Polycarbonate resin composition and molded article

Abstract

To provide a polycarbonate resin composition that has high chemical resistance and thermal aging resistance, barely shows a poor appearance during injection molding, and has excellent thermostability, and a molding including the resin composition.SOLUTION: A polycarbonate resin composition contains at least two polycarbonate resins that are different in the content of constitutional units derived from dihydroxy compounds represented by general formula (1). The polycarbonate resins each have a reduced viscosity that satisfies specific conditions.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded article containing a plurality of polycarbonate resins.

Background Art

[0002] Polycarbonate resins are used for various applications as engineering plastics due to their excellent physical properties. Polycarbonate resins using isosorbide as a monomer exhibit excellent performance different from that of conventional aromatic polycarbonate resins, and thus various studies have been conducted (Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, polycarbonate resins using isosorbide as a monomer have room for improvement in chemical resistance and heat aging resistance. As a result of the studies by the present inventors, it has been found that by increasing the molecular weight of polycarbonate resins using isosorbide as a monomer, the chemical resistance and heat aging resistance of the resins are improved. However, polycarbonate resins obtained from isosorbide have a low upper limit processing temperature, and thus problems caused by a decrease in fluidity occur due to an increase in molecular weight. For example, when the resin temperature during molding is increased as a method for improving the fluidity of the resin, a heat history The appearance of the molded product may change due to discoloration of the resin caused by the decomposition gas, or silver streaks caused by the generated decomposition gas. There is a worsening problem.

[0005] The object of the present invention is to provide a molded article having high chemical resistance and heat aging resistance and having few defects in appearance during injection molding. Polycarbonate resin composition having good heat resistance and a method for manufacturing the same To provide a molded article. [Means for solving the problem]

[0006] In order to solve the above problems, the present inventors have conducted extensive research and have found that a compound represented by the following general formula (1) At least two kinds of polycarbonates having different content ratios of structural units derived from dihydroxy compounds The reduced viscosity of each polycarbonate resin meets certain conditions. The polycarbonate resin composition not only improves chemical resistance and heat aging resistance, but also The inventors have found that the composition has excellent impact resistance, heat resistance, moldability, and appearance of molded products, and have arrived at the present invention. Reached. That is, the gist of the present invention lies in the following.

[0007] [1] Polycarbonate containing polycarbonate resin (A) and polycarbonate resin (B) A resin composition comprising: The polycarbonate resin (A) and the polycarbonate resin (B) are both represented by the following formula ( 1), which has a structural unit (a) derived from a dihydroxy compound represented by the formula (1), The content of the structural unit (a) in the polycarbonate resin (A) is 60 mol % or more of the structural units derived from all dihydroxy compounds in the nate resin (A) The content of the structural unit (a) in the polycarbonate resin (B) is Less than 60 mol with respect to the structural unit derived from all dihydroxy compounds in the carbonate resin (B). %, and The reduced viscosity of the polycarbonate resin (A) is 0.45 dL / g or more and less than 0.50 dL / g. And The reduced viscosity of the polycarbonate resin (B) is higher than that of the polycarbonate resin (A). A polycarbonate resin composition.

[0008] [Chemical formula]

[0009] [2] The reduced viscosity of the polycarbonate resin (B) is 0.45 dL / g or more and less than 0.55 dL / g, and the polycarbonate resin composition according to [1] above. dL / g, and the polycarbonate resin composition according to [1] above. [3] The reduced viscosity of the polycarbonate resin (B) is 0.55 dL / g or more and 0.65 dL / g or less, and the polycarbonate resin composition according to [1] above. dL / g or less, and the polycarbonate resin composition according to [1] above. [4] At least one of the polycarbonate resin (A) and the polycarbonate resin (B) contains a structural unit (a2-1) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and ether group-containing dihydroxy compounds other than the dihydroxy compound represented by the formula (1), and the polycarbonate resin composition according to any one of [1] to [3] above. Selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and ether group-containing dihydroxy compounds other than the dihydroxy compound represented by the formula (1). One or more dihydroxy compounds, and the polycarbonate resin composition according to any one of [1] to [3] above. [5] The content of the polycarbonate resin (A) is 25 parts by weight or more with respect to 100 parts by weight in total of the polycarbonate resin composition, and the polycarbonate resin composition according to any one of [1] to [4] above. 00 parts by weight, and the polycarbonate resin composition according to any one of [1] to [4] above. [6] Further, an elastomer (C) having a core-shell structure is included, and the above [1] to [5 The polycarbonate resin composition according to any one of the above. [7] The content of the elastomer (C) having the core - shell structure is 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polycarbonate resin composition, the polycarbonate resin composition according to the above [6]. [8] A molded article obtained by molding the polycarbonate resin composition according to any one of the above [1] to [7]. [9] The molded article according to the above [8], which is a part for an automobile.

[0010] [Reasons for the effectiveness of the present invention] The reason why the present invention exhibits an effect is not yet clear, but it is presumed as follows. That is, by including the polycarbonate resin (A) having a reduced viscosity within a specific range, the entanglement points of the molecules increase, and it is considered that the effect of suppressing the strength reduction due to heat and chemicals is achieved. Also, by including the polycarbonate resin (B) having a reduced viscosity higher than that of the polycarbonate resin (A), the decomposition of the resin when the processing temperature during molding is increased is suppressed, and the effect of suppressing the occurrence of appearance defects is achieved.

Effects of the invention

[0011] According to the present invention, it is possible to provide a polycarbonate resin composition having high chemical resistance and heat - aging resistance, having few appearance defects during injection molding, and having good heat resistance. Therefore, it is possible to provide a polycarbonate resin composition and its molded articles applicable to a wide range of fields such as injection molding fields for electrical and electronic parts, automobile parts, film and sheet fields, and further building material applications.

Modes for carrying out the invention

[0012] Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following description and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the present invention, when expressing numerical values or physical property values with "~" sandwiched before and after, the values before and after are used as including those values. In addition, in the present invention, those obtained by mixing at least a plurality of polycarbonate resins having different compositions are referred to as "polycarbonate resin compositions". In the present invention, various additives may be blended in the polycarbonate resin composition. In the present invention, when expressing with numerical values or physical property values sandwiched before and after using "~", the values before and after are used as including those values. Also, in the present invention, those obtained by mixing at least a plurality of polycarbonate resins having different compositions are referred to as "polycarbonate resin compositions". In the present invention, various additives may be blended in the polycarbonate resin composition. In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit. In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit. In the present invention, the polycarbonate resin composition may contain various additives.

[0013] In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit. In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit. In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit. In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit. In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit. In the present specification, a "structural unit" means a partial structure constituting a resin, which means a specific partial structure included in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a polymerization reactive group present at the terminal portion of a polymer and a partial structure sandwiched between the linking group adjacent to the polymerizable reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is a linking group, and a partial structure sandwiched between adjacent carbonyl groups is expressed as a structural unit.

[0014] [Polycarbonate Resin Composition] The polycarbonate resin composition (hereinafter, may be simply referred to as "resin composition") contains at least two or more polycarbonate resins containing a structural unit represented by the following formula (1). The structural unit represented by the following formula (1) may be hereinafter referred to as structural unit (a). Specifically, the polycarbonate resin composition of the present invention contains at least polycarbonate resin (A) and polycarbonate resin (B). The polycarbonate resin composition (hereinafter, may be simply referred to as "resin composition") contains at least two or more polycarbonate resins containing a structural unit represented by the following formula (1). The structural unit represented by the following formula (1) may be hereinafter referred to as structural unit (a). Specifically, the polycarbonate resin composition of the present invention contains at least polycarbonate resin (A) and polycarbonate resin (B). The structural unit represented by the following formula (1) may be hereinafter referred to as structural unit (a). Specifically, the polycarbonate resin composition of the present invention contains at least polycarbonate resin (A) and polycarbonate resin (B). The polycarbonate resin composition of the present invention contains at least polycarbonate resin (A) and polycarbonate resin (B). The carbonate resins (B) all contain the structural unit (a), but the molar ratios of the structural unit (a) constituting each resin are at least different. The polycarbonate resin (A) is a resin containing 60 mol% or more of the structural unit (a) with respect to the structural unit derived from all dihydroxy compounds in the polycarbonate resin (A). The polycarbonate resin (B) is a resin containing less than 60 mol% of the structural unit (a) with respect to the structural unit derived from all dihydroxy compounds in the polycarbonate resin (B). In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5.

[0015]

Chemical formula

[0016] The polycarbonate resin (A) is mainly responsible for improving the heat aging resistance, chemical resistance, and heat resistance in the polycarbonate resin composition of the present invention. Therefore, when the content is above the lower limit of the above range, the heat aging resistance, chemical resistance, and heat resistance are more excellent, and when it is below the upper limit of the above range, the moldability, In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5. In the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (where polycarbonate resin (A) / polycarbonate resin (B)) is not particularly limited, but is usually 1 / 99 to 99 / 1. From the viewpoint of obtaining more excellent heat resistance, mechanical properties, and moldability, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) is preferably 50 / 50 to 99 / 1, more preferably 60 / 40 to 98 / 2, even more preferably 65 / 35 to 97 / 3, particularly preferably 70 / 30 to 95 / 5, and most preferably 85 / 15 to 95 / 5.

[0017] The polycarbonate resin (A) is mainly responsible for improving the heat aging resistance, chemical resistance, and heat resistance in the polycarbonate resin composition of the present invention. Therefore, when the content is above the lower limit of the above range, the heat aging resistance, chemical resistance, and heat resistance are more excellent, and when it is below the upper limit of the above range, the moldability, The polycarbonate resin (A) is mainly responsible for improving the heat aging resistance, chemical resistance, and heat resistance in the polycarbonate resin composition of the present invention. Therefore, when the content is above the lower limit of the above range, the heat aging resistance, chemical resistance, and heat resistance are more excellent, and when it is below the upper limit of the above range, the moldability, The polycarbonate resin (A) is mainly responsible for improving the heat aging resistance, chemical resistance, and heat resistance in the polycarbonate resin composition of the present invention. Therefore, when the content is above the lower limit of the above range, the heat aging resistance, chemical resistance, and heat resistance are more excellent, and when it is below the upper limit of the above range, the moldability, Excellent appearance of molded products.

[0018] The polycarbonate resin (B) is mainly used for molding in the polycarbonate resin composition of the present invention. Since it plays a role in improving the properties and appearance of molded products, the content is equal to or more than the lower limit of the above range. When the composition is equal to or less than the lower limit of the above range, the composition has excellent heat aging resistance, chemical resistance, and heat resistance. It is more durable.

