Polycarbonate resin composition and molded article thereof

Abstract

The present invention provides a polycarbonate resin composition and molded articles thereof that possess self-healing properties and exhibit excellent compatibility with bisphenol A type polycarbonate resin and polymerization efficiency. [Solution] A polycarbonate resin composition comprising a carbonate structural unit (X) derived from a dihydroxy compound in which both terminal hydroxyl groups are alcoholic, a carbonate structural unit (Y) derived from a dihydroxy compound in which both terminal hydroxyl groups are phenolic, and a carbonate structural unit (Z) derived from a crosslinkable compound, wherein the glass transition temperature (Tg) is 60°C or lower. A molded article containing this polycarbonate resin composition.

Description

[Technical Field]

[0001] This invention relates to a polycarbonate resin composition and molded articles such as injection-molded and extruded articles made from this polycarbonate resin composition. [Background technology]

[0002] Polycarbonate resin has excellent mechanical strength, electrical properties, and transparency, and is used in a variety of fields, including electrical and electronic equipment and the automotive industry.

[0003] However, polycarbonate resin has the disadvantage of being more easily scratched than glass, which can compromise the aesthetic appearance of products. To overcome this drawback, materials with improved surface hardness and scratch resistance have been developed (Patent Documents 1, 2, and 3). However, the polycarbonate resins described in Patent Documents 1-3 are not completely scratch-proof; over time, scratches gradually accumulate, impairing their appearance.

[0004] On the other hand, in recent years, materials that don't just make surfaces scratch-resistant, but instead allow existing scratches to heal naturally—so-called self-healing polymers—have been reported. Because scratches on self-healing polymers disappear over time, the aesthetic appearance is maintained for a long period of time. However, self-healing polycarbonate resins have not been proposed to date.

[0005] Patent Document 4 proposes a method for producing a branched aromatic polycarbonate resin having a desired degree of branching, which includes a step of linking an aromatic polycarbonate prepolymer with a branched structure and a minor aliphatic diol compound in a high molecular weight linking reaction under reduced pressure. However, this branched aromatic polycarbonate resin has a low proportion of structural units derived from aliphatic dihydroxy compounds, and therefore cannot lower its glass transition temperature. As a result, it does not exhibit self-healing properties, and scratches occur when rubbed with a material with a certain level of hardness or higher, impairing its aesthetic appearance. As a means to solve this problem, it is conceivable to apply a hard coat to the polycarbonate resin to further improve the surface hardness. However, it is generally known that applying a hard coat causes adverse effects on physical properties such as embrittlement of the material.

[0006] On the other hand, when considering the recycling of waste and the like of polycarbonate resin products, since many general polycarbonate resin products are composed of bisphenol A type polycarbonate resin, it is desirable to have excellent compatibility with bisphenol A type polycarbonate resin. That is, in the case of recycling a laminated film with a bisphenol A type polycarbonate resin layer using a polycarbonate resin with poor compatibility with bisphenol A type polycarbonate resin, the transparency of the recycled resin is impaired due to its poor compatibility. Therefore, it is desirable to have excellent compatibility with bisphenol A type polycarbonate resin.

[0007] Furthermore, in industrial applications, it is desirable to have excellent polymerization efficiency during the production of polycarbonate resin, a short time to reach the desired molecular weight (melt viscosity) in the polycondensation reaction process, and excellent productivity.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0009] The object of the present invention is to provide a polycarbonate resin composition and molded article thereof that has self-healing properties and excellent compatibility with bisphenol A type polycarbonate resin and polymerization efficiency. [Means for solving the problem]

[0010] The present inventors have discovered that by creating a polycarbonate resin composition comprising carbonate structural units derived from a specific dihydroxy compound, carbonate structural units derived from another specific dihydroxy compound, and carbonate structural units derived from a crosslinkable compound, and having a specific glass transition temperature, it is possible to obtain a polycarbonate resin that has self-healing properties, where scratches disappear with heat while maintaining its shape, and also exhibits excellent compatibility with bisphenol A type polycarbonate resin and polymerization efficiency. This invention is based on the aforementioned findings and is summarized as follows.

[0011] [1] A polycarbonate resin composition comprising a carbonate structural unit (X) derived from a dihydroxy compound in which both terminal hydroxyl groups are alcoholic, a carbonate structural unit (Y) derived from a dihydroxy compound in which both terminal hydroxyl groups are phenolic, and a carbonate structural unit (Z) derived from a crosslinkable compound, wherein the glass transition temperature (Tg) is 60°C or less.

[0012] [2] The polycarbonate resin composition according to [1], wherein the content of the carbonate structural unit (X) in 100% by mass of the total carbonate structural units of the polycarbonate resin composition is 10% by mass or more and 70% by mass or less.

[0013] [3] The polycarbonate resin composition according to [1] or [2], wherein the content of the carbonate structural unit (Y) in 100% by mass of the total carbonate structural units of the polycarbonate resin composition is 20% by mass or more and 90% by mass or less.

[0014] [4] The polycarbonate resin composition according to any one of [1] to [3], wherein the content of the carbonate structural unit (Z) in 100% by mass of the total carbonate structural units of the polycarbonate resin composition is 0.1% by mass or more and 10% by mass or less.

[0015] [5] A polycarbonate resin composition according to any one of [1] to [4], wherein the viscosity-average molecular weight (Mv) is in the range of 15,000 to 50,000.

[0016] [6] The polycarbonate resin composition according to any one of [1] to [5], wherein the carbonate structural unit (X) is derived from a dihydroxy compound that does not have an aromatic ring.

[0017] [7] The polycarbonate resin composition according to any one of [1] to [6], wherein the carbonate structural unit (Y) is derived from a dihydroxy compound represented by the following formula (1).

[0018] [ka]

[0019] (In formula (1), W1 to W4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and W5 is a single bond, or -CR1R2- (R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms), or a cycloalkylidene group having 3 to 10 carbon atoms.)

[0020] [8] The polycarbonate resin composition according to any one of [1] to [7], wherein the carbonate structural unit (Z) is derived from a compound having three or more hydroxyl groups.

[0021] [9] The polycarbonate resin composition according to any one of [1] to [8], wherein the carbonate structural unit (X) is derived from one or more dihydroxy compounds represented by the following formula (2), dihydroxy compounds represented by the following formula (3), and dihydroxy compounds represented by the following formula (4).

[0022] [ka]

[0023] (In equations (2) and (3), n is an integer greater than or equal to 1.)

[0024]

[10] The polycarbonate resin composition according to [9], wherein the number average molecular weight of the dihydroxy compound represented by formula (2) and / or the dihydroxy compound represented by formula (3) is 5,000 or less.

[0025]

[11] The polycarbonate resin composition according to any one of [7] to

[10] , wherein the carbonate structural unit (Y) is derived from a dihydroxy compound represented by the following formula (5) and / or a dihydroxy compound represented by the following formula (6).

[0026] [ka]

[0027]

[12] The polycarbonate resin composition according to any one of [8] to

[11] , wherein the carbonate structural unit (Z) is derived from a compound represented by the following formula (7).

[0028] [ka]

[0029]

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

[12] , comprising the carbonate structural unit (X), the carbonate structural unit (Y), and the carbonate structural unit (Z) as a copolymerized polycarbonate resin.

[0030]

[14] A molded article containing a polycarbonate resin composition as described in any of [1] to

[13] .

[15] An injection-molded article containing a polycarbonate resin composition as described in any of [1] to

[13] .

[16] An extruded article containing a polycarbonate resin composition as described in any of [1] to

[13] .

[17] A laminated film comprising the polycarbonate resin composition described in any of [1] to

[13] . [Effects of the Invention]

[0031] According to the present invention, it is possible to provide a polycarbonate resin composition and molded articles thereof that have excellent self-healing properties, compatibility with bisphenol A type polycarbonate resin, and polymerization efficiency. The polycarbonate resin composition of the present invention has excellent self-healing properties, compatibility with bisphenol A type polycarbonate resin, and polymerization efficiency, making it widely applicable in industrial fields such as automotive interior parts. In particular, because the polycarbonate resin composition of the present invention has excellent compatibility with bisphenol A type polycarbonate resin, when considering the recycling of composite molded products such as laminated films with bisphenol A type polycarbonate resin, the transparency of the recycled resin is not impaired even if the polycarbonate resin composition of the present invention is included, and high-quality recycled resin can be obtained. [Modes for carrying out the invention]

[0032] The present invention will be described in detail below with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples shown below. In this specification, unless otherwise specified, "~" means that the numerical values ​​described before and after it are included as the lower limit and upper limit.

