermal stability, light resistance, softness, mechanical strength, low-temperature mechanical strength, and rubber elasticity.

[0501] In contrast, the polycarbonate resin compositions of Comparative Example 1 and Comparative Example 2, which contain neither carbonate structural unit (X) nor carbonate structural unit (Y2), are worse in any two of the following: heat resistance, long-term thermal stability, light resistance, softness, mechanical strength, low-temperature mechanical strength, and rubber elasticity.

[0502] The present invention has been described in detail using specific methods, but it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.

[0503] This application is based on Japanese Patent Application No. 2024-010350, filed on January 26, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) of formula (1) and a carbonate structural unit (Y1) derived from a dihydroxy compound (3) of formula (3). [Chemical Formula 1] In formula (1), A represents a divalent linker without a ring structure, consisting of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and hydrogen atom. Multiple A's in formula (1) are identical. B represents a non-cyclic divalent linker consisting of 1 to 40 carbon and hydrogen atoms, where n is an integer from 2 to 100. [Chemical Formula 2] 。 2. The polycarbonate resin composition according to claim 1, wherein, The polycarbonate resin composition has a melting point peak temperature when heated using a differential operating calorimeter at a heating rate of 20°C / min and the melting point peak temperature is measured.

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 in 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 all 100% by mass 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) shown in formula (1) is 400 or more and 10,000 or less.

8. The polycarbonate resin composition according to claim 1, wherein, The aliphatic polyester polyol (1) is selected from one or more of the aliphatic polyester polyols shown in formula (2) and formulas (10) to (12) below. [Chemical Formula 3] In the above formula, n, o, p, q, r, and s are integers from 2 to 100, and X is nonylene or 2-methyl-1,8-octylene.

9. The polycarbonate resin composition according to claim 1, wherein, The polycarbonate resin composition has the melting point peak temperature in the range above 100°C.

10. The polycarbonate resin composition according to claim 1, wherein, The polycarbonate resin composition has the melting point peak temperature in the range below 300°C.

11. The polycarbonate resin composition according to claim 1, wherein, The polycarbonate resin composition comprises the carbonate structural unit (X) and the carbonate structural unit (Y) in the form of a copolymer polycarbonate resin.

12. The polycarbonate resin composition according to claim 1, wherein, The polycarbonate resin composition 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, wherein, The viscosity-average molecular weight is above 20,000 and below 150,000.

14. The polycarbonate resin composition according to claim 1, wherein, When the glass transition temperature is measured by heating with a differential operating calorimeter at a heating rate of 20°C / min, the polycarbonate resin composition has a glass transition temperature below 30°C.

15. The polycarbonate resin composition according to claim 1, wherein, The tensile modulus of the sample obtained by hot pressing of 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 the sample obtained by hot pressing of the polycarbonate resin composition is more than 100%.

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

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

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

20. The polycarbonate resin composition according to claim 1, wherein, The viscosity-average molecular weight was retained at over 90% after treatment at 80℃ and 96% relative humidity for 168 hours.

21. The polycarbonate resin composition according to claim 1, wherein, Using a xenon lamp with an irradiation intensity of 60W / m 2 The viscosity-average molecular weight was retained at over 90% after 100 hours of treatment.

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

23. A thermoplastic resin composition comprising 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 a polycarbonate resin composition according to any one of claims 1 to 22 or a thermoplastic resin composition according to claim 23.

25. An extruded article obtained by extruding a polycarbonate resin composition according to any one of claims 1 to 22 or a thermoplastic resin composition according to claim 23.

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

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

28. A vibration damping material for electric vehicles (EVs), obtained using a polycarbonate resin composition according to any one of claims 1 to 22 or a thermoplastic resin composition according to claim 23.

29. A watch strap obtained using a polycarbonate resin composition according to any one of claims 1 to 22 or a thermoplastic resin composition according to claim 23.

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

31. A conduit fitting, obtained using a polycarbonate resin composition according to any one of claims 1 to 22 or a thermoplastic resin composition according to claim 23.

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

33. A polycarbonate resin composition for use in membrane materials selected from membrane structure buildings, vibration damping materials for electric vehicles (EVs), watch straps, camera handles, conduit fittings, and shoe midsoles, the polycarbonate resin composition comprising a carbonate structural unit (X) derived from an aliphatic polyester polyol (1) as shown in formula (1) below and a carbonate structural unit (Y2) derived from a dihydroxy compound (2) satisfying condition I below. When heated using a differential calorimeter at a heating rate of 20°C / min and the melting point peak temperature is measured, the polycarbonate resin composition exhibits a melting point peak temperature of [temperature value missing]. [Chemical Formula 4] In formula (1), A represents a divalent linker without a ring structure composed of 1 to 15 carbon atoms, 0 to 1 oxygen atom, and hydrogen atom. Multiple A's in formula (1) are the same. B represents a divalent linker without a ring structure composed of 1 to 40 carbon atoms and hydrogen atoms. n is an integer from 2 to 100. Requirement I: The dihydroxy compound (2) is a dihydroxy compound with a melt volumetric flow rate (MVR) of 5–120 cm⁻¹ at 260 °C and 2.16 kg load, obtained by transesterification with a carbonate source. 3 When polycarbonate resin (2) is heated at a heating rate of 20°C / min using a differential calorimeter and the melting point peak temperature is measured, the polycarbonate resin (2) has a melting point peak temperature.

34. The polycarbonate resin composition according to claim 33, wherein, The dihydroxy compound (2) is selected from any one or more of the dihydroxy compounds shown in formulas (3) to (7) below. [Chemical Formula 5] 。 35. The polycarbonate resin composition according to claim 33, wherein, The viscosity-average molecular weight retention rate after heating at 100°C for 100 hours using a hot air dryer is over 80%.

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