[0019] [Polycarbonate resin (A), (B)] The polycarbonate resins (A) and (B) used in the polycarbonate resin composition of the present invention are Polycarbonate in which structural units derived from dihydroxy compounds are linked by carbonate bonds The dihydroxy compound represented by the general formula (1) (hereinafter referred to as "dihydroxy compound") is a hydroxyl group-containing resin. The compound (1) may be referred to as "a compound (1)". The structure derived from the dihydroxy compound constituting the polycarbonate resins (A) and (B) used The synthetic unit is formed by removing a hydrogen atom from a hydroxyl group of a dihydroxy compound.

[0020] A dihydroxy compound forming a structural unit represented by the above formula (1) (hereinafter, “compound (1)”) The stereoisomeric forms of isosorbide, isomannide, and isosorbide are referred to as isosorbide. These may be used alone or in combination of two or more. Among them, various starches are abundant and easily available as plant-derived resources. Isosorbide, which is obtained by dehydrating and condensing sorbitol produced from sorbitol, is available and manufactured. Ease of molding, moldability, properties of the resulting molded product (e.g., heat resistance, impact resistance, surface hardness, carbon Neutral) is the most preferable.

[0021] The polycarbonate resin (A) and the polycarbonate resin (B) differ from each other at least in the molar ratio of the structural unit (a).

[0022] The polycarbonate resin (A) contains 60 mol% or more of the structural unit (a) with respect to the structural units derived from all the dihydroxy compounds in the polycarbonate resin. The polycarbonate resin (A) may be a homopolymer substantially free of structural units other than the structural unit (a), or may also be a copolymerized polycarbonate resin containing structural units other than the structural unit (a). A homopolymer of the structural unit (a) has high heat resistance but has insufficient impact resistance or has characteristics such as high water absorption and poor dimensional stability. Therefore, from the viewpoint of improving various physical property balances for use as a molding material, the polycarbonate resin (A) is preferably a copolymerized polycarbonate resin containing the structural unit (a) and other structural units. Since the polycarbonate resin (A) mainly serves as a component responsible for heat resistance, chemical resistance, and heat aging resistance, the upper limit of the content of the structural unit (a) in the polycarbonate resin (A) is preferably 90 mol%, particularly preferably 80 mol%, and even more preferably 75 mol%. Also, the lower limit of the content of the structural unit (a) is preferably 65 mol%. By adjusting the content ratio of the constitutional unit (a) within this range, both the impact resistance and heat resistance of the polycarbonate resin can be enhanced well in balance. In this specification, structural units other than the structural unit (a) constituting the polycarbonate resin are appropriately referred to as "structural unit (b)". In this specification, when indicating numerical values of the upper limit and the lower limit, it means a range including those numerical values. That is, it means that the value is less than or equal to the upper limit value and greater than or equal to the lower limit value. ​​​​​​​​ 。

[0023] The polycarbonate resin (B) contains less than 60 mol% of the structural unit (a) with respect to all the structural units derived from the dihydroxy compounds in the polycarbonate resin. Since the polycarbonate resin (B) contains the structural unit (a) in the same manner as the polycarbonate resin (A), the polycarbonate resin (B) is likely to exhibit compatibility with the polycarbonate resin (A). The polycarbonate resin (B) contains the structural unit (a) to such an extent that compatibility with the polycarbonate resin (A) can be ensured, and it is preferable to increase the content of the structural unit (b), for example, more than the content of the structural unit (b) in the polycarbonate resin (A). The polycarbonate resin (B) preferably contains 55 mol% or less of the structural unit (a), and more preferably 50 mol% or less. Also, in order to ensure compatibility with the polycarbonate resin (A), the lower limit of the content of the polycarbonate resin (B) is usually 1 mol%, preferably 5 mol%, and more preferably 10 mol%.

[0024]

[0025] It is preferable that at least one of the polycarbonate resin (A) and the polycarbonate resin (B) is a copolymerized polycarbonate resin containing the structural unit (a) and the structural unit (b), and it is more preferable that both the polycarbonate resin (A) and the polycarbonate resin (B) are copolymerized polycarbonate resins containing the structural unit (a) and the structural unit (b).

[0025] When the polycarbonate resin (A) contains the structural unit (b), the proportion of the structural unit (b) in the polycarbonate (A) is the total dihydroxylation in the polycarbonate resin. For the structural units derived from the compound, 5 mol% or more is preferable, 10 mol% or more is more preferable, and 20 mol% or more is even more preferable. Also, 40 mol% or less is preferable, and 35 mol% or less is more preferable. Being within the above range results in excellent balance among heat resistance, impact resistance, and chemical resistance.

[0026] In the polycarbonate resin (B), the content ratio of the structural unit (b) is preferably 40 mol% or more with respect to the structural units derived from all dihydroxy compounds in the polycarbonate resin, more preferably 45 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. When within the above range, impact resistance, chemical resistance, and high fluidity, which are in a trade-off relationship with each other, are excellently balanced at a high level.

[0027] As the structural unit (b), structural units derived from dihydroxy compounds other than the formula (1) are preferable, but structural units derived from compounds other than dihydroxy compounds may also be used. At least one of the polycarbonate resin (A) and the polycarbonate resin (B) is preferably composed of a copolymer containing structural units (hereinafter sometimes referred to as structural units (a2-1)) derived from one or more dihydroxy compounds selected from the group consisting of aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and ether group-containing dihydroxy compounds other than the dihydroxy compound represented by the formula (1). It is more preferable that both the polycarbonate resin (A) and the polycarbonate resin (B) are copolymer polycarbonate resins containing the structural unit (a2-1). These dihydroxy compounds have a flexible molecular structure. Since they have [the relevant property], by using these dihydroxy compounds as raw materials, the chemical resistance, heat aging resistance, and impact resistance of the obtained poly carbonate resin can be improved. Among these dihydroxy compounds, dihydroxy compounds of aliphatic hydrocarbons and dihydroxy compounds of alicyclic hydrocarbons with a large effect of improving chemical resistance, heat aging resistance, and impact resistance are preferably used, and it is most preferred to use dihydroxy compounds of alicyclic hydrocarbons. From the viewpoint of further enhancing heat resistance and impact resistance, among the alicyclic dihydroxy compounds, cyclobutanediol, cyclohexanedimethanol, and tricyclodecanedimethanol are particularly preferred. Specific examples of dihydroxy compounds of aliphatic hydrocarbons, dihydroxy compounds of alicyclic hydrocarbons, and ether-containing dihydroxy compounds are as follows . .

[0028] As the dihydroxy compounds of aliphatic hydrocarbons, for example, the following dihydroxy compounds can be employed. Linear aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.; branched-chain aliphatic dihydroxy compounds such as 1,2-propanediol, 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

[0029] As the dihydroxy compounds of alicyclic hydrocarbons, for example, the following dihydroxy compounds can be can be adopted. 1,2-cyclohexanedimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-deca ringdimethanol, 2,3-decalindimethanol, 2,3-norbornanedimethanol , 2,5-norbornanedimethanol, 1,3-adamantanediol, limonene, etc. Dihydroxy compounds derived from terpene compounds such as those exemplified above, alicyclic hydrocarbons are primary alcohols of dihydroxy compounds; 1,2-cyclohexanediol, 1,4 -cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, 2 ,2,4,4-tetramethyl-1,3-cyclobutanediol, etc. are secondary or tertiary alcohols of alicyclic hydrocarbons dihydroxy compounds.

[0030] Examples of ether-containing dihydroxy compounds include oxyalkylene glycols and dihydroxy compounds containing an acetal ring. Examples of oxyalkylene glycols include, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol, etc. can be adopted.

[0031] Examples of dihydroxy compounds containing an acetal ring include, for example, spiroglycol represented by the following formula (2) and dioxane glycol represented by the following formula (3), etc. can be adopted.

[0032] [Chemical formula]

[0033]

Chem.

[0034] Further, the polycarbonate resins (A) and (B) (hereinafter referred to as "polycarbonate resin" ") may further contain structural units other than the structural unit (a) and the structural unit (a2-1). As such other dihydroxy compounds for forming such structural units, for example, dihydroxy compounds containing an aromatic group can be employed. However, when the polycarbonate resin contains many structural units derived from a dihydroxy compound containing an aromatic group, as described above, a polycarbonate resin with a high molecular weight cannot be obtained due to the aforementioned reasons, and the effect of improving impact resistance may decrease. Also, as will be described later, in the case of a polycarbonate resin containing many structural units derived from a dihydroxy compound containing an aromatic group as a structural unit of the polycarbonate resin, there is a possibility that it may be decomposed by adding an amine-based compound, resulting in a decrease in the impact resistance and color tone of the polycarbonate resin composition. Therefore, from the viewpoint of further improving impact resistance and color tone, with respect to 100 mol% of the structural units derived from all dihydroxy compounds, the content ratio of the structural units derived from a dihydroxy compound containing an aromatic group is preferably less than 50 mol%, more preferably 10 mol% or less, even more preferably 5 mol% or less, and most preferably the polycarbonate resin does not contain structural units derived from a dihydroxy compound containing an aromatic group.

[0035] Examples of the dihydroxy compound containing an aromatic group include the following dihydroxy compounds although these can be adopted, it is also possible to adopt dihydroxy compounds other than these . 2,2-Bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphen yl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane , 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis (4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hy droxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)meth ane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphe nyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4 -hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphe nylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1- bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl) methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3-bis(2-(4- hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxy phenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexa fluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4 -hydroxyphenyl)sulfone, 2,4’-dihydroxydiphenylsulfone, bis( 4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)s Rufide, bis(4-hydroxyphenyl) disulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, etc. Aromatic bisphenol compounds; 2,2-bis(4-(2-hydroxyethoxy)phenyl) propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl) propane, 1 ,3-bis(2-hydroxyethoxy) benzene, 4,4'-bis(2-hydroxyethoxy) biphenyl, bis(4-(2-hydroxyethoxy)phenyl) sulfone, etc. Dihydroxy compounds having an ether group bonded to an aromatic group; 9,9-bis(4-(2-hydroxyethoxy)phenyl) fluorene, 9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl) fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl) fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl) fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl) fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl) fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl) fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl) fluorene, 9, ,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl) fluorene, 9, ,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl) fluorene, etc. etc. etc. etc. etc. etc. etc. etc. etc. etc. etc. etc. 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene and other dihydroxy compounds having a fluorene ring and the like. The other dihydroxy compounds can be appropriately selected according to the properties required for the polycarbonate resin. Further, only one kind of the other dihydroxy compounds may be used, or a plurality of kinds may be used in combination. By using the other dihydroxy compounds in combination with compound (1), it is possible to obtain effects such as improvement of the flexibility and mechanical properties of the polycarbonate resin and improvement of the moldability. The dihydroxy compounds used as raw materials for the polycarbonate resin may contain stabilizers such as reducing agents, antioxidants, deoxidizers, light stabilizers, antacids, pH stabilizers or heat stabilizers. In particular, compound (1) has a property of being easily deteriorated in an acidic state. Therefore, by using a basic stabilizer in the synthesis process of the polycarbonate resin, the deterioration of compound (1) can be suppressed. As a result, the quality of the obtained polycarbonate resin composition can be further improved.