[0033] [Polycarbonate resin composition] The polycarbonate resin composition of the present invention (hereinafter sometimes referred to as "the polycarbonate resin composition of the present invention") is a polycarbonate resin composition comprising a carbonate structural unit (X) derived from a dihydroxy compound in which both terminal hydroxyl groups are alcoholic (hereinafter sometimes simply referred to as "carbonate structural unit (X)"), a carbonate structural unit (Y) derived from a dihydroxy compound in which both terminal hydroxyl groups are phenolic (hereinafter sometimes simply referred to as "carbonate structural unit (Y)"), and a carbonate structural unit (Z) derived from a crosslinkable compound (hereinafter sometimes simply referred to as "carbonate structural unit (Z)"), wherein the glass transition temperature (Tg) is 60°C or lower.

[0034] Preferably, the polycarbonate resin composition of the present invention contains 10% to 50% by mass of carbonate structural units (X) out of 100% by mass of all carbonate structural units, 20% to 90% by mass of carbonate structural units (Y), and 0.1% to 10% by mass of carbonate structural units (Z).

[0035] Furthermore, the polycarbonate resin composition of the present invention may contain other carbonate structural units other than carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z).

[0036] The following percentages of carbonate structural units (X), carbonate structural units (Y), carbonate structural units (Z), and other carbonate structural units are all expressed as weight percentages relative to 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0037] <Mechanism> In the present invention, carbonate structural units (X) form soft segments, carbonate structural units (Y) form hard segments, and carbonate structural units (Z) form a cross-linked structure. As a result, when heat is applied, damage caused by the heat disappears while the shape is maintained, exhibiting self-healing properties. Specifically, the soft segments formed by the carbonate structural unit (X) provide excellent self-healing properties. Furthermore, the hard segments formed by the carbonate structural unit (Y) allow the shape to be maintained. Therefore, it is possible to produce polycarbonate resin compositions and molded articles that retain their shape and possess self-healing properties even when subjected to heat above the glass transition temperature (Tg). Furthermore, by including the carbonate structural unit (Y), it is possible to achieve excellent compatibility with bisphenol A type polycarbonate resin. Furthermore, the carbonate structural unit (Z) introduces a crosslinkable branched structure during polymerization, resulting in excellent polymerization efficiency.

[0038] Furthermore, one of the characteristic features of the polycarbonate resin composition of the present invention is that its glass transition temperature (Tg) is 60°C or lower, which is lower than the glass transition temperature (Tg) of typical polycarbonate resin compositions. In other words, conventionally, polycarbonate resins have generally been required to have high impact resistance, and no consideration has been given to lowering the Tg (transistor temperature). The inventors have found that lowering the Tg of a polycarbonate resin composition lowers the self-healing temperature, resulting in superior self-healing properties.

[0039] <Carbonate structural unit (X)> The carbonate structural unit (X) contained in the polycarbonate resin composition of the present invention is a carbonate structural unit (X) derived from a dihydroxy compound in which both terminal hydroxyl groups are alcoholic. From the viewpoint of effectively obtaining the effect of carbonate structural unit (X) as a soft segment and enhancing self-healing properties, it is preferable that the carbonate structural unit (X) is derived from a dihydroxy compound that does not have an aromatic ring, and examples include carbonate structural units derived from aliphatic dihydroxy compounds or alicyclic dihydroxy compounds, and preferably carbonate structural units derived from aliphatic dihydroxy compounds.

[0040] Among aliphatic dihydroxy compounds, from the viewpoint of enhancing self-healing properties, it is preferable that the carbonate structural unit (X) is derived from one or more of the following dihydroxy compounds: polytrimethylene ether glycol (hereinafter abbreviated as "PO3G" or sometimes referred to as "dihydroxy compound (2)"), polytetramethylene ether glycol (hereinafter abbreviated as "PTMG" or sometimes referred to as "dihydroxy compound (3)"), and dihydroxy compound (hereinafter abbreviated as "1,10-DD" or sometimes referred to as "dihydroxy compound (4)"), as a carbonate structural unit derived from one or more of these.

[0041] [ka]

[0042] (In equations (2) and (3), n is an integer greater than or equal to 1.)

[0043] The number average molecular weights of dihydroxy compound (2) and dihydroxy compound (3) are preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less, from the viewpoint of compatibility between the dihydroxy compound constituting the carbonate structural unit (X) and the dihydroxy compounds constituting the carbonate structural unit (Y) and carbonate structural unit (Z), and from the viewpoint of enhancing self-healing properties. If the number average molecular weights of dihydroxy compound (2) and dihydroxy compound (3) are below the above lower limit, the compatibility with the dihydroxy compounds constituting the carbonate structural unit (Y) and carbonate structural unit (Z) is good, and polymerization failure due to poor compatibility can be prevented. On the other hand, from the viewpoint of effectively obtaining the effect of carbonate structural unit (X) as a soft segment and suppressing fluctuations in the composition ratio, the number average molecular weights of dihydroxy compound (2) and dihydroxy compound (3) are preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more. Therefore, it is preferable that n in formulas (2) and (3) is a number that satisfies the preferred range of the number-average molecular weight.

[0044] Furthermore, dihydroxy compound (2) and dihydroxy compound (3) may be provided as mixtures of two or more dihydroxy compounds with different numbers of n in formulas (2) and (3), respectively. In such cases, the n of dihydroxy compound (2) and dihydroxy compound (3) as mixtures is expressed as a real number including decimal places as an average value.

[0045] The number-average molecular weights of dihydroxy compound (2) and dihydroxy compound (3) are: 1 It can be calculated using a measurement method involving H-NMR.

[0046] Furthermore, the dihydroxy compound constituting the carbonate structural unit (X) may be a dihydroxy compound manufactured from plant-derived raw materials. For example, as the dihydroxy compound (1), PO3G with a biomass content of 100%, synthesized by condensing 1,3-propanediol, can be used. Whether or not PO3G etc. are manufactured from plant-derived resources can be determined, for example, by radiocarbon ( 14 This can be confirmed by measuring the concentration in C).

[0047] The dihydroxy compounds constituting the carbonate structural unit (X) may consist of only one type of dihydroxy compound in which both terminal hydroxyl groups are alcoholic, or two or more types. Therefore, the dihydroxy compounds constituting the carbonate structural unit (X) may consist of only one type of dihydroxy compound (2), or two or more types; only one type of dihydroxy compound (3), or two or more types; or only one type of dihydroxy compound (4), or two or more types. The carbonate structural unit (X) may consist of two or more dihydroxy compounds selected from dihydroxy compound (2), dihydroxy compound (3), and dihydroxy compound (4).

[0048] <Carbonate structural unit (Y)> The carbonate structural unit (Y) is a carbonate structural unit (Y) derived from a dihydroxy compound in which both terminal hydroxyl groups are phenolic, and an example of such a carbonate structural unit is derived from an aromatic dihydroxy compound.

[0049] From the viewpoint of compatibility with bisphenol A type polycarbonate resin, it is preferable that the carbonate structural unit (Y) is a carbonate structural unit derived from a dihydroxy compound represented by the following formula (1) (hereinafter sometimes referred to as "dihydroxy compound (1)").

[0050] [ka]

[0051] (In formula (1), W 1~W 4 is, independently of one another, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and W 5 is a single bond, or -CR1R2- (R1 and R2 are, independently of one another, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.), or a cycloalkylidene group having 3 to 10 carbon atoms.)

[0052] In the formula (1), W 1 ~W 4 is, independently of one another, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0053] In the present invention, the number of carbon atoms of a group such as an alkyl group is, when the alkyl group has a substituent, the total number of carbon atoms of the entire group including the carbon atoms of the substituent. Regarding an aryl group having 6 to 12 carbon atoms, when the aryl group has a substituent, the number of carbon atoms thereof is the sum of the number of carbon atoms of the substituent and the number of carbon atoms of the aryl group.

[0054] W 1 ~W 4 The alkyl group having 1 to 10 carbon atoms represented by may be unsubstituted or may have a substituent. Further, it may be linear, branched or cyclic. Examples of the substituent that the alkyl group may have include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, an acyloxy group, etc.

[0055] In the formula (1), specific examples of the alkyl group of W 1 ~W 4 having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; Methyl ethyl group, methyl propyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methylheptyl group, methyl octyl group, methyl nonyl group; Dimethyl ethyl group, dimethyl propyl group, dimethyl butyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group; Trimethylpropyl group, trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group; Ethylbutyl group, ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group; Cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group, tetramethylcyclohexyl group, ethylcyclohexyl group, diethylcyclohexyl group, methylethylcyclohexyl group: These are some examples.

[0056] W 1 ~W 4 The aryl group having 6 to 12 carbon atoms, represented by , may be unsubstituted or substituted. Examples of substituents that the aryl group may have include halogen atoms, nitro groups, cyano groups, hydroxyl groups, alkyl groups, alkoxy groups, aryloxy groups, carboxyl groups, alkoxycarbonyl groups, acyl groups, and acyloxy groups.