[0036] As the basic stabilizer, for example, the following compounds can be employed. Hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates and fatty acid salts of metals in Group 1 or Group 2 in the Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005); tetramethylammonium hydroxide, tetraethylammonium hydroxide The other dihydroxy compounds can be appropriately selected according to the properties required for the polycarbonate resin. Also, only one kind of the other dihydroxy compounds may be used, or a plurality of kinds may be used in combination. By using the other dihydroxy compounds in combination with compound (1), effects such as improvement of the flexibility and mechanical properties of the polycarbonate resin and improvement of the moldability can be obtained. When the other dihydroxy compounds are used in combination with compound (1), effects such as improvement of the flexibility and mechanical properties of the polycarbonate resin and improvement of the moldability can be obtained. When the other dihydroxy compounds are used in combination with compound (1), effects such as improvement of the flexibility and mechanical properties of the polycarbonate resin and improvement of the moldability can be obtained. When the other dihydroxy compounds are used in combination with compound (1), effects such as improvement of the flexibility and mechanical properties of the polycarbonate resin and improvement of the moldability can be obtained.

[0037] The dihydroxy compounds used as raw materials for the polycarbonate resin may contain stabilizers such as reducing agents, antioxidants, deoxidizers, light stabilizers, antacids, pH stabilizers or heat stabilizers. The dihydroxy compounds used as raw materials for the polycarbonate resin may contain stabilizers such as reducing agents, antioxidants, deoxidizers, light stabilizers, antacids, pH stabilizers or heat stabilizers. In particular, compound (1) has a property of being easily deteriorated in an acidic state. Therefore, by using a basic stabilizer in the synthesis process of the polycarbonate resin, the deterioration of compound (1) can be suppressed. In particular, compound (1) has a property of being easily deteriorated in an acidic state. Therefore, by using a basic stabilizer in the synthesis process of the polycarbonate resin, the deterioration of compound (1) can be suppressed. In particular, compound (1) has a property of being easily deteriorated in an acidic state. Therefore, by using a basic stabilizer in the synthesis process of the polycarbonate resin, the deterioration of compound (1) can be suppressed. As a result, the quality of the obtained polycarbonate resin composition can be further improved.

[0038] As the basic stabilizer, for example, the following compounds can be employed. In the Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005), hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates and fatty acid salts of metals in Group 1 or Group 2; tetramethylammonium hydroxide, tetraethylammonium hydroxide Roxide, tetrapropylammonium hydroxide, tetrabutylammonium hydro xide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammo nium hydroxide, triethylbenzylammonium hydroxide, triethylpheny lammonium hydroxide, tributylbenzylammonium hydroxide, tributy lphenylammonium hydroxide, tetraphenylammonium hydroxide, ben zyltriphenylammonium hydroxide, methyltriphenylammonium hydroxi de and butyltriphenylammonium hydroxide and other basic ammonium compounds; Diethylamine, dibutylamine, triethylamine, morpholine, N-methylmorpholi ne, pyrrolidine, piperidine, 3-amino-1-propanol, ethylenediamine, N- methyldiethanolamine, diethylethanolamine, diethanolamine, trietha nolamine, 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-ami nopridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyr idine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidaz ole, imidazole, 2-mercaptoimidazole, 2-methylimidazole and amino quinoline and other amine compounds, as well as di-(tert-butyl)amine and 2,2,6, 6-tetramethylpiperidine and other hindered amine compounds.

[0039] There is no particular limitation on the content of the basic stabilizer in the dihydroxy compound, but in chemical Since the compound (1) is unstable in an acidic state, the content of the basic stabilizer is preferably set so that the pH of the aqueous solution of the dihydroxy compound containing the basic stabilizer is around 7. Preferably, the content of the basic stabilizer is set so that the pH of the aqueous solution of the dihydroxy compound containing the basic stabilizer is around 7.

[0040] The content of the basic stabilizer with respect to the compound (1) is preferably 0.0001 to 1% by weight. In this case, the effect of preventing the deterioration of the compound (1) can be sufficiently obtained. From the viewpoint of further enhancing this effect, the content of the basic stabilizer is more preferably 0.001 to 0.1% by weight. From the viewpoint of further enhancing this effect, the content of the basic stabilizer is more preferably 0.001 to 0.1% by weight. More preferably, it is in this range.

[0041] As the carbonic acid diester used as the raw material of the polycarbonate resin, usually, a compound represented by the following formula (4 ) can be adopted. These carbonic acid diesters may be used alone or in combination of two or more. These carbonic acid diesters may be used alone or in combination of two or more.

[0042]

Chemical formula

[0043] In the above formula (4), A 1 and A 2 are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A and A 1 and A 2 may be the same or different. A 1 and A 2 are preferably a substituted or unsubstituted aromatic hydrocarbon group, and more preferably an unsubstituted aromatic hydrocarbon group. More preferably, it is an unsubstituted aromatic hydrocarbon group.

[0044] Examples of the carbonic acid diester represented by the formula (4) include diphenyl carbonate ( DPC) and substituted diphenyl carbonates such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate can be employed. Among these diester carbonates, it is preferable to use diphenyl carbonate or substituted diphenyl carbonate, and it is particularly preferred to use diphenyl carbonate. Note that the diester carbonate may contain impurities such as chloride ions, and in some cases, the impurities may inhibit the polycondensation reaction or deteriorate the color tone of the resulting polycarbonate resin. Therefore, if necessary, it is preferable to use a purified product obtained by distillation or the like.

[0045] [Method for Producing Polycarbonate Resins (A) and (B)] The polycarbonate resins (A) and (B) can be synthesized by subjecting the above-described dihydroxy compound and diester carbonate to polycondensation by a transesterification reaction. More specifically, it can be obtained by removing by-products such as monohydroxy compounds generated in the transesterification reaction out of the system during the polycondensation.

[0046] The transesterification reaction proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst is referred to as a "polymerization catalyst"). The type of the polymerization catalyst can have a very significant influence on the reaction rate of the transesterification reaction and the quality of the resulting polycarbonate resin.

[0047] The polymerization catalyst is not limited as long as it can satisfy the transparency, color tone, heat resistance, weather resistance, and mechanical strength of the resulting polycarbonate resin. Examples of the polymerization catalyst include, for example, Group I or Group II in the long-period form of the periodic table (hereinafter, simply referred to as "Group 1" and "Group 2"). The metal compound of ), and basic boron compounds, basic phosphorus compounds, basic ammonium compounds and basic compounds such as amine compounds can be used. Among them, Group 1 metal compounds and / or Group 2 metal compounds are preferred.

[0048] As the above-mentioned Group 1 metal compound, for example, the following compounds can be adopted. Hydroxide sodium, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate , potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate , lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, acetic acid cesium, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, boron hydride lithium, cesium borohydride, sodium phenylborate, potassium phenylborate , lithium phenylborate, cesium phenylborate, sodium benzoate, benzoic acid potassium, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, phosphorus dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate sodium diphenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, diphenyl phosphate cesium, alcoholates of sodium, potassium, lithium, cesium, phenolates, bismuth 2 sodium salts, 2 potassium salts, 2 lithium salts and 2 cesium salts of phenol A, etc. As the Group 1 metal compound, from the viewpoints of polymerization activity and the color tone of the obtained polycarbonate resin , lithium compounds are preferred.

[0049] As the above-mentioned Group 2 metal compound, for example, the following compounds can be adopted. Hydroxide Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, hydrogen carbonate Calcium, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, carbonate Calcium, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, Barium acetate, magnesium acetate, strontium acetate, calcium stearate, ste Barium aluminate, magnesium stearate and strontium stearate, etc. As the Group 2 metal compound, a magnesium compound, a calcium compound or a barium compound is preferable, and from the viewpoints of polymerization activity and the color tone of the obtained polycarbonate resin, a magnesium compound and / or a calcium compound is more preferable, and a calcium compound is most preferable.

[0050] In addition, auxiliary to the above Group 1 metal compound and / or Group 2 metal compound, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds and other basic compounds can also be used in combination, but it is particularly preferable to use only the Group 1 metal compound and / or Group 2 metal compound .

[0051] As the above basic phosphorus compound, for example, the following compounds can be adopted. Tri Ethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri -n-butylphosphine, triphenylphosphine, tributylphosphine and quaternary pho sphonium salts, etc.

[0052] As the above basic ammonium compound, for example, the following compounds can be adopted. Tetramethylammonium hydroxide, tetraethylammonium hydroxide , tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydro xide, trimethylphenylammonium hydroxide, triethylmethylammonium h ydroxide, triethylbenzylammonium hydroxide, triethylphenylammoniu m hydroxide, tributylbenzylammonium hydroxide, tributylphenylammo nium hydroxide, tetraphenylammonium hydroxide, benzyltri phenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide and the like.

[0053] As the amine compound, for example, the following compounds can be employed. 4- aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-di ethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxy pyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole , 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and guanidi ne and the like.

[0054] The amount of the polymerization catalyst used is preferably 0.1 ~300 μmol per 1 mol of the total dihydroxy compound used in the reaction, more preferably 0.5~100 μmol, and particularly preferably 1~50 μmol.

[0055] When using, as the polymerization catalyst, a compound containing at least one metal selected from the group consisting of Group 2 metals and lithium in the long-period type periodic table, particularly magnesium compounds and / or ​ When using a calcium compound, the amount of the polymerization catalyst used is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more per mole of all the dihydroxy compounds used in the reaction, in terms of the metal atom weight of the compound containing the metal. When using a calcium compound, the amount of the polymerization catalyst used is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more per mole of all the dihydroxy compounds used in the reaction, in terms of the metal atom weight of the compound containing the metal. When using a calcium compound, the amount of the polymerization catalyst used is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more per mole of all the dihydroxy compounds used in the reaction, in terms of the metal atom weight of the compound containing the metal. Also, as the upper limit, it is preferably 10 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less. Also, as the upper limit, it is preferably 10 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less.

[0056] By adjusting the amount of the polymerization catalyst used within the above range, the polymerization rate can be increased, so that it becomes possible to obtain a polycarbonate resin having a desired molecular weight without necessarily increasing the polymerization temperature, and thus the deterioration of the color tone of the polycarbonate resin can be suppressed. By adjusting the amount of the polymerization catalyst used within the above range, the polymerization rate can be increased, so that it becomes possible to obtain a polycarbonate resin having a desired molecular weight without necessarily increasing the polymerization temperature, and thus the deterioration of the color tone of the polycarbonate resin can be suppressed. By adjusting the amount of the polymerization catalyst used within the above range, the polymerization rate can be increased, so that it becomes possible to obtain a polycarbonate resin having a desired molecular weight without necessarily increasing the polymerization temperature, and thus the deterioration of the color tone of the polycarbonate resin can be suppressed. Moreover, since it is possible to prevent the unreacted raw materials from volatilizing during the polymerization and the molar ratio of the dihydroxy compound and the carbonic acid diester from being disrupted, it becomes possible to more reliably obtain a resin having a desired molecular weight. By adjusting the amount of the polymerization catalyst used within the above range, the polymerization rate can be increased, so that it becomes possible to obtain a polycarbonate resin having a desired molecular weight without necessarily increasing the polymerization temperature, and thus the deterioration of the color tone of the polycarbonate resin can be suppressed. Moreover, since it is possible to prevent the unreacted raw materials from volatilizing during the polymerization and the molar ratio of the dihydroxy compound and the carbonic acid diester from being disrupted, it becomes possible to more reliably obtain a resin having a desired molecular weight. By adjusting the amount of the polymerization catalyst used within the above range, the polymerization rate can be increased, so that it becomes possible to obtain a polycarbonate resin having a desired molecular weight without necessarily increasing the polymerization temperature, and thus the deterioration of the color tone of the polycarbonate resin can be suppressed. Moreover, since it is possible to prevent the unreacted raw materials from volatilizing during the polymerization and the molar ratio of the dihydroxy compound and the carbonic acid diester from being disrupted, it becomes possible to more reliably obtain a resin having a desired molecular weight. Furthermore, since the co-occurrence of side reactions can be suppressed, the deterioration of the color tone of the polycarbonate resin or the coloring during the molding process can be further prevented. Furthermore, since the co-occurrence of side reactions can be suppressed, the deterioration of the color tone of the polycarbonate resin or the coloring during the molding process can be further prevented.

[0057] Considering the adverse effects on the color tone of the polycarbonate resin caused by sodium, potassium, or cesium among the Group 1 metals, and the adverse effects on the color tone of the polycarbonate resin caused by iron, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is preferably 1 weight ppm or less. Considering the adverse effects on the color tone of the polycarbonate resin caused by sodium, potassium, or cesium among the Group 1 metals, and the adverse effects on the color tone of the polycarbonate resin caused by iron, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is preferably 1 weight ppm or less. Considering the adverse effects on the color tone of the polycarbonate resin caused by sodium, potassium, or cesium among the Group 1 metals, and the adverse effects on the color tone of the polycarbonate resin caused by iron, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is preferably 1 weight ppm or less. In this case, the deterioration of the color tone of the polycarbonate resin can be further prevented, and the color tone of the polycarbonate resin can be made better. In this case, the deterioration of the color tone of the polycarbonate resin can be further prevented, and the color tone of the polycarbonate resin can be made better. From the same viewpoint, the total content of sodium, potassium It is more preferable that the total content of sodium, potassium, cesium, and iron is 0.5 ppm by weight or less. These metals may be introduced not only from the catalyst used but also from raw materials or the reaction apparatus. Regardless of the source, the total amount of these metal compounds in the polycarbonate resin is preferably within the above range as the total content of sodium, potassium, cesium, and iron.

[0058] The polycarbonate resin composition may contain a single resin as the polycarbonate resin (A), but resins having different types of structural units (a2) derived from other dihydroxy compounds, copolymerization ratios, physical properties, etc. may be mixed in two or more kinds.

[0059] [Synthesis of Polycarbonate Resin] The polycarbonate resin is obtained by polycondensing a dihydroxy compound used as a raw material such as compound (1) and a carbonic acid diester by a transesterification reaction in the presence of a polymerization catalyst.

[0060] The dihydroxy compound and the carbonic acid diester as raw materials are preferably uniformly mixed before the transesterification reaction. The mixing temperature is usually 80°C or higher, preferably 90°C or higher, and usually 250°C or lower, preferably 200°C or lower, more preferably 150°C or lower. Among them, a range of 100°C to 120°C is preferable. In this case, the dissolution rate can be increased, the solubility can be sufficiently improved, and problems such as solidification can be sufficiently avoided. Furthermore, in this case, the thermal degradation of the dihydroxy compound can be sufficiently suppressed, and as a result the color tone of the obtained polycarbonate resin can be made even better. ​​​Weather resistance can also be improved.

[0061] The operation of mixing the raw material dihydroxy compound and the carbonic acid diester is carried out in an atmosphere with an oxygen concentration of 10 vol % or less, more preferably 0.0001 to 10 vol%, especially 0.0001 to 5 vol%, and particularly 0.0001 to 1 vol%. In this case, the color tone can be made better while enhancing the reactivity.

[0062] To obtain a polycarbonate resin, it is preferable to use the carbonic acid diester in a molar ratio of 0.90 to 1.20 with respect to all the dihydroxy compounds used in the reaction. In this case it is possible to suppress an increase in the amount of hydroxyl group terminals in the polycarbonate resin, so that the thermal stability of the polymer can be improved. Therefore, coloring during molding can be further prevented, or the rate of transesterification reaction can be increased. Also, a desired high molecular weight polymer can be obtained more reliably. Furthermore, by adjusting the amount of the carbonic acid diester used within the above range it is possible to suppress a decrease in the rate of the transesterification reaction, enabling more reliable production of a polycarbonate resin with a desired molecular weight. Also, in this case, an increase in the thermal history during the reaction can be suppressed, resulting in better color tone and weather resistance of the polycarbonate resin. Furthermore, in this case, the amount of residual carbonic acid di ester in the polycarbonate resin can be reduced, avoiding or alleviating the generation of stains and odors during molding. From the same perspective as above, the amount of the carbonic acid diester used with respect to all the dihydroxy compounds is more preferably 0.95 to 1.10 in terms of molar ratio.

[0063] The method of polycondensing a dihydroxy compound and a diester carbonate is carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The reaction mode includes batch type, continuous type, or a combination of batch type and continuous type. However, it is preferable to adopt a continuous type in which a polycarbonate resin can be obtained with less heat history and excellent productivity. From the viewpoints of controlling the polymerization rate and the quality of the obtained polycarbonate resin, it is important to appropriately select the jacket temperature, the internal temperature, and the pressure in the reaction system according to the reaction stage. Specifically, in the initial stage of the polycondensation reaction, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the later stage of the reaction, to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum. In this case, the distillation of unreacted monomers is suppressed, and it becomes easier to adjust the molar ratio of the dihydroxy compound and the diester carbonate to a desired ratio. As a result, a decrease in the polymerization rate can be suppressed.

[0064] Moreover, the polymerization rate in the polycondensation reaction is controlled by the balance between the hydroxy group end and the carbonate group end. Therefore, when the balance of the end groups changes due to the distillation of unreacted monomers, it becomes difficult to control the polymerization rate constantly, and the molecular weight of the obtained resin may vary greatly. Since the molecular weight of the resin correlates with the melt viscosity, when the obtained resin is melt-processed, the melt viscosity may vary, making it difficult to keep the quality of the molded product constant. Such problems are likely to occur particularly when carrying out the polycondensation reaction in a continuous manner. This makes it possible to more reliably obtain a polymer having a desired molecular weight and end groups. In this case, the distillation of unreacted monomers is suppressed, and it becomes easier to adjust the molar ratio of the dihydroxy compound and the diester carbonate to a desired ratio. As a result, a decrease in the polymerization rate can be suppressed. This makes it possible to more reliably obtain a polymer having a desired molecular weight and end groups. Moreover, the polymerization rate in the polycondensation reaction is controlled by the balance between the hydroxy group end and the carbonate group end. Therefore, when the balance of the end groups changes due to the distillation of unreacted monomers, it becomes difficult to control the polymerization rate constantly, and the molecular weight of the obtained resin may vary greatly. Since the molecular weight of the resin correlates with the melt viscosity, when the obtained resin is melt-processed, the melt viscosity may vary, making it difficult to keep the quality of the molded product constant.

[0065] Moreover, the polymerization rate in the polycondensation reaction is controlled by the balance between the hydroxy group end and the carbonate group end. Therefore, when the balance of the end groups changes due to the distillation of unreacted monomers, it becomes difficult to control the polymerization rate constantly, and the molecular weight of the obtained resin may vary greatly. Since the molecular weight of the resin correlates with the melt viscosity, when the obtained resin is melt-processed, the melt viscosity may vary, making it difficult to keep the quality of the molded product constant. Such problems are likely to occur particularly when carrying out the polycondensation reaction in a continuous manner. Since the molecular weight of the resin correlates with the melt viscosity, when the obtained resin is melt-processed, the melt viscosity may vary, making it difficult to keep the quality of the molded product constant. Such problems are likely to occur particularly when carrying out the polycondensation reaction in a continuous manner. Such problems are likely to occur particularly when carrying out the polycondensation reaction in a continuous manner.

[0066] In order to suppress the amount of unreacted monomer left, it is effective to use a reflux condenser in the polymerization reactor, which shows a high effect especially at the initial stage of the reaction where there is a large amount of unreacted monomer. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but usually, the temperature of the refrigerant introduced into the reflux condenser is 45 to 180 °C at the inlet of the reflux condenser, preferably 80 to 150 °C, particularly preferably 100 to 130 °C. By adjusting the refrigerant temperature within these ranges, the reflux amount can be sufficiently increased, and the effect can be sufficiently obtained, and at the same time the distillation efficiency of the monohydroxy compound to be distilled off can be sufficiently improved. As a result, it is possible to prevent a decrease in the reaction rate and further prevent the coloring of the resulting resin. As the refrigerant, hot water, steam, heat transfer oil, etc. are used, and steam and heat transfer oil are preferred.

[0067] In order to appropriately maintain the polymerization rate and suppress the distillation of the monomer while making the color tone of the resulting polycarbonate resin better, it is important to select the type and amount of the above-mentioned polymerization catalyst.

[0068] Polycarbonate resin is usually produced through two or more steps using a polymerization catalyst. The polycondensation reaction may be carried out in two or more steps by sequentially changing the conditions using one polycondensation reactor, but from the viewpoint of production efficiency, it is preferable to use a plurality of reactors and carry out the reaction in multiple steps by changing the conditions of each reactor.

[0069] From the viewpoint of efficiently carrying out the polycondensation reaction, at the initial stage of the reaction where there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomer while maintaining the required polymerization rate. Also, In the later stage of the reaction, it is important to sufficiently distill off the by-produced monohydroxy compound to shift the equilibrium to the polycondensation reaction side. Therefore, the reaction conditions suitable for the initial stage of the reaction are usually different from those suitable for the later stage of the reaction. Therefore, by using a plurality of reactors arranged in series, each condition can be easily changed, and the production efficiency can be improved.

[0070] As described above, the polymerization reactor used for producing the polycarbonate resin may have at least two or more. From the viewpoint of production efficiency and the like, it is three or more, preferably 3 to 5, particularly preferably 4. If there are two or more polymerization reactors, in each polymerization reactor, different reaction stages may be carried out a plurality of times, or the temperature and pressure may be continuously changed.