[0057] In the above equation (1), W 1 ~W 4 Specific examples of aryl groups with 6 to 12 carbon atoms include the phenyl group, tolyl group, and naphthyl group.

[0058] In the above equation (1), W 5 -CR 1 R 2 -(R 1 and R 2 Each of these is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ) or a cycloalkylidene group having 3 to 10 carbon atoms.

[0059] W 5 "-CR" is represented as 1 R 2 -" R 1 and R 2 The hydrogen atom, the alkyl group having 1 to 10 carbon atoms, or the aryl group having 6 to 12 carbon atoms is W 1 ~W 4 It is the same as in [the case mentioned earlier].

[0060] W 5 The cycloalkylidene group having 3 to 10 carbon atoms, represented by , may have a branched structure and may be unsubstituted or substituted. The substituents that the cycloalkylidene group may have are the W 1 ~W 4 This is similar to the substituents that the alkyl group may have.

[0061] W 5 Specific examples of cycloalkylidene groups having 3 to 10 carbon atoms, represented by the formula, include cyclopentylidene groups and cyclohexylidene groups.

[0062] Among these, W 1 ~W 4 Each is independently a hydrogen atom or a methyl group, and W 5 -CR 1 R 2 -(R 1 and R 2 It is preferable that each of these is independently a hydrogen atom or a methyl group, and W 1 ~W 4 Each is independently a hydrogen atom or a methyl group, and W 5 This is a 2,2-propyridene group (-CR 1 R 2 - R 1 and R 2 It is more preferable that it is a methyl group.

[0063] Specific examples of aromatic dihydroxy compounds (1) include the dihydroxy compound represented by the following formula (5), namely 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A) (hereinafter sometimes abbreviated as "BPA"), and the dihydroxy compound represented by the following formula (6), namely 2,2-bis(4-hydroxy-3-methylphenyl)propane (=bisphenol C) (hereinafter sometimes abbreviated as "BPC").

[0064] [ka]

[0065] The dihydroxy compounds constituting the carbonate structural unit (Y) may consist of only one type of dihydroxy compound in which both terminal hydroxyl groups are phenolic, or there may be two or more types. Therefore, the dihydroxy compounds constituting the carbonate structural unit (Y) may consist of only one type of dihydroxy compound (1), or there may be two or more types.

[0066] For example, it is preferable that the carbonate structural unit (Y) contains both carbonate structural units derived from BPA and carbonate structural units derived from BPC, as this allows for adjustment of compatibility with bisphenol A type polycarbonate resin and self-healing properties. In this case, the ratio of carbonate structural units derived from BPA to carbonate structural units derived from BPC in the carbonate structural unit (Y) is preferably 1:0.01 to 0.50 by mass, and particularly preferably 1:0.05 to 0.30.

[0067] <Carbonate structural unit (Z)> The carbonate structural unit (Z) is a carbonate structural unit (Z) derived from a crosslinkable compound.

[0068] The crosslinkable compound that constitutes the carbonate structural unit (Z) can be any compound that can introduce a branched structure into the molecular chain of the polycarbonate resin. For example, a polyfunctional compound having three or more, preferably three to six, functional groups in one molecule can be used. As such polyfunctional compounds, compounds having hydroxyl groups such as phenolic hydroxyl groups and carboxyl groups are preferably used.

[0069] Specific examples of trifunctional compounds include 1,1,1-tris(4-hydroxyphenyl)ethane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, α-methyl-α,α',α"-tris(4-hydroxyphenyl)-1,4-diethylbenzene, α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, phloroglysine, and 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-ethyl-4-isopropylbenzene. Examples include xyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 2,2-bis[4,4-(4,4'-dihydroxyphenyl)-cyclohexyl]-propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, trimethylolpropane, 1,2,5-pentatriol, 3,4-dihydroxybenzyl alcohol, 1,2,6-hexatriol, and 1,3,5-adamantanetriol.

[0070] Specific examples of compounds with four or more functions include purpurogalin, 2,3,4,4'-telolahydroxybenzophenone, 2,3,4,4'-telolahydroxydiphenylmethane, gallein, and 2,3,3',4,4',5'-hexahydroxybenzophenone.

[0071] Of these, as crosslinkable compounds constituting the carbonate structural unit (Z), compounds having three or more hydroxyl groups, preferably phenolic hydroxyl groups, are preferred from the viewpoint of polymerization efficiency. From the viewpoint of compound stability and ease of obtaining high-purity products, 1,1,1-tris(4-hydroxyphenyl)ethane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and trimethylolpropane are particularly preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane represented by the following formula (7) (hereinafter sometimes abbreviated as "THPE") is particularly preferred.

[0072] [ka]

[0073] The dihydroxy compounds constituting the carbonate structural unit (Z) may consist of only one crosslinkable compound, or two or more.

[0074] <Forms of carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z)> The polycarbonate resin composition of the present invention may contain carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z), and there are no particular restrictions on the form in which the carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) are contained. Typically, carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) are contained within polycarbonate resin.

[0075] The polycarbonate resin composition of the present invention may be a polycarbonate resin mixture (blend) of a polycarbonate resin containing carbonate structural unit (X), a polycarbonate resin containing carbonate structural unit (Y), and a polycarbonate resin containing carbonate structural unit (Z), or it may contain a copolymer type polycarbonate resin containing carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z) simultaneously.

[0076] The polycarbonate resin composition of the present invention may be a mixture of a polycarbonate resin containing one or two of carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) and a copolymerized polycarbonate resin containing carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z), or it may be a mixture of a polycarbonate resin containing one or two of carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) and a polycarbonate resin containing the other two or one of carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z). Furthermore, the polycarbonate resin composition of the present invention may be a mixture of a polycarbonate resin containing carbonate structural unit (X), a polycarbonate resin containing carbonate structural unit (Y), and a polycarbonate resin containing carbonate structural unit (Z), or it may include a copolymerized polycarbonate resin containing carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z), in addition to a polycarbonate resin that does not contain any of carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z).

[0077] In this invention, the term "polycarbonate resin composition" encompasses both the concepts of "polycarbonate resin mixture containing multiple polycarbonate resins" and "copolymerized polycarbonate resin."

[0078] When the polycarbonate resin composition of the present invention contains carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) as a copolymerized polycarbonate resin, the polycarbonate resin composition of the present invention is referred to as "polycarbonate resin".

[0079] When the polycarbonate resin composition of the present invention is a mixture of a polycarbonate resin containing carbonate structural unit (X), a polycarbonate resin containing carbonate structural unit (Y), and a polycarbonate resin containing carbonate structural unit (Z), it is usually referred to as a "polycarbonate resin composition." The same applies to the other formulations described above.

[0080] In the present invention, the term "polycarbonate resin composition" will also refer to a case in which the composition consists of one type of copolymerized polycarbonate resin containing carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z). In Examples 1-6 and Comparative Examples 1-6 described below, a single copolymerized polycarbonate resin is produced, and therefore it is referred to as "polycarbonate resin" (the "polycarbonate resin" of the present invention), but these are also included in the polycarbonate resin composition of the present invention.

[0081] From the viewpoint of compatibility with bisphenol A type polycarbonate resin and polymerization efficiency, the polycarbonate resin composition of the present invention preferably contains carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z) as a copolymerized polycarbonate resin containing all of them.

[0082] <Content ratio of each carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z)> From the viewpoint of self-healing properties, the content of carbonate structural units (X) in the polycarbonate resin composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. On the other hand, from the viewpoint of compatibility with bisphenol A type polycarbonate resin and polymerization efficiency, the content of carbonate structural units (X) is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0083] From the viewpoint of compatibility with bisphenol A type polycarbonate resin, the content of carbonate structural units (Y) in the polycarbonate resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. On the other hand, from the viewpoint of self-healing properties, the content of carbonate structural units (Y) is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0084] From the viewpoint of polymerization efficiency, the content of carbonate structural units (Z) in the polycarbonate resin composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. On the other hand, from the viewpoint of moldability, the content of carbonate structural units (Z) is 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0085] As mentioned above, the content ratios of carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) are each weight percentages relative to 100% by mass of all carbonate structural units in the polycarbonate resin composition.

[0086] Specifically, the content of each carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z) in the polycarbonate resin composition of the present invention can be determined as the proportion of carbonate units derived from each dihydroxy compound in the total carbonate units derived from all dihydroxy compounds used in the production of the polycarbonate resin composition of the present invention, i.e., the proportion of carbonate units derived from dihydroxy compounds in which both of the two terminal hydroxyl groups are alcoholic, the proportion of carbonate structural units derived from dihydroxy compounds in which both of the two terminal hydroxyl groups are phenolic, and the proportion of carbonate structural units derived from crosslinkable compounds.