[0071] The polymerization catalyst can be added to the raw material preparation tank or the raw material storage tank, or can be directly added to the polymerization reactor. From the viewpoints of supply stability and control of the polycondensation reaction, a catalyst supply line is installed in the middle of the raw material line before being supplied to the polymerization reactor, and it is preferred to supply the polymerization catalyst with an aqueous solution.

[0072] By adjusting the temperature of the polycondensation reaction, it is possible to improve productivity and avoid an increase in the thermal history of the product . Furthermore, it is possible to further prevent the volatilization of the monomer and the decomposition and coloring of the polycarbonate resin. Specifically, as the reaction conditions in the first-stage reaction, the following conditions can be adopted. That is, the maximum temperature of the internal temperature of the polymerization reactor is usually 15 0 to 250 °C, preferably 160 to 240 °C, more preferably in the range of 170 to 230 °C . ​Set. Further, the pressure of the polymerization reactor (hereinafter, the pressure refers to the absolute pressure) is usually set in the range of 1 to 11 0 kPa, preferably 5 to 70 kPa, more preferably 7 to 30 kPa. Also, the reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.5 to 3 hours . The first-stage reaction is preferably carried out while distilling off the generated monohydroxy compound out of the reaction system .

[0073] In the subsequent stages, the pressure of the reaction system is gradually lowered from the pressure of the first stage, and while continuously removing the generated monohydroxy compound out of the reaction system, finally, the pressure (absolute pressure) of the reaction system is preferably set to 1 kPa or less. Also, the maximum temperature of the internal temperature of the polymerization reactor is usually set in the range of 200 to 260 °C, preferably 210 to 250 °C. Also, the reaction time is usually set in the range of 0. 1 to 10 hours, preferably 0.3 to 6 hours, particularly preferably 0.5 to 3 hours .

[0074] From the viewpoint of further suppressing the coloring and thermal degradation of the polycarbonate resin and obtaining a polycarbonate resin (A) with an even better color tone, the maximum temperature of the internal temperature of the polymerization reactor in all reaction stages is preferably 210 to 240 °C. Also, in order to suppress the decrease in the polymerization rate in the latter half of the reaction and minimize the degradation due to the heat history, it is preferable to use a horizontal reactor excellent in plug flow property and interfacial renewal property in the final stage of the polycondensation reaction . .

[0075] In continuous polymerization, in order to control the molecular weight of the finally obtained polycarbonate resin to a certain level, it is preferable to adjust the polymerization rate as necessary. In that case, adjusting the pressure of the polymerization reactor in the final stage is an operationally good method . ​​​​​

[0076] Also, as described above, the polymerization rate varies depending on the ratio of the hydroxy group terminal to the carbonate group terminal. Therefore, deliberately reducing one of the terminal groups suppresses the polymerization rate, and by maintaining the pressure in the final-stage polymerization reactor at high vacuum, residual low-molecular components in the resin, including the monohydroxy compound, can be reduced. However, in this case, if one of the terminals becomes too few, even a slight variation in the terminal group balance will extremely reduce the reactivity, and the molecular weight of the resulting polycarbonate resin may fall short of the desired molecular weight. To avoid such problems, the polycarbonate resin obtained in the final-stage polymerization reactor preferably contains 10 mol / ton or more of both the hydroxy group terminal and the carbonate group terminal. On the other hand, if both terminal groups are too many, the polymerization rate will increase and the molecular weight will become too high, so it is preferable that one of the terminal groups is 60 mol / ton or less. By thus adjusting the amount of the terminal group and the pressure in the final-stage polymerization reactor to a preferable range, the residual amount of the monohydroxy compound in the resin at the outlet of the polymerization reactor can be reduced. The residual amount of the monohydroxy compound in the resin at the outlet of the polymerization reactor is preferably 2000 weight ppm or less, more preferably 1500 weight ppm or less, and still more preferably 1000 weight ppm or less. By reducing the content of the monohydroxy compound at the outlet of the polymerization reactor in this way, devolatilization of the monohydroxy compound and the like can be easily carried out in the subsequent process. Although it is preferable that the residual amount of the monohydroxy compound is small, it is reduced to less than 100 weight ppm. To avoid such problems, the polycarbonate resin obtained in the final-stage polymerization reactor preferably contains 10 mol / ton or more of both the hydroxy group terminal and the carbonate group terminal. On the other hand, if both terminal groups are too many, the polymerization rate will increase and the molecular weight will become too high, so it is preferable that one of the terminal groups is 60 mol / ton or less.

[0077] By thus adjusting the amount of the terminal group and the pressure in the final-stage polymerization reactor to a preferable range, the residual amount of the monohydroxy compound in the resin at the outlet of the polymerization reactor can be reduced. The residual amount of the monohydroxy compound in the resin at the outlet of the polymerization reactor is preferably 2000 weight ppm or less, more preferably 1500 weight ppm or less, and still more preferably 1000 weight ppm or less. By reducing the content of the monohydroxy compound at the outlet of the polymerization reactor in this way, devolatilization of the monohydroxy compound and the like can be easily carried out in the subsequent process.

[0078] Although it is preferable that the residual amount of the monohydroxy compound is small, it is reduced to less than 100 weight ppm. Then, it is necessary to adopt operating conditions such as extremely reducing the amount of one terminal group and maintaining the pressure in the polymerization reactor at a high vacuum. In this case, as described above, it becomes difficult to maintain the molecular weight of the resulting polycarbonate resin at a certain level. Therefore, it is usually 100 weight ppm or more, preferably 150 weight ppm or more.

[0079] The by-produced monohydroxy compound is preferably purified as necessary from the viewpoint of effective utilization of resources and then reused as a raw material for other compounds. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A, etc. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A, etc. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A, etc. It can be used.

[0080] The polycarbonate resin preferably contains a catalyst deactivator. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters. The catalyst deactivator is not particularly limited as long as it is an acidic substance having a function of deactivating the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl phosphonium octylsulfonate, tetramethyl phosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate, tetrabutyl phosphonium dodecylbenzenesulfonate, tetrabutyl phosphonium p-toluenesulfonate and other phosphonium salts; decylsulfonic acid tetramethylammonium salt, dodecylbenzenesulfonic acid tetrabutylammonium salt and other ammonium salts; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, ethyl hexadecylsulfonate and other alkyl esters.

[0081] The catalyst deactivator preferably contains a phosphorus compound (hereinafter referred to as "specific phosphorus compound") containing any of the partial structures represented by the following formula (5) or the following formula (6). After the polycondensation reaction is completed, that is, for example, during a kneading step or a pelletizing step, etc., the specific phosphorus compound is added to deactivate the polymerization catalyst described later, and thereafter, the polycondensation reaction can be suppressed from proceeding unnecessarily. As a result, in a molding step or the like, the progress of polycondensation when the polycarbonate resin is heated can be suppressed, and thus the elimination of the monohydroxy compound can be suppressed. Further, by deactivating the polymerization catalyst, the coloring of the polycarbonate resin at high temperature can be further suppressed. 。 。 。 。 。 。

[0082]

Chemical formula

[0083]

Chemical formula

[0084] Examples of the specific phosphorus compound containing the partial structure represented by the formula (6) or formula (7) include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid ester, acidic phosphoric acid ester, etc. Among the specific phosphorus compounds, phosphorous acid, phosphonic acid, and phosphonic acid ester have more excellent effects on catalyst deactivation and coloring suppression, and phosphorous acid is particularly preferred. 。 。 。 。

[0085] Examples of the phosphonic acid that can be adopted include the following compounds. Phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, 。 Phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid Phosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid , nitrilotris(methylenephosphonic acid), propylphosphonic anhydride, etc.

[0086] As the phosphonate ester, for example, the following compounds can be used: Phosphonic acid dimethyl, diethyl, bis(2-ethylhexyl), phosphonic acid Dilauryl, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, Dimethyl ethylphosphonate, Diphenyl methylphosphonate, Diethyl ethylphosphonate, Diethyl phenylphosphonate, Dimethyl phenylphosphonate, Diethyl phenylphosphonate , dipropyl phenylphosphonate, diethyl (methoxymethyl)phosphonate, vinyl phosphonate Diethyl phosphonate, diethyl hydroxymethylphosphonate, (2-hydroxyethyl)phosphonate Dimethyl p-methylbenzylphosphonate, Diethyl p-methylbenzylphosphonate, Diethylphosphonoacetate, Diethyl Ethyl ethylphosphonoacetate, tert-butyl diethylphosphonoacetate, 4-chlorobenzyl ) diethyl phosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, 3,5-Di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, diethyl Phosphonoacetaldehyde diethyl acetal, (methylthiomethyl)phosphonic acid diethyl Le et al.

[0087] As the acidic phosphate ester, for example, the following compounds can be used: diphosphate Methyl, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, phosphate Bis(butoxyethyl), bis(2-ethylhexyl) phosphate, diisotridecyl phosphate 、dioleyl phosphate, distearyl phosphate, diphenyl phosphate, dibenzyl phosphate, etc. diesters of phosphoric acid, or mixtures of diesters and monoesters, diethyl chlorophosphate, zinc stearyl phosphate, etc.

[0088] The above-mentioned specific phosphorus compounds may be used alone, or two or more of them may be mixed and used in any combination and ratio.

[0089] The content of the specific phosphorus compound in the polycarbonate resin is preferably 0.1 weight ppm or more and 5 weight ppm or less as phosphorus atoms. In this case, the effects of catalyst deactivation and coloring suppression by the above-mentioned specific phosphorus compound can be sufficiently obtained. Also, in this case, in particular, in the durability test under high temperature and high humidity, the coloring of the polycarbonate resin can be further prevented.

[0090] In addition, by adjusting the content of the specific phosphorus compound according to the amount of the polymerization catalyst, the effects of catalyst deactivation and coloring suppression can be obtained more surely. The content of the specific phosphorus compound is preferably 0.5 times mol or more and 5 times mol or less as the amount of phosphorus atoms with respect to 1 mol of the metal atom of the polymerization catalyst, more preferably 0.7 times mol or more and 4 times mol or less, and particularly preferably 0.8 times mol or more and 3 times mol or less.

[0091] [Physical properties of polycarbonate resins (A) and (B)] The preferred physical properties of polycarbonate resins (A) and (B) are shown below. [Glass transition temperature] The glass transition temperature of polycarbonate resin (A) is preferably 100 °C or higher. In this case This improves the heat resistance of the polycarbonate resin composition. From the same perspective, the glass transition temperature of polycarbonate resin (A) is more preferably 110°C or higher, and even more preferably 120°C or higher. On the other hand, the glass transition temperature of polycarbonate resin (A) is preferably 150°C or lower. In this case, the fluidity during molding is enhanced, and even for a molded product with a complex shape, the resin composition can easily reach the end of the mold during molding, and a desired molded product can be obtained. Also, a decrease in strength at the weld part can be suppressed. From the perspective of further enhancing these effects, the glass transition temperature of polycarbonate resin (A) is more preferably 140°C or lower, and even more

[0092] preferably 130°C or lower. The glass transition temperature of polycarbonate resin (B) is preferably 85°C or higher. In this case, the heat resistance of the polycarbonate resin composition is further improved. From the same perspective, the glass transition temperature of polycarbonate resin (B) is more preferably 90°C or higher, and even more preferably 95°C or higher. On the other hand, the glass transition temperature of polycarbonate resin (B) is preferably 130°C or lower. In this case, the fluidity during molding is enhanced, and even for a molded product with a complex shape, the resin composition can easily reach the end of the mold during molding, and a desired molded product can be obtained. Also, a decrease in strength at the weld part can be suppressed. From the perspective of further enhancing these effects, the glass transition temperature of polycarbonate resin

[0093] <Reduced viscosity> The molecular weights of polycarbonate resins (A) and (B) can be represented by reduced viscosity, and the The higher the degree, the larger the molecular weight. Incidentally, the reduction viscosities of the polycarbonate resins (A) and (B) were precisely adjusted to a concentration of the polycarbonate resin of 0.6 g / d L using methylene chloride as a solvent, and measured using an Ubbelohde viscometer under the condition of a temperature of 20.0 °C ± 0.1 °C.

[0094] The reduction viscosity of the polycarbonate resin (A) used in the polycarbonate resin composition of the present invention needs to be 0.45 dL / g or more and less than 0.50 dL / g. As a result of the study by the present inventors, when the reduction viscosity of the polycarbonate resin (A) is within the above range, the heat aging resistance and chemical resistance of the resin composition containing the polycarbonate resin (A) are significantly improved. This is presumably due to an increase in the entanglement points of the molecules as the molecular weight increases. From the viewpoint of more excellent heat aging resistance and chemical resistance, the reduction viscosity is preferably 0.46 dL / g or more, more preferably 0.47 dL / g or more. Also, from the viewpoint of more excellent fluidity and appearance during molding, less than 0.49 dL / g is preferable. When the reduction viscosity of the polycarbonate resin (A) is less than 0.45 dL / g, sufficient heat aging resistance and chemical resistance cannot be obtained. Also, when the reduction viscosity is 0.50 dL / g or more, it is presumed that the fluidity is poor and the moldability is significantly deteriorated.

[0095] The reduction viscosity of the polycarbonate resin (B) used in the polycarbonate resin composition of the present invention needs to be equal to or higher than the reduction viscosity of the polycarbonate resin (A). In this case, the effects of excellent balance in heat aging resistance, chemical resistance, fluidity, appearance during molding, and heat resistance of the resin composition can be obtained. From the same viewpoint, the reduction viscosity of the polycarbonate resin (B) is ​​​​​​​​ It is preferably greater than the reduced viscosity of the carbonate resin (A). Specifically, the reduced viscosity of the polycarbonate resin (B) is 0.45 dL / g or more and 1.0 dL / g or less, preferably 0.46 dL / g or more and 0.80 dL / g or less, more preferably 0.50 dL / g or more and 0.63 dL / g or less. In this case, the heat aging resistance, chemical resistance, fluidity, appearance during molding, and heat resistance of the resin composition become even more excellent.

[0096] In the polycarbonate resin composition of the present invention, by adjusting the reduced viscosity of the polycarbonate resin (B) within a specific range, the physical properties of the obtained polycarbonate resin composition can be adjusted to desirable ones. Specifically, when the polycarbonate resin composition is used in applications where higher formability is required, the reduced viscosity of the polycarbonate resin ( (B) is more preferably 0.45 dL / g or more, even more preferably 0.48 dL / g or more, and particularly preferably 0.50 dL / g or more. Also, it is preferably 0.60 dL / g or less, more preferably less than 0.55 dL / g. When the reduced viscosity is within the above range, the polycarbonate resin composition is excellent in chemical resistance, heat aging resistance, and heat resistance, and also has even better formability. On the other hand, when the polycarbonate resin composition is used in applications where higher chemical resistance and heat aging resistance are required, the reduced viscosity of the polycarbonate resin (B) is preferably 0.50 dL / g or more, more preferably 0.55 dL / g or more, even more preferably 0.60 dL / g or more. Also, it is preferably 0.70 dL / g or less, more preferably 0.65 dL / g or less. When the reduced viscosity is within the above range, the polycarbonate resin composition resin composition The carbonate resin composition is excellent in moldability, molded article appearance, and heat resistance, and also has further excellent chemical resistance and heat aging resistance. It becomes even more excellent.

[0097] In particular, when the reduced viscosity of the polycarbonate resin (B) is 0.55 dL / g or more and 0.65 dL / g or less, the fluidity is good and the heat aging resistance of the resin composition is significantly improved. This is preferable because an effect is obtained. This is because as the molecular weight of the polycarbonate resin (B) increases and the entanglement points of the molecules increase, in addition to the entanglement points between the polycarbonate resins (B), the entanglement points between the molecules of both the polycarbonate resin (A) and the polycarbonate resin (B) increase, so the heat aging resistance is significantly improved compared to the case of each resin alone. It is presumed to be the case. From the same viewpoint, the reduced viscosity of the polycarbonate resin (B) is more preferably 0.6 0 dL / g or more and 0.63 dL / g or less.

[0098] <Difference in reduced viscosity> In the polycarbonate resin composition of the present invention, when the polycarbonate resin composition is used for applications where higher moldability is required the difference (absolute value) in the reduced viscosity between the polycarbonate resin (A) and the polycarbonate resin (B) is preferably 0.010 or more and less than 0.10, more preferably 0.015 or more and 0.070 or less, and particularly preferably 0.020 or more and 0 .050 or less. When the difference in reduced viscosity is within the above range, the polycarbonate resin composition is excellent in chemical resistance, heat aging resistance, and heat resistance, and also has even better moldability. On the other hand, when the polycarbonate resin composition is used for applications where higher chemical resistance and heat aging resistance are required at a higher level, when the polycarbonate resin (A) and the polycarbonate ​​The difference (absolute value) in reduced viscosity of the polycarbonate resin (B) is preferably 0.10 or more and 0.20 or less, more preferably 0.11 or more and 0.15 or less, and particularly preferably 0.12 or more and 0.14 or less. When the difference in reduced viscosity is within the above range, the polycarbonate resin composition is excellent in moldability, the appearance of the molded product, and heat resistance, and is further excellent in chemical resistance and heat aging resistance.

[0099] The polycarbonate resin composition of the present invention contains at least the above-mentioned polycarbonate resin (A) and polycarbonate resin (B), but within a range that does not prevent the effects of the present disclosure, it is also possible to further contain a polycarbonate resin having a structural unit (a) other than the polycarbonate resin (A) and polycarbonate resin (B). In this case, the polycarbonate resin composition will have three or more polycarbonate resins. The polycarbonate resin having a structural unit (a) other than the polycarbonate resin (A) and polycarbonate resin (B) specifically has a content ratio of at least the structural unit (a) different from both the polycarbonate resin (A) and polycarbonate resin (B). Also, the polycarbonate resin in the polycarbonate resin composition can be substantially composed only of the polycarbonate resin (A) and polycarbonate resin (B).

[0100] The content of the polycarbonate resin (A) in the polycarbonate resin composition of the present invention is not particularly limited, but is preferably 25 parts by weight or more with respect to 100 parts by weight in total of the polycarbonate resin composition. More preferably 50 parts by weight or more, and even more preferably 60 parts by weight or more. ​​​is more preferable, and 70 parts by weight or more is particularly preferable. Further, 95 parts by weight or less is preferable, and 9 0 parts by weight or less is more preferable. When the content of the polycarbonate resin (A) is within the above range, the chemical resistance, heat aging resistance, moldability, appearance during molding, and heat resistance of the polycarbonate resin composition are more excellent.

[0101] In the polycarbonate resin composition of the present invention, the content of the polycarbonate resin (B) is not particularly limited, but with respect to 100 parts by weight in total of the polycarbonate resin composition, it is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and preferably 10 parts by weight or more Further, 50 parts by weight or less is preferable, 30 parts by weight or less is more preferable, and 20 parts by weight or less is even more preferable. When the content of the polycarbonate resin (B) is within the above range, the chemical resistance, heat aging resistance, moldability, appearance during molding, and heat resistance of the polycarbonate resin composition are more excellent.

[0102] The polycarbonate resin composition of the present invention may also contain an elastomer component. Specifically, for example, it can contain an elastomer (C) having a core-shell structure.

[0103] When containing the elastomer (C) having a core-shell structure, the content is not particularly limited. However, when the total of the polycarbonate resin composition is 100 parts by weight, the content of the elastomer having a (C) core-shell structure is preferably 0.1 to 50 parts by weight. More preferably, it is 0.5 part by weight or more, still more preferably 1 part by weight or more, and most preferably 5 parts by weight or more. On the other hand, it is more preferably 40 parts by weight or less. It is more preferably 30 parts by weight or less, particularly preferably 25 parts by weight or less. It is most preferably 20 parts by weight or less. The elastomer having a core - shell structure When the blending amount is at least the lower limit value, the effects of improving impact resistance and surface impact resistance are exhibited. On the other hand, when the blending amount of the elastomer having a core - shell structure is at most the upper limit value, it is possible to suppress appearance defects and deterioration of heat resistance of the obtained molded product.

[0104] By the way, the inventors of the present invention have found that in the polycarbonate resin composition of the present invention, in addition to the polycarbonate resin (A) and the polycarbonate (B), by containing an elastomer (C) having a core - shell structure, surprisingly, the heat - aging resistance of the resin composition is remarkably improved. This is because when a polycarbonate resin (A) having a specific reduced viscosity, a polycarbonate resin (B), and an elastomer component (C) having a core - shell structure co - exist, in addition to the excellent heat - aging resistance of component (A), even when fine cracks occur, component (C) can inhibit the crack growth. This is presumably a synergistic effect. The "elastomer having a core - shell structure" is composed of an innermost layer (core layer) and one or more layers (shell layers) covering it, and is a core - shell type graft copolymer in which a monomer component copolymerizable with the core layer is graft - copolymerized as the shell layer. The elastomer (C) having a core - shell structure is usually a core - shell type graft copolymer in which a polymer component called a rubber component is used as the core layer and a monomer component copolymerizable with this is used as the shell layer and graft - copolymerized. It is preferably a core - shell type graft copolymer in which a monomer component copolymerizable with the core layer is graft - copolymerized as the shell layer.

[0105] The elastomer (C) having a core - shell structure is preferably a core - shell type graft copolymer in which a polymer component (usually called a rubber component) is used as the core layer and a monomer component copolymerizable with this is used as the shell layer and graft - copolymerized. As a method for producing this core-shell type graft copolymer, any production method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. may be used, and the copolymerization method may be single-stage graft or multi-stage graft. However, in the second aspect of the present invention, usually, a commercially available core-shell type elastomer can be used as it is. Examples of commercially available core-shell type elastomers will be listed later.