[0087] Furthermore, the content ratios of each carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z) in the polycarbonate resin composition are as follows: 1 This can be calculated using 1H-NMR, but it can also be determined from the amount of dihydroxy compound used as a raw material during the production of polycarbonate resin. The same applies to other carbonate structural units described later.

[0088] As described above, any of dihydroxy compounds (2), dihydroxy compound (3), and dihydroxy compound (4) are preferred as the dihydroxy compounds constituting the carbonate structural unit (X) in the polycarbonate resin composition of the present invention. From the viewpoint of effectively obtaining the effects of containing these carbonate structural units, the content ratio of carbonate structural units derived from dihydroxy compound (2), carbonate structural units derived from dihydroxy compound (3), and carbonate structural units derived from dihydroxy compound (4) in the carbonate structural unit (X) is preferably 80% by mass or more, particularly 85% by mass or more, and especially 90-100% by mass.

[0089] Furthermore, as described above, dihydroxy compound (1) is preferred as the dihydroxy compound constituting the carbonate structural unit (Y) in the polycarbonate resin composition of the present invention. From the viewpoint of effectively obtaining the effects of containing this carbonate structural unit, the content ratio of carbonate structural units derived from dihydroxy compound (1) in the carbonate structural unit (Y) is preferably 80% by mass or more, particularly 85% by mass or more, and especially 90-100% by mass.

[0090] Furthermore, as the dihydroxy compound constituting the carbonate structural unit (Z) in the polycarbonate resin composition of the present invention, as described above, 1,1,1-tris(4-hydroxyphenyl)ethane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and trimethylolpropane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being the most preferred. From the viewpoint of effectively obtaining the effects of containing these carbonate structural units, the content of carbonate structural units (Z) derived from these suitable crosslinkable compounds is preferably 80% by mass or more, particularly 85% by mass or more, and especially 90-100% by mass.

[0091] <Other carbonate structural units> The polycarbonate resin composition of the present invention may contain carbonate structural units derived from carbonate structural units other than carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z), to the extent that it does not impair the purpose of the present invention. Other compounds that constitute the carbonate structural unit include dihydroxy compounds in which one of the two terminal hydroxyl groups is alcoholic and the other is phenolic, and compounds in which the terminal hydroxyl group acts as a terminal encapsulant.

[0092] Other carbonate structural units may also be included as copolymerized polycarbonate resins with one or more of the carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z), and polycarbonate resins consisting of other carbonate structural units may be mixed with polycarbonate resins containing carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z).

[0093] 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 the total carbonate structural units of the polycarbonate resin composition is preferably 10% by mass or less, particularly 5% by mass or less, and especially 2% by mass or less. That is, the total content of carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) in 100% by mass of the total carbonate structural units is preferably 90% by mass or more, particularly 95% by mass or more, and especially 98% by mass or more.

[0094] While polycarbonate resin compositions containing other carbonate structural units may provide improvements such as reduced water absorption due to these other units, excessive amounts of these units may impair the effects of the present invention, including self-healing properties, compatibility with bisphenol A type polycarbonate resin, and improved polymerization efficiency, due to the presence of carbonate structural units (X), (Y), and (Z).

[0095] 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.

[0096] <Other ingredients> The polycarbonate resin composition of the present invention may contain, as necessary, a polycarbonate resin containing one or more of carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z), or a polycarbonate resin that does not contain any of the carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z), as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resin, various resin additives, and so on.

[0097] Examples of resins other than polycarbonate resins that may be contained in the polycarbonate resin composition of the present invention include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; styrene 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. The other resins may consist of one type, or two or more types in any combination and ratio.

[0098] Examples of resin additives include heat stabilizers, antioxidants, mold release agents, lightfastness agents (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, dyes, and pigments. These resin additives may be present in any single form, or in any combination and ratio of two or more forms.

[0099] <Viscosity-average molecular weight of polycarbonate resin composition> The viscosity-average molecular weight (Mv) of the polycarbonate resin composition of the present invention is not particularly limited, but from the viewpoint of mechanical strength and moldability, it is preferably 15,000 to 50,000, and more preferably 20,000 to 40,000. The viscosity-average molecular weight of the polycarbonate resin composition of the present invention is measured by the method described in the Examples section below.

[0100] <Glass transition temperature of polycarbonate resin composition> As described above, the polycarbonate resin composition of the present invention is characterized by having a glass transition temperature (Tg) of 60°C or lower, from the viewpoint of self-healing properties at low temperatures. From the viewpoint of self-healing properties, the glass transition temperature (Tg) of the polycarbonate resin composition of the present invention is preferably 50°C or lower, and more preferably 40°C or lower. On the other hand, from the viewpoint of shape retention, the glass transition temperature (Tg) of the polycarbonate resin composition of the present invention is preferably -20°C or higher, and particularly preferably -10°C or higher. The glass transition temperature (Tg) of the polycarbonate resin composition of the present invention is measured by the method described in the Examples section below.

[0101] [Method for producing polycarbonate resin composition] <Method for manufacturing polycarbonate resin> The polycarbonate resin constituting the polycarbonate resin composition of the present invention can be produced by conventionally known polymerization methods, and the polymerization method is not particularly limited. Examples of polymerization methods include interfacial polymerization, molten transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among these, molten transesterification and interfacial polymerization are preferred. Particularly preferred methods among these will be described in detail below.

[0102] (interfacial polymerization method) In the interfacial polymerization method, polycarbonate resin is obtained by reacting a starting dihydroxy compound with a carbonate-forming compound in the presence of an organic solvent and an alkaline aqueous solution that are inert to the reaction, usually maintaining a pH of 9 or higher, and then carrying out interfacial polymerization in the presence of a polymerization catalyst. Molecular weight modifiers (end-terminating agents) may be present in the reaction system as needed, and antioxidants may be present to prevent oxidation of the starting dihydroxy compound.

[0103] The organic solvent that is inert to the reaction is not particularly limited, but examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; and so on. One organic solvent may be used, or two or more may be used in any combination and ratio.

[0104] The alkali compounds contained in the alkaline aqueous solution are not particularly limited, but examples include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate, as well as alkaline earth metal compounds. Among these, sodium hydroxide and / or potassium hydroxide are preferred. One alkali compound may be used, or two or more may be used in any combination and ratio.

[0105] There are no restrictions on the concentration of the alkali compound in the alkaline aqueous solution, but typically, to control the pH of the alkaline aqueous solution to 10-12, an alkali compound concentration of 5-10% by mass is used. For example, when bubbling in phosgene, to control the pH of the aqueous phase to 10-12, preferably 10-11, the alkali compound is typically used in an amount of 1.9 mol or more, preferably 2.0 mol or more, typically 3.2 mol or less, and preferably 2.5 mol or less, per mol of the starting material dihydroxy compound.

[0106] By using a dihydroxy compound in which both terminal hydroxyl groups are alcoholic, a dihydroxy compound in which both terminal hydroxyl groups are phenolic, and a crosslinking compound as raw material dihydroxy compounds, a copolymer polycarbonate resin containing carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z) can be produced. By using a dihydroxy compound in which both terminal hydroxyl groups are alcoholic, a polycarbonate resin containing carbonate structural unit (X) can be produced. By using a dihydroxy compound in which both terminal hydroxyl groups are phenolic, a polycarbonate resin containing carbonate structural unit (Y) can be produced. By using a crosslinking compound, a polycarbonate resin containing carbonate structural unit (Z) can be produced. When producing polycarbonate resins containing the other carbonate structural units mentioned above, one or more dihydroxy compounds other than those with two alcoholic terminal hydroxyl groups, those with two phenolic terminal hydroxyl groups, and crosslinkable compounds may be used.

[0107] Carbonyl halides are preferably used as carbonate-forming compounds, and phosgene is particularly preferred. The method using phosgene is specifically called the phosgene method.

[0108] The polymerization catalyst is not particularly limited, but examples include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; guanine; salts of guanidine; and the like. One polymerization catalyst may be used, or two or more may be used in any combination and ratio.

[0109] Molecular weight modifiers are not particularly limited, but examples include phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; and phthalimides. Among these, phenols are preferred. Phenols specifically include phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, mn-nonylphenol, pn-nonylphenol, Examples include o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, monoalkylphenols having a linear or branched alkyl group with an average of 12 to 35 carbon atoms in the ortho, meta, or para position, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, 4-(1-adamantyl)phenol, etc. Among these, pt-butylphenol, p-phenylphenol, and p-cumylphenol are preferably used. The molecular weight adjusting agent may be used alone, or two or more may be used in any combination and ratio.

[0110] The amount of molecular weight adjusting agent used is not particularly limited, but for example, it is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the raw material dihydroxy compound.

[0111] While not particularly limited, examples of antioxidants include hindered phenol-based antioxidants. Specific examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4, Examples include 6-tolyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[0112] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Examples of commercially available phenolic antioxidants include BASF's "Irganox® 1010" and "Irganox® 1076," and ADEKA's "ADEKA Stab® AO-50" and "ADEKA Stab® AO-60." The antioxidant may be used alone, or two or more may be used in any combination and ratio.

[0113] The amount of antioxidant used is not particularly limited, but for example, it is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, per 100 parts by mass of the raw material dihydroxy compound. If the amount of antioxidant used is below the lower limit of the above range, the antioxidant effect may be insufficient. If the amount of antioxidant used exceeds the upper limit of the above range, gas may be more easily released during injection molding.

[0114] The order in which the reaction substrate (reaction raw material), reaction solvent (organic solvent), catalyst, additives, etc. are mixed during the reaction is arbitrary as long as the desired polycarbonate resin is obtained, and any appropriate order can be set. For example, when phosgene is used as the carbonate-forming compound, the molecular weight modifier can be mixed at any time between the reaction between the starting material dihydroxy compound and phosgene (phosgenation) and the start of the polymerization reaction.

[0115] The reaction temperature is not particularly limited, but is usually between 0 and 40°C. The reaction time is not particularly limited, but is usually between a few minutes (e.g., 10 minutes) and several hours (e.g., 6 hours).

[0116] (Fresh transesterification method) In the molten transesterification method, for example, a transesterification reaction is carried out between a carbonate ester and a starting dihydroxy compound. The starting dihydroxy compound is the same as in the interfacial polymerization method.

[0117] Examples of carbonate esters include compounds represented by the following formula (8), such as diaryl carbonates, dialkyl carbonates, biscarbonate forms of dihydroxy compounds, monocarbonate forms of dihydroxy compounds, and carbonate forms of dihydroxy compounds such as cyclic carbonates.

[0118] [ka]

[0119] In equation (8) above, R 11 and R 12 Each independently represents an alkyl group or an aryl group. 11 and R 12 The alkyl and aryl groups represented by may be unsubstituted or substituted. The substituents that these substituents may have are, respectively, R in formula (9) shown below. 13 , R 14 This is similar to the substituents that the aryl group may have. Also, R 11 and R 12 The number of carbon atoms in the alkyl group represented is preferably 1 to 30. 11 and R 12 The number of carbon atoms in the aryl group represented by is preferably 6 to 30, and more preferably 6 to 12.

[0120] Below, R 11 and R 12 However, when it is an alkyl group, it is sometimes called a dialkyl carbonate, and when it is an Ally group, it is sometimes called a diaryl carbonate.

[0121] In particular, from the perspective of reactivity with dihydroxy compounds, R 11 and R 12Each of these is preferably an aryl group which may have substituents. The carbonate ester is more preferably a diaryl carbonate which may have substituents, represented by the following formula (9).

[0122] [ka]

[0123] In equation (9) above, R 13 and R 14 Each of these is independently a halogen atom, a nitro group, a cyano group, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, a carboxylic acid group, an alkoxycarbonyl group with 2 to 20 carbon atoms, or an acyloxy group with 1 to 20 carbon atoms. p and q each independently represent an integer from 0 to 5.

[0124] The alkoxycarbonyl group is -C(=O)-OR 20 (R 20 is an alkyl group. It is a group represented as ), and specific examples include the methoxycarbonyl group and the ethoxycarbonyl group. The acyloxy group is -OC(=O)-R 21 (R 21 is a hydrogen atom, an alkyl group, or an aryl group. The group is represented by ( ), and specific examples include the formyloxy group and the acetyloxy group. p and q are each independently preferably integers from 0 to 3, and more preferably integers from 0 to 2.

[0125] Examples of carbonate esters represented by formula (8) and / or formula (9) include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), diaryl carbonates such as bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate, bis(4-fluorophenyl) carbonate, bis(2-chlorophenyl) carbonate, bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, bis(2-nitrophenyl) carbonate, bis(methylsalicylphenyl) carbonate, and ditril carbonate. Diphenyl carbonate is preferred among these. These carbonate esters may be used individually or in any combination and ratio of two or more.

[0126] The carbonate ester may be substituted with a dicarboxylic acid or dicarboxylic acid ester in an amount of preferably 50 mol% or less, and more preferably 30 mol% or less. Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

[0127] The ratio of the raw material dihydroxy compound to the carbonate ester is arbitrary as long as the desired polycarbonate resin can be obtained, however, it is preferable to use these carbonate esters in excess of the raw material dihydroxy compound when polymerizing them with the dihydroxy compound. The amount of carbonate ester used is preferably 1.01 to 1.30 moles, and more preferably 1.01 to 1.20 moles, per mole of dihydroxy compound. If this mole ratio is too low, the resulting polycarbonate resin will have many terminal OH groups, which tends to worsen the thermal stability of the resin. On the other hand, if this mole ratio is too high, the reaction rate of transesterification will decrease, making it difficult to produce a polycarbonate resin with the desired molecular weight, or the amount of residual carbonate ester in the resin will increase, which may cause odor during molding or in the molded product.

[0128] When producing polycarbonate resin by the molten transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, alkali metal compounds and / or alkaline earth metal compounds are preferred. As an auxiliary, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. One type of transesterification catalyst may be used, or two or more types may be used in any combination and ratio.

[0129] In the molten transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 300°C. The reaction pressure is not particularly limited, but is usually under reduced pressure of 2 Torr or less. Specifically, the molten polycondensation reaction can be carried out under the above conditions while removing by-products.

[0130] 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 color. Therefore, it is preferable to keep the reaction temperature below 300°C. To prevent oxygen leakage from the equipment due to excessive pressure reduction, it is preferable to select pressure conditions with a lower limit of approximately 0.05 Torr.

[0131] The reaction can be carried out using either a batch or continuous method. In the batch method, the order in which the reaction substrate (reaction raw materials), catalyst, additives, etc. are mixed is arbitrary as long as the desired polycarbonate resin is obtained, and any appropriate order can be set.

[0132] In the molten transesterification process, a catalyst deactivator may be used as needed. Any compound that neutralizes the transesterification catalyst can be used as the catalyst deactivator. Examples include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc. One catalyst deactivator may be used, or two or more may be used in any combination and ratio.

[0133] The amount of catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, and usually 50 equivalents or less, preferably 10 equivalents or less, and more preferably 8 equivalents or less, relative to the transesterification catalyst. The amount of catalyst deactivator used is typically 1 ppm or more and 100 ppm or less relative to the polycarbonate resin, preferably 50 ppm or less.

[0134] <Method for producing polycarbonate resin composition> The polycarbonate resin composition of the present invention is a mixture of a polycarbonate resin containing carbonate structural unit (X), a polycarbonate resin containing carbonate structural unit (Y), and a polycarbonate resin containing carbonate structural unit (Z), or a polycarbonate resin containing one or two of carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z), and a polycarbonate resin containing the other two or one of carbonate structural unit (X), carbonate structural unit (Y), and carbonate structural unit (Z). In the case of a polycarbonate resin composition containing two or more types of polycarbonate resins, such as a mixture with a resin, or a mixture containing a polycarbonate resin that does not contain carbonate structural unit (X), carbonate structural unit (Y), or carbonate structural unit (Z), there are no particular limitations on the method for producing the polycarbonate resin composition of the present invention by mixing multiple polycarbonate resins, for example, two types of polycarbonate resins such as polycarbonate resin (a) and polycarbonate resin (b), but the following methods 1) to 4) are examples. 1) A method of melting and kneading polycarbonate resin (a) and polycarbonate resin (b); 2) A method of melt-mixing molten polycarbonate resin (a) and molten polycarbonate resin (b); 3) A method for mixing polycarbonate resin (a) and polycarbonate resin (b) in solution; 4) A method for dry blending polycarbonate resin (a) and polycarbonate resin (b); The following describes each method. In the following, we will describe a method for producing the polycarbonate resin composition of the present invention by mixing two types of polycarbonate resins, but the same method can be used when mixing three or more types of polycarbonate resins.

[0135] 1) A method of melting and kneading polycarbonate resin (a) and polycarbonate resin (b); Pellets or powders of polycarbonate resin (a) and pellets or powders of polycarbonate resin (b) are melt-kneaded together using a mixing device such as a kneader, twin-screw extruder, or single-screw extruder. The pellets or powders of polycarbonate resin (a) and polycarbonate resin (b) may be mixed together in a solid state beforehand and then kneaded together, or one of them may be melted first in the mixing device, and then the other polycarbonate resin may be added and kneaded together.