[0106] The elastomer (C) having a core-shell structure used in the present invention is not particularly limited but is particularly preferably an acrylic-styrene based rubber having a core-shell structure . In this case, the polycarbonate resin composition can obtain the effect of being excellently balanced in heat aging resistance, chemical resistance, moldability, molded product appearance, and heat resistance.

[0107] The polymer component forming the core layer usually has a glass transition temperature of 0 °C or lower, particularly preferably -10 °C or lower , more preferably -20 °C or lower, and still more preferably -30 °C or lower. Specific examples of the polymer component forming the core layer include polybutadiene, polyisoprene, polybutyl acry ylate, poly(2-ethylhexyl acrylate), polyalkyl acrylates such as butyl acrylate·2-ethyl hexyl acrylate copolymer, silicone rubbers such as polyorganosiloxane rubber, butadiene-acrylic composites, IPN (Interpenetrati ng Polymer Network) type composite rubbers composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer , etc. Ethylene-α-olefin copolymers such as a body, ethylene-acrylic copolymers, fluororubbers and the like can be mentioned. These may be used alone or in combination of two or more. These Among them, from the viewpoints of mechanical properties and surface appearance, polybutadiene, polyalkyl acrylate , polyorganosiloxane, a composite of polyorganosiloxane and polyalkyl acrylate, and butadiene-styrene copolymer are preferable.

[0108] Specific examples of the monomer component capable of graft copolymerization with the polymer component of the core layer, which constitutes the shell layer include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylate esterified compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylate compounds such as glycidyl (meth)acrylate; maleimide, N-methyl maleimide, N-phenyl maleimide compounds such as maleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, itaconic acid and their anhydrides (for example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, from the viewpoints of mechanical properties and surface appearance, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylate ester compounds, (meth)acrylic acid compounds are preferable, and more preferably (meth) acrylate ester compounds. Specific examples of the (meth)acrylate ester compounds include (meth)methyl acrylate, (meth)ethyl acrylate, (meth)butyl acrylate , (meth)cyclohexyl acrylate, (meth)octyl acrylate and the like. Among these, (meth)methyl acrylate and (meth)ethyl acrylate, which are relatively easily available , are mentioned. is preferred, and methyl (meth)acrylate is more preferred. Here, "(meth)acrylic" is a general term for "acrylic" and "methacrylic."

[0109] Elastomers with a core-shell structure are, among others, polybutadiene-containing rubbers, polybutadiene-containing rubbers, Chiller acrylate-containing rubber, polyorganosiloxane rubber, polyorganosiloxane rubber and polyalkyl acrylate rubber. A polymer component is used as the core layer, and (meth)acrylic ester is graft-copolymerized around it. A core-shell type graft copolymer having a shell layer formed by the above-mentioned process is particularly preferred. In the above core-shell type graft copolymer, the polymer component of the core layer is contained in an amount of 40% by weight or more. It is preferable that the content of the shell layer is 60% by weight or more, and more preferable that the content of the shell layer is 60% by weight or more. The (meth)acrylic acid ester component is preferably contained in an amount of 10% by weight or more.

[0110] A preferred example of the core-shell type graft copolymer is methyl methacrylate. Methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile Methyl methacrylate-butadiene-styrene copolymer (MABS), Methyl methacrylate-butadiene Copolymer (MB), Methyl methacrylate-acrylic rubber copolymer (MA), Methyl methacrylate Acrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic Acrylic-butadiene rubber copolymer, Methyl methacrylate-acrylic-butadiene rubber Styrene copolymer, methyl methacrylate-(acrylic silicone complex) copolymer, etc. Some examples include:

[0111] Examples of such core-shell graft copolymers include, for example, those manufactured by Rohm and Haas Japan Co., Ltd., such as "Paraloid (registered trademark) EXL2602", "Paraloid (registered trademark) EXL2603", "Paraloid (registered trademark) EXL2655", "Paraloid (registered trademark) EXL2311", "Paraloid (registered trademark) EXL2313", "Paraloid (registered trademark) EXL2315", "Paraloid (registered trademark) KM330", "Paraloid (registered trademark) KM336P", "Paraloid (registered trademark) KCZ201"; those manufactured by Mitsubishi Rayon Co., Ltd., such as "Metablen (registered trademark) C-223A", "Metablen (registered trademark) E-901", "Metablen (registered trademark) S-2001", "Metablen (registered trademark) W-450A", "Metablen (registered trademark) SRK-200"; and those manufactured by Kaneka Corporation, such as "Kaneka Ace (registered trademark) M-511", "Kaneka Ace (registered trademark) M-600", "Kaneka Ace (registered trademark) M-400", "Kaneka Ace (registered trademark) M-580", "Kaneka Ace (registered trademark) MR-01", etc.

[0112] These impact strength modifiers having a core-shell structure, such as core-shell graft copolymers, may be used alone or in combination of two or more.

[0113] [Other Components] The polycarbonate resin composition of the present invention may contain various well-known additives, such as antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, fillers such as fillers, neutralizing agents, lubricants, anti-fogging agents, anti-blocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, crosslinking agents, crosslinking aids, metal deactivators, and molecular weight regulators, within a range that does not impair the object of the present invention. ​​​​​​​​​​​Examples include antibacterial agents, antifungal agents, optical brighteners, and light diffusing agents such as organic and inorganic diffusing agents.

[0114] [Physical properties of polycarbonate resin and polycarbonate resin composition] <Melt viscosity> The melt viscosity of the polycarbonate resin composition can be evaluated, for example, by the measurement method of fluidity evaluation (melt viscosity) detailed in the examples described below. The melt viscosity is preferably 1100 P a·s or less. The lower this value, the better the fluidity.

[0115] <Heat resistance> The heat resistance of the polycarbonate resin composition can be evaluated, for example, by the measurement method of heat resistance detailed in the examples described below. As the value of the heat distortion temperature (HDT), preferably it is 95 °C or higher. By being in this range, it has excellent heat resistance.

[0116] <Impact strength> The impact strength of the polycarbonate resin composition can be evaluated, for example, by the notched Charpy impact strength test detailed in the examples described below. The notched Charpy impact strength with a notch tip radius R of 0.25 m m is preferably 5 kJ / m 2 or more, thereby having excellent impact resistance.

[0117] <Heat aging resistance> The heat aging resistance of the polycarbonate resin composition can be evaluated, for example, by the constant strain heat aging resistance detailed in the examples described below.

[0118] <Chemical resistance> The chemical resistance of the polycarbonate resin composition can be evaluated, for example, by the constant strain chemical resistance detailed in the examples described below.

[0119] <Moldability> The moldability of the polycarbonate resin composition can be evaluated, for example, by the appearance evaluation of the molded article detailed in the examples described below. Preferably, it has excellent moldability by disappearing within 1 to 11 pieces in the continuous molding after the appearance defect (silver streak) remains.

[0120] [Mixing method] In the polycarbonate resin composition of the present invention, as a mixing method of the aforementioned carbonate copolymer and various additives such as those described above, for example, a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder, etc. are used for mixing and kneading. kneading method, or, for example, a solution blending method in which they are mixed in a state of being dissolved in a common good solvent such as methylene chloride, etc. There is no particular limitation on this, and any commonly used blending method may be used.

[0121] Also, there is no limitation on the timing of blending the aforementioned carbonate copolymer and various additives such as those described above. After mixing and pelletizing a plurality of carbonate copolymers having different compositions, various additives etc. may be blended, or various additives etc. may be blended for each of a plurality of carbonate copolymers having different compositions to form composition pellets, and they may be mixed, or a plurality of carbonate copolymers having different compositions may be mixed and various additives etc. may be blended simultaneously.

[0122] [Method for producing resin composition] The resin composition of the present invention can be produced, for example, by a method of mechanically melt-kneading the above components. As the melt-kneading machine that can be used here, for example, a single-screw extruder, a twin-screw extruder, a Brabender, a Banbury mixer, a kneader blender, a roll mill, etc. It can be mentioned. Among them, a twin-screw extruder is preferable. From the viewpoint of removing residual phenol , it is preferably carried out while reducing the pressure. The lower limit of the kneading temperature is usually 100 °C or higher, preferably 145 °C or higher, more preferably 160 °C or higher. The upper limit of the kneading temperature is usually 350 °C, preferably 300 °C, more preferably 250 °C. When kneading, all components can be kneaded together , or a multi-stage divided kneading method can also be used, in which any component is kneaded first, and then the remaining other components are added and kneaded. The extruded kneaded product is made into pellets using a strand cutter or the like, and it is preferably dried appropriately before use and then used.

[0123] [Molding method of resin composition] The resin composition of the present invention can be processed into various molded articles by molding methods such as injection molding (insert molding method, two-color molding method, sandwich molding method, gas injection molding method, etc.), extrusion molding method, inflation molding method, T die film molding method, laminating molding method, blow molding method, hollow molding method, compression molding method, calender molding method, etc. There is no particular limitation on the shape of the molded article, and examples include sheet, film, plate-like, particulate, massive, fiber, rod-like, porous body, foamed body, etc., and preferably sheet, film, and plate-like. In addition, the molded film can also be uniaxially or biaxially stretched. Examples of the stretching method include roll method, tenter method , tubular method, etc. Furthermore, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., which are usually industrially used, can also be performed. , etc.