[0136] There are no specific regulations regarding the mixing temperature, but a temperature of 200°C or higher is preferred, 220°C or higher is more preferred, and 230°C or higher is even more preferred. Furthermore, a temperature of 320°C or lower is preferred, and 300°C or lower is particularly preferred. If the mixing temperature is too low, the mixing of polycarbonate resin (a) and polycarbonate resin (b) will not be complete, which may result in variations in hardness and impact resistance when manufacturing molded products, and is therefore undesirable. If the mixing temperature is too high, the color tone of the polycarbonate resin composition may deteriorate, which is also undesirable.

[0137] 2) A method of melt-mixing molten polycarbonate resin (a) and molten polycarbonate resin (b); Molten polycarbonate resin (a) and molten polycarbonate resin (b) are mixed using a mixing device such as a stirring tank, static mixer, kneader, twin-screw extruder, or single-screw extruder. In this case, if the polycarbonate resin is obtained by a melt polymerization method, for example, it may be introduced into the mixing device in a molten state without cooling or solidifying.

[0138] 3) A method for mixing polycarbonate resin (a) and polycarbonate resin (b) in solution; This method involves dissolving polycarbonate resin (a) and polycarbonate resin (b) in a suitable solvent to form a solution, mixing them in solution, and then isolating the resulting polycarbonate resin composition. The pellets or powders of polycarbonate resin (a) and the pellets or powders of polycarbonate resin (b) may be mixed in a solid state beforehand and then dissolved in a suitable solvent to form a solution. Alternatively, one of them may be dissolved in a suitable solvent first to form a solution, and then the other polycarbonate resin may be added to it to form a solution.

[0139] 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; substituted aromatic hydrocarbons such as nitrobenzene and acetophenone; and cyclic ethers such as tetrahydrofuran. Among these, chlorinated hydrocarbons such as dichloromethane or chlorobenzene are preferably used. These solvents can be used alone or in mixtures with other solvents.

[0140] Mixing equipment can include a stirring tank or a static mixer. There are no specific requirements for the mixing temperature, as long as the conditions are such that polycarbonate resin (a) and polycarbonate resin (b) dissolve; it is usually carried out at a temperature below the boiling point of the solvent used.

[0141] 4) A method for dry blending polycarbonate resin (a) and polycarbonate resin (b); This method involves dry blending pellets or powders of polycarbonate resin (a) with pellets or powders of polycarbonate resin (b) using a tumbler, super mixer, Henschel mixer, Nauter mixer, or the like.

[0142] Among the methods 1) to 4) described above, methods 1) and 2), which involve melt-kneading polycarbonate resin (a) and polycarbonate resin (b), and method 4), which involves dry-blending polycarbonate resin (a) and polycarbonate resin (b), are preferred.

[0143] In producing the polycarbonate resin composition, pigments, dyes, mold release agents, heat stabilizers, etc., can be added as appropriate in any of the above methods, as long as they do not impair the objective of the present invention.

[0144] [Molded products] The molded articles of the present invention contain the polycarbonate resin composition of the present invention and are obtained using the polycarbonate resin composition of the present invention. A conventional extrusion molding machine or injection molding machine is used to manufacture molded articles from the polycarbonate resin composition of the present invention.

[0145] The molding temperature for the polycarbonate resin composition of the present invention is preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. Furthermore, it is preferably 320°C or lower, and more preferably 300°C or lower. If the molding temperature is too low, the melt viscosity will increase, fluidity will decrease, and moldability may be reduced. If the molding temperature is too high, the polycarbonate resin composition may become discolored, and the color tone of the resulting molded product may deteriorate, which is undesirable. Additionally, polycarbonate resin compositions containing structural units derived from aliphatic dihydroxy compounds, such as carbonate structural units (X), may decompose at high temperatures.

[0146] When performing injection molding or extrusion molding, pigments, dyes, mold release agents, heat stabilizers, etc., can be appropriately added to the polycarbonate resin composition of the present invention, as long as they do not impair the objectives of the present invention.

[0147] <Injection molded products> The injection-molded articles of the present invention contain the polycarbonate resin composition of the present invention and are obtained using the polycarbonate resin composition of the present invention. A conventional injection molding machine is used to manufacture injection-molded articles from the polycarbonate resin composition of the present invention.

[0148] When using an injection molding machine or the like, the mold temperature is preferably 120°C or lower, more preferably 90°C or lower. It is also preferably 20°C or higher, and more preferably 30°C or higher. If the mold temperature is too high, the cooling time during molding will need to be extended, which may 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 may become too high, making it difficult to obtain a uniform molded product, which may result in problems such as unevenness on the surface of the molded product, and is undesirable.

[0149] <Extruded product> The extruded articles of the present invention contain the polycarbonate resin composition of the present invention and are obtained using the polycarbonate resin composition of the present invention. A conventional extruder is used to manufacture extruded articles from the polycarbonate resin composition of the present invention. The extruder is generally equipped with T-dies, round dies, etc., and can produce extruded articles of various shapes. Examples of extruded products include sheets, films, plates, tubes, and pipes. Among these, sheets or films are preferred.

[0150] <Laminated film> The laminated film of the present invention contains the polycarbonate resin composition of the present invention and is obtained using the polycarbonate resin composition of the present invention. In other words, a laminated film can be formed by co-extruding the polycarbonate resin composition of the present invention with another resin using an extrusion molding machine. In this laminated film, bisphenol A type polycarbonate resin is preferred as the resin constituting the layer laminated with the layer made of the polycarbonate resin composition of the present invention. In other words, since the polycarbonate resin composition of the present invention has excellent compatibility with bisphenol A type polycarbonate resin, a laminated film with excellent interlayer adhesion can be obtained by co-extruding the bisphenol A type polycarbonate resin and the polycarbonate resin composition of the present invention. Furthermore, when recycling this laminated film, a recycled product with excellent transparency can be obtained due to the excellent compatibility between the bisphenol A type polycarbonate resin and the polycarbonate resin composition of the present invention.

[0151] <Application> The molded articles of the polycarbonate resin composition of the present invention exhibit excellent self-healing properties, compatibility with bisphenol A type polycarbonate resin, and polymerization efficiency, making them suitable for a wide range of applications, including vehicle interiors. [Examples]

[0152] The present invention will be described in more detail below based on the following examples. However, the present invention is not limited to the following examples.

[0153] [Measurement and Evaluation Methods] The physical properties of the polycarbonate resins or polycarbonate resin compositions obtained in the following examples and comparative examples were measured and evaluated by the methods described below.

[0154] (2) Glass transition temperature (Tg) Measurements were performed using a differential scanning calorimeter (DSC6220, manufactured by SII). The obtained polycarbonate resin or polycarbonate resin composition was used as the measurement sample without drying. An aluminum sample pan containing approximately 10 mg of the measurement sample was heated from 30°C to 300°C at a nitrogen gas flow rate of 50 mL / min and a heating rate of 20°C / min, and then cooled to -90°C at a cooling rate of 40°C / min. After that, it was heated again to 300°C at a heating rate of 20°C / min. The differential scanning calorimeter curve obtained from the second heating was analyzed as the measurement curve. The analysis of the glass transition temperature (Tg) was performed in accordance with JIS K7121-1987. The extrapolation glass transition onset temperature was determined as the temperature at the intersection of a straight line extending from the low-temperature baseline to the high-temperature side and a tangent line drawn at the point where the slope of the curve of the step-like change portion of the glass transition is maximum. The extrapolated glass transition temperature was defined as the glass transition temperature (Tg).

[0155] (3) Viscosity average molecular weight (Mv) Polycarbonate resin or a polycarbonate resin composition was dissolved in methylene chloride (concentration 6.0 g / L), and the intrinsic viscosity (intrinsic viscosity) [η] (unit dL / g) at 20°C was determined using an Ubbelohde viscosity tube (manufactured by Moritomo Rika Kogyo Co., Ltd.). The viscosity-average molecular weight (Mv) was then calculated from Schnell's viscosity formula (see below). η = 1.23 × 10 -4 Mv 0.83

[0156] (4)Self-repairability The obtained polycarbonate resin or polycarbonate resin composition was dried at 100°C for 3 hours or more. 4 g of the dried polycarbonate resin or polycarbonate resin composition was placed in a hot press machine using a SUS spacer with a thickness of 0.5 mm, a length of 70 mm, and a width of 70 mm. The press was preheated for 4 minutes at a hot press temperature of 200-240°C, pre-pressed at a pressure of 2 MPa for 1 minute, and then pressurized at a pressure of 10 MPa for 1 minute. After that, the spacer and the resin were removed and cooled at room temperature to prepare a 0.5 mm thick pressed piece, which was used as a test specimen. The obtained test specimens were scratched using a pencil hardness tester (manufactured by Toyo Seiki) with a 4H pencil with a lead length of 5-6 mm, applying a load of 750 g. These specimens were then placed in a drying oven (manufactured by Tokyo Rikakikai Co., Ltd.) and heated at various temperatures (55°C, 60°C, 65°C) for 6 hours. The condition of the scratches after being left at room temperature for 1 day was also evaluated. The presence or absence of scratches after heating was confirmed by visual inspection and tactile examination. A "◎" rating indicated that the sample's wounds disappeared at room temperature, a "〇" rating indicated that the wounds disappeared at all temperatures, a "△" rating indicated that the wounds disappeared by touch but not by visual inspection when heated to 65°C, and a "×" rating indicated that no improvement in the wounds was perceived by either visual inspection or touch when heated to 65°C. Samples that could not be prepared were marked with a "-". "◎", "〇", and "△" ratings indicated self-healing properties.

[0157] (5) Compatibility test Polycarbonate resin or a polycarbonate resin composition, bisphenol A polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name Novalex 7022J), and methylene chloride were mixed in a weight ratio of 10:10:134. After drying this mixed solution at room temperature, a 100 μm thick film was obtained by hot pressing, and its transparency was evaluated by visual observation. The evaluation was as follows: "○" if the film was transparent, "△" if it was slightly cloudy, and "×" if it was cloudy white. If the evaluation was "○" or "△", it was evaluated as having compatibility with bisphenol A type polycarbonate resin.

[0158] (6) Polymerization efficiency Samples that easily reached the specified melt viscosity within a polycondensation time of less than 300 minutes were judged as "○", those requiring a polycondensation time of more than 300 minutes but 340 minutes or less to reach the specified melt viscosity were judged as "△", and those that did not reach the specified melt viscosity even after a polycondensation time of more than 340 minutes, or those for which the sample could not be recovered in pellet form, were judged as "×". Samples judged as "○" or "△" were judged to have excellent polymerization efficiency.

[0159] [raw materials] The compounds and resins used in the following examples and comparative examples are abbreviated as follows. Furthermore, the compounds and resins used were from the following manufacturers.

[0160] <Dihydroxy compounds> • PO3G500: Polytrimethylene ether glycol, number average molecular weight 562 (manufactured by ALLESSA, trade name: VELVETOL®) • 1,10-DD: 1,10-decanediol (manufactured by Kanto Chemical Co., Ltd.) • PTMG3000: Polytetramethylene ether glycol, number average molecular weight 2840 (manufactured by Mitsubishi Chemical Corporation) • THPE: 1,1,1-Tris(4-hydroxyphenyl)ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) • BPA: 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A) (manufactured by Mitsubishi Chemical Corporation) • BPC: 2,2-bis(4-hydroxy-3-methylphenyl)propane (=bisphenol C) (manufactured by Honshu Chemical Co., Ltd.)

[0161] <Carbonate ester> • DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

[0162] <Polymerization catalyst> • Cesium carbonate (manufactured by Kishida Chemical Co., Ltd.)

[0163] <Bisphenol A type polycarbonate resin> Bisphenol A type polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Corporation, trade name Novalex® 7022J, viscosity-average molecular weight 21,000)

[0164] [Example 1] A raw material mixture was prepared by adding PO3G500: 42.5 g (approximately 75.7 mmol), BPA: 65.2 g (approximately 0.29 mol), BPC: 7.2 g (approximately 28.3 mmol), DPC: 89.1 g (approximately 0.42 mol), THPE: 1.8 g (approximately 4.4 mmol), and a 0.04 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.00 μmol per mole of total dihydroxy compounds, to a glass reactor with a capacity of approximately 570 mL equipped with a reactor stirrer, reactor heater, and reactor pressure regulator.

[0165] Next, the pressure inside the glass reactor was reduced to approximately 100 Pa, and then the pressure was restored to atmospheric pressure with nitrogen. This process was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purging, the external temperature of the reactor was raised to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Then, the stirrer was rotated at 100 rpm. While distilling off the phenol produced as a by-product by the oligomerization reaction of the dihydroxy compound and DPC taking place inside the reactor, the pressure inside the reactor was reduced from an absolute pressure of 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) over 40 minutes.

[0166] Next, the reactor pressure was maintained at 13.3 kPa, and the transesterification reaction was carried out for 65 minutes while the phenol was further distilled off. After that, the external temperature of the reactor was raised to 260°C over 15 minutes, and the reactor pressure was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) over 40 minutes to remove the distilled phenol from the system. Then, the absolute pressure inside the reactor was reduced to approximately 50 Pa (approximately 0.4 Torr), and the polycondensation reaction was carried out. The rotation speed of the stirrer was gradually reduced as the reaction time progressed, and the polycondensation reaction was terminated when the reactor stirrer reached a predetermined stirring power.

[0167] Next, the reactor was repressurized to an absolute pressure of 101.3 kPa using nitrogen, and then increased to a gauge pressure of 0.1 MPa. The polycarbonate resin was then extracted in strand form from the bottom of the reactor to obtain the copolymerized polycarbonate resin in strand form, which was then pelletized using a rotary cutter.

[0168] The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 1.

[0169] [Example 2] The process was carried out in the same manner as in Example 1, except that a raw material mixture was prepared by adding PO3G500: 51.7 g (approximately 92.0 mmol), BPA: 56.9 g (approximately 0.25 mol), BPC: 6.3 g (approximately 24.7 mmol), DPC: 83.8 g (approximately 0.39 mol), THPE: 1.8 g (approximately 4.4 mmol), and a 0.04 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.00 μmol per mole of total dihydroxy compounds, to a glass reactor with a capacity of approximately 570 mL equipped with a reactor stirrer, reactor heater, and reactor pressure regulator. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 1.

[0170] [Example 3] The process was carried out in the same manner as in Example 1, except that a raw material mixture was prepared by adding PO3G500: 29.0 g (approximately 51.7 mmol), BPA: 69.7 g (approximately 0.31 mol), BPC: 17.4 g (approximately 68.0 mmol), DPC: 96.1 g (approximately 0.45 mol), THPE: 0.6 g (approximately 1.5 mmol), and a 0.04 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.00 μmol per mole of total dihydroxy compounds, to a glass reactor with a capacity of approximately 570 mL equipped with a reactor stirrer, reactor heater, and reactor pressure regulator. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 1.

[0171] [Example 4] The procedure described in Example 1 was carried out in a glass reactor with a capacity of approximately 570 mL, equipped with a reactor stirrer, reactor heater, and reactor pressure regulator. The raw material mixture was prepared by adding PO3G500: 28.6 g (approximately 51.0 mmol), BPA: 85.8 g (approximately 0.38 mol), DPC: 97.9 g (approximately 0.46 mol), THPE: 2.3 g (approximately 5.9 mmol), and a 0.04 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.00 μmol per mole of total dihydroxy compounds. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 1.

[0172] [Example 5] The procedure described in Example 1 was carried out in a glass reactor with a capacity of approximately 570 mL, equipped with a reactor stirrer, reactor heater, and reactor pressure regulator. The raw material mixture was prepared by adding PO3G500: 22.6 g (approximately 40.3 mmol), BPC: 90.6 g (approximately 0.35 mol), DPC: 91.5 g (approximately 0.43 mol), THPE: 3.5 g (approximately 8.8 mmol), and a 0.04 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.00 μmol per mole of total dihydroxy compounds. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 1.

[0173] [Example 6] In a glass reactor with a capacity of approximately 570 mL, equipped with a reactor stirrer, reactor heater, and reactor pressure regulator, a raw material mixture was prepared by adding PO3G500 to 1,10-DD, with 1,10-DD: 45.8 g (approximately 0.26 mol), BPA: 68.63 g (approximately 0.30 mol), DPC: 126.2 g (approximately 0.31 mol), THPE: 2.3 g (approximately 5.9 mmol), and a 0.4 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 2.00 μmol per mole of total dihydroxy compounds. The procedure was carried out in the same manner as in Example 1, except that the external heating temperature after the transesterification reaction was changed from 260°C to 240°C. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 1.

[0174] [Comparative Example 1] The evaluations for bisphenol A type polycarbonate resin were carried out using the procedure described above. The results are shown in Table 2.

[0175] [Comparative Example 2] A raw material mixture was prepared by adding 116.7 g (approximately 0.51 mol) of BPA, 111.2 g (approximately 0.52 mol) of DPC, 3.5 g (approximately 8.8 mmol) of THPE, and a 0.4 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 2.0 μmol per mole of total dihydroxy compounds. The procedure was carried out in the same manner as in Example 1, except that the external heating temperature after the transesterification reaction was changed from 260°C to 290°C. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 2.