[0124] [Applications] The applications of the molded article formed by molding the resin composition of the present invention are not particularly limited. As an example, ​​​​The following uses can be cited. That is, wires in the field of electric and electronic components, cables, coating materials such as wire harnesses, insulating sheets, displays and touch panels of OA equipment, membrane switches, photo covers, relay parts, coil bobbins, IC sockets , fuse cases, camera pressure plates, FDD collars, floppy hubs, in the field of optical components optical disc substrates, pickup lenses for optical discs, optical lenses, LCD substrates, PDP substrates, television screens for projection TVs, retardation films, fog lamp lenses , illumination switch lenses, sensor switch lenses, Fresnel lenses, protective glasses, projectors lenses, camera lenses, sunglasses, light guide plates, camera strobe reflectors , LED reflectors, headlamp lenses in automotive parts, turn signal lamp lenses , tail lamp lenses, resin window glasses, meter covers, outer panels, door handles, rear bumpers , wheel caps, visors, roof rails, sunroofs, instrument panels, panels, coating materials for control cables, airbag covers, mud guards, bumpers, boots , air hoses, lamp packings, gaskets, various moldings such as window moldings, EMI shields, weather strips, glass run channels, grommets, vibration damping and sound insulation members, joint materials, handrails, windows, table edge materials, sashes, bathtubs, window frames in the building materials field, signboards, lighting covers, water tanks, staircase waistboards, carports, highway sound insulation walls, multi-wall sheets , steel wire coating materials, lighting lamp globes, switch breakers, protective covers for machine tools, industrial deep drawing vacuum forming containers, pump housings, household appliances, various packings in the field of low-voltage electricity, greases, belts, foot rubbers, rollers, protectors, suction cups, gaskets for refrigerators, etc. Switches, connector covers, game machine covers, pachinko machines, OA housings, notebooks PC housing, HDD head tray, instrument window, transparent housing, with OA gear Rollers, switch case sliders, gas cock knobs, clock frames, clock train intermediate units, Bar caps, various rolls for office equipment, hoses, tubes and other tubular moldings, irregular extrusion Products, leather-like products, bite tools, soft-touch dolls and other toys, pen grips, straps, etc. General goods such as cups, suction cups, watches, umbrella bones, cosmetic cases, toothbrush handles, housewares, Containers such as utensils, cable ties, blow molded infusion bottles, food bottles, Water bottles, bottles for personal care such as cosmetics, various bottles, medical parts, etc. Catheters, syringes, syringe gaskets, drip tubes, tubing, ports, and caps , rubber stoppers, dialyzers, blood connectors, dentures, disposable containers, etc. It can also be used in foam molding applications. Among the above, the tube is particularly suitable for medical use, as it can prevent the absorption of medicinal ingredients. In the case of multi-layer tubes, it is most suitable for the inner or intermediate layer material. EXAMPLES

[0125] The present invention will be described in more detail below using examples. The following examples are not intended to be limiting unless otherwise stated. [Measurement method]

[0126] In the following, the physical properties and characteristics of polycarbonate resin compositions and molded products are evaluated as follows: This was done by the method. (1) Reduced viscosity evaluation Dissolved using methylene chloride as a solvent to prepare a polycarbonate resin solution with a concentration of 0.6 g / dL. Using a Ubbelohde viscometer manufactured by Moritomo Chemical Industry Co., Ltd., the measurement was carried out at a temperature of 20.0 °C ± 0 .1 °C. From the passing time t0 of the solvent and the passing time t of the solution, the relative viscosity ηrel was determined from the following formula (i), and the specific viscosity ηsp was determined from the relative viscosity using the following formula (ii). ηrel = t / t0 (i) ηsp = (η - η0) / η0 = ηrel - 1 (ii) The specific viscosity was divided by the concentration c (g / dL) to obtain the reduced viscosity ηsp / c. The higher this value, the larger the molecular weight.

[0127] (2) Fluidity evaluation (melt viscosity) The pellets of the polycarbonate resin composition were dried at 90 °C for 4 hours or more using a hot air dryer. Next, the dried pellets were measured using a Gottfert rheograph under the conditions of a temperature of 240 °C, a shear rate of 100 sec-1, an orifice hole diameter of 20.0 mm, and an orifice length of 1.0 mm. The lower this value, the higher the fluidity. Those with a melt viscosity of 800 Pa·s or less were evaluated as "◎", those with 801 - 1100 Pa·s as "〇", and those with 1101 Pa·s or more were evaluated as "×".

[0128] (3) Appearance evaluation of molded products The pellets of the polycarbonate resin composition were dried at 90 °C for 4 hours or more. Next, the dried pellets were injection molded using a 200t injection molding machine manufactured by Meiki Seisakusho Co., Ltd. A plate with dimensions of 100 mm × 100 mm × thickness 2 mm was molded at a molding temperature of 265 °C and a mold temperature of 60 °C using a side gate. After weighing, it was retained for 20 minutes and continuous molding was carried out. The appearance of the designed surface side of the molded product thus obtained was observed, and the appearance defects (silver streaks) were within 1 to 3 during continuous molding after retention. Those that disappeared were marked as "◎", and those that disappeared within 4 to 1 0 pieces after continuous molding with appearance defects (silver streaks) remaining were marked as "〇", and those that did not disappear within 10 pieces after continuous molding with appearance defects (silver streaks) remaining were evaluated as "×".

[0129] (4) Notched Charpy Impact Test The pellets of the polycarbonate resin composition were dried at 90 °C for 4 hours or more using a hot air dryer. Next, the dried pellets were molded into dumbbell-shaped test pieces for mechanical properties at a molding temperature of 240 °C and a mold temperature of 60 °C using an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). The ISO test pieces for mechanical properties obtained above were subjected to a notched Charpy impact test in accordance with ISO179-1 (2010). Regarding the notch, the tip radius R was measured for 0.2 5 mm. Note that the higher the value of the notched Charpy impact strength, the better the impact resistance, but those with 5 J / m or more were judged to have excellent mechanical strength. 2

[0130] (5) Heat Resistance (Heat Deflection Temperature) The pellets of the polycarbonate resin composition were dried at 90 °C for 4 hours or more using a hot air dryer. Next, the dried pellets were molded into dumbbell-shaped test pieces for tensile tests using an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). This dumbbell-shaped test piece was cut to produce a test piece for measuring the heat deflection temperature. Using this test piece for measuring the heat deflection temperature, the heat deflection temperature (HDT) was measured in accordance with ISO 75 (2004). The test was conducted in a flat wise manner, and the temperature at which the deflection of the test piece reached the specified deflection was defined as the heat deflection temperature. The load was measured at 1.80 MPa. The higher this value, the higher the heat resistance.​​ In the examples, those with a temperature of 100 °C or higher were evaluated as "◎", those with a temperature of 95 °C to 99 °C were evaluated as "〇", and those with a temperature of 94 °C or lower were evaluated as "×".

[0131] (6) Constant deflection bending test The pellets of the polycarbonate resin composition were dried at 90 °C for 4 hours or more using a hot air dryer Next, the dried pellets were injection molded into a dumbbell-shaped test piece for mechanical properties (ISO 527-2 Type 1A and the same shape) having a weld line at the center using an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.) at a molding temperature of 260 °C and a mold temperature of 60 °C. Both ends of this dumbbell were cut to a size of 8 0 mm to prepare a test piece for bending test measurement. Using this test piece, a strain of 1.00% was constantly applied to the weld line at a measurement temperature of 80 °C using a Strograth VES1D manufactured by Toyo Seiki Seisaku-sho, Ltd. The time from the start of applying the strain until the weld part broke was measured, and it was judged that the higher this value, the better the mechanical strength. Those with a time to break of 60 minutes or more were evaluated as "◎", and those with a time to break of less than 60 minutes or those in which the test piece deformed during the test were evaluated as "×".

[0132] (7) Evaluation of constant strain chemical resistance Regarding the test piece for bending test measurement obtained in (6) above, after heat treatment at 100 °C for 24 hours using a hot air dryer, an emulsion mainly composed of poly(oxyethylene)=alkyl ether was applied to the sample and left for 24 hours Then, a constant deflection bending test was carried out on the test piece for bending test after the chemical resistance treatment obtained using the above method, and the time until the weld part broke was measured It was judged that the higher this value, the better the mechanical strength after the chemical resistance treatment. The time until break ​​​​​​Those with a score of 60 or above were rated as "◎", those with a time to breakage of less than 60 minutes or those in which the test piece was deformed during the test were rated as "×".

[0133] (8) Evaluation of constant strain heat aging For the test piece for bending test measurement obtained in (6) above, using a hot air dryer at 100 °C heat treatment was carried out for 24 hours. Using the obtained test piece for bending test after heat treatment, constant strain bending test was carried out, and the time until the weld part broke was measured. The higher this value, the more excellent the mechanical strength after heat treatment was judged. Those with a time to breakage of 30 minutes or more were rated as "◎", and those with a time to breakage of 15 minutes or more and less than 30 minutes were rated as "〇", and those with a time to breakage of less than 14 minutes or those in which the test piece was deformed during the test were rated as "×".

[0134] (9) Comprehensive evaluation Based on the results of the above fluidity, molded product appearance, heat resistance, constant strain bending test, constant strain heat aging evaluation, and constant strain chemical resistance evaluation, a comprehensive evaluation was made. Note that even those that meet the following passing criteria, the more the number of "◎", the more preferable. Pass: Those with only "〇" or "◎", Fail: Those including even one "×" were judged.

[0135] [Raw materials used in production examples] The abbreviations of the compounds used in the following production examples and the manufacturers are as follows. ○ Polycarbonate resins A-1, A-2, B-1, B-2 <Dihydroxy compound> · ISB: Isosorbide [manufactured by Rocket Fleure Co., Ltd.] · CHDM: 1,4-Cyclohexanedimethanol [manufactured by SK Chemical Co., Ltd.] <Carbonic acid diester> · DPC: Diphenyl carbonate [manufactured by Mitsubishi Chemical Corporation] <Catalyst deactivator> · Phosphorous acid [manufactured by Taihei Chemical Industry Co., Ltd.] (molecular weight 82.0) <Heat stabilizer (antioxidant)> · Irganox 1010: Pentaerythritol-tetrakis[3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate] [manufactured by BASF Co., Ltd.] · AS2112: Tris(2,4-di-tert-butylphenyl)phosphite [A manufactured by DEKA Co., Ltd.] (molecular weight 646.9) <Release agent> · E-275: Ethylene glycol distearate [manufactured by NOF Corporation]

[0136] [Production Example 1 Polycarbonate Resin (A-1)] ISB / CHDM Using a continuous polymerization facility consisting of three vertical stirring reactors, one horizontal stirring reactor, and a twin-screw extruder, the polymerization of the polycarbonate resin was carried out. Specifically, first, ISB, CHDM, and DPC were each melted in a tank, and ISB was fed continuously to the first vertical stirring reactor at a flow rate of 35.2 kg / hr, CHDM at 14 .9 kg / hr, and DPC at 74.5 kg / hr (molar ratio of ISB / CHDM / DPC = 0 .700 / 0.300 / 1.010). At the same time, an aqueous solution of calcium acetate monohydrate as a catalyst was fed to the first vertical stirring reactor so that the addition amount of calcium acetate monohydrate was 1.5 μmol per 1 mol of all dihydroxy compounds . The reaction temperature, internal pressure, and residence time of each reactor were, respectively, for the first vertical stirring reactor : 190 °C, 25 kPa, 90 minutes, for the second vertical stirring reactor: 195 °C, 10 kPa, 45 minutes , for the third vertical stirring reactor: 210 °C, 3 kPa, 45 minutes, for the fourth horizontal stirring reactor: 225 °C, 0.5 kPa, 90 minutes. While finely adjusting the internal pressure of the fourth horizontal stirring reactor so that the reduced viscosity of the resulting polycarbonate resin is 0.45 dL / g or more and less than 0.50 dL / g It was operated.

[0137] Polycarbonate resin was extracted from the fourth horizontal type stirring reactor in an amount of 60 kg / hr, and then the resin was supplied in a molten state to a vent type twin-screw extruder [TEX30α manufactured by Nippon Steel Works, L / D: 42 .0, L (mm): length of screw, D (mm): diameter