[0176] [Comparative Example 3] A glass reactor with a capacity of approximately 570 mL, equipped with a reactor stirrer, reactor heater, and reactor pressure regulator, was used to prepare a raw material mixture by adding PTMG3000: 114.4 g (approximately 29.6 mmol), DPC: 8.95 g (approximately 0.04 mol), THPE: 2.3 g (approximately 7.4 mmol), and a 0.4 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 10.0 μmol per mole of total dihydroxy compounds. The procedure was carried out in the same manner as in Example 1, except that the external heating temperature after the transesterification reaction was changed from 260°C to 240°C. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 2.

[0177] [Comparative Example 4] The process was carried out in the same manner as in Example 1, except that a raw material mixture was prepared by adding PO3G500: 11.6 g (approximately 20.6 mmol), BPA: 83.2 g (approximately 0.36 mol), BPC: 20.8 g (approximately 81.1 mmol), DPC: 105.8 g (approximately 0.49 mol), THPE: 1.2 g (approximately 2.9 mmol), and a 0.04 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.0 μmol per mol of total dihydroxy compounds, to a glass reactor with a capacity of approximately 570 mL equipped with a reactor stirrer, reactor heater, and reactor pressure regulator. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 2.

[0178] [Comparative Example 5] The procedure described in Example 1 was followed, except that a raw material mixture was prepared by adding 40.9 g (approximately 72.7 mmol) of PO3G500, 60.7 g (approximately 0.27 mol) of BPA, 15.2 g (approximately 59.2 mmol) of BPC, 89.5 g (approximately 0.42 mol) of DPC, and a 0.04 wt% aqueous solution of cesium carbonate as a catalyst, to a glass reactor with a capacity of approximately 570 mL equipped with a reactor stirrer, reactor heater, and reactor pressure regulator, so that the amount of cesium carbonate was 1.0 μmol per mole of total dihydroxy compounds. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 2.

[0179] [Comparative Example 6] A glass reactor with a capacity of approximately 570 mL, equipped with a reactor stirrer, reactor heater, and reactor pressure regulator, was used to prepare a raw material mixture by adding 35.0 g (approximately 0.20 mol) of 1,10-DD, 81.7 g (approximately 0.36 mol) of BPA, 124.5 g (approximately 0.58 mol) of DPC, and a 0.4 wt% aqueous solution of cesium carbonate as a catalyst, so that the amount of cesium carbonate was 1.5 μmol per mole of total dihydroxy compounds. The procedure was carried out in the same manner as in Example 1, except that the external heating temperature after the transesterification reaction was changed from 260°C to 240°C. The obtained copolymerized polycarbonate resin was evaluated using the procedure described above. The results are shown in Table 2.

[0180] [Example 7] 2.5 g of the copolymerized polycarbonate resin produced in Example 1 (referred to as "PC1" in Table 3) and 1.5 g of bisphenol A type polycarbonate resin (referred to as "PC2" in Table 3) were dissolved in 20 mL of methylene chloride and dried at room temperature for 24 hours to obtain a polycarbonate resin composition. The polycarbonate resin compositions obtained in this manner were subjected to the evaluations described above. The results are shown in Table 3.

[0181] [Example 8] 3.0 g of the copolymerized polycarbonate resin produced in Example 1 (referred to as "PC1" in Table 3) and 1.0 g of bisphenol A type polycarbonate resin (referred to as "PC2" in Table 3) were dissolved in 20 mL of methylene chloride and dried at room temperature for 24 hours to obtain a polycarbonate resin composition. The polycarbonate resin compositions obtained in this manner were subjected to the evaluations described above. The results are shown in Table 3.

[0182] [Comparative Example 7] 2.0 g of the copolymerized polycarbonate resin (referred to as "PC1" in Table 3) produced in Example 1 and 2.0 g of bisphenol A type polycarbonate resin (referred to as "PC2" in Table 3) were dissolved in 20 mL of methylene chloride and dried at room temperature for 24 hours to obtain a polycarbonate resin composition. The polycarbonate resin compositions obtained in this manner were subjected to the evaluations described above. The results are shown in Table 3.

[0183] [Table 1]

[0184] [Table 2]

[0185] [Table 3]

[0186] [Consideration] From the above results, the following can be concluded. The copolymerized polycarbonate resins of Examples 1 to 5 have a Tg of 60°C or less and possess self-healing properties. The self-healing properties are not impaired in Examples 7 and 8, which are blends of the copolymerized polycarbonate resin of Example 1 with a bisphenol A type polycarbonate resin. Example 6, which used 1,10-DD instead of PO3G, also showed self-healing properties. Comparative Examples 1 and 2 are general BPA polycarbonate resins or equivalents, and do not possess self-healing properties. Comparative Example 3, which has carbonate structural units (X) and carbonate structural units (Z) but lacks carbonate structural unit (Y), exhibits poor compatibility with bisphenol A type polycarbonate resin and inferior polymerization efficiency. Even with carbonate structural units (X), carbonate structural units (Y), and carbonate structural units (Z), Comparative Example 4, where the glass transition temperature (Tg) exceeds 60°C, does not exhibit self-healing properties. The copolymerized polycarbonate resins of Comparative Examples 5 and 6, which have carbonate structural units (X) and carbonate structural units (Y) but lack carbonate structural unit (Z), exhibit low polymerization efficiency. Even when the copolymerized polycarbonate resin of Example 1 and the bisphenol A type polycarbonate resin are blended, Comparative Example 7, which has a glass transition temperature (Tg) exceeding 60°C, does not exhibit self-healing properties.

Claims

1. A polycarbonate resin composition comprising a carbonate structural unit (X) derived from a dihydroxy compound in which both terminal hydroxyl groups are alcoholic, a carbonate structural unit (Y) derived from a dihydroxy compound in which both terminal hydroxyl groups are phenolic, and a carbonate structural unit (Z) derived from a crosslinkable compound, wherein the glass transition temperature (Tg) is 60°C or lower.

2. The polycarbonate resin composition according to claim 1, wherein the content of the carbonate structural unit (X) in 100% by mass of the total carbonate structural units of the polycarbonate resin composition is 10% by mass or more and 70% by mass or less.

3. The polycarbonate resin composition according to claim 1, wherein the content of the carbonate structural unit (Y) in 100% by mass of the total carbonate structural units of the polycarbonate resin composition is 20% by mass or more and 90% by mass or less.

4. The polycarbonate resin composition according to claim 1, wherein the content of the carbonate structural unit (Z) in 100% by mass of the total carbonate structural units of the polycarbonate resin composition is 0.1% by mass or more and 10% by mass or less.

5. The polycarbonate resin composition according to claim 1, wherein the viscosity-average molecular weight (Mv) is in the range of 15,000 to 50,000.

6. The polycarbonate resin composition according to claim 1, wherein the carbonate structural unit (X) is derived from a dihydroxy compound that does not have an aromatic ring.

7. The polycarbonate resin composition according to claim 1, wherein the carbonate structural unit (Y) is derived from a dihydroxy compound represented by the following formula (1). 【Chemistry 1】 (In formula (1), W 1 ~W 4 Each of these is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, W 5 is a single bond, or -CR 1 R 2 - (R 1 and R 2 Each of these is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Alternatively, each of these is a cycloalkylidene group having 3 to 10 carbon atoms.

8. The polycarbonate resin composition according to claim 1, wherein the carbonate structural unit (Z) is derived from a compound having three or more hydroxyl groups.

9. The polycarbonate resin composition according to claim 1, wherein the carbonate structural unit (X) is derived from one or more dihydroxy compounds represented by the following formula (2), dihydroxy compounds represented by the following formula (3), and dihydroxy compounds represented by the following formula (4). 【Chemistry 2】 (In equations (2) and (3), n is an integer greater than or equal to 1.)

10. The polycarbonate resin composition according to claim 6, wherein the number average molecular weight of the dihydroxy compound represented by formula (2) and / or the dihydroxy compound represented by formula (3) is 5,000 or less.

11. The polycarbonate resin composition according to claim 7, wherein the carbonate structural unit (Y) is derived from a dihydroxy compound represented by the following formula (5) and / or a dihydroxy compound represented by the following formula (6). 【Transformation 3】

12. The polycarbonate resin composition according to claim 8, wherein the carbonate structural unit (Z) is derived from a compound represented by the following formula (7). 【Chemistry 4】

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

14. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 13.

15. An injection-molded article comprising the polycarbonate resin composition according to any one of claims 1 to 13.

16. An extruded article comprising the polycarbonate resin composition according to any one of claims 1 to 13.

17. A laminated film comprising the polycarbonate resin composition according to any one of claims 1 to 13.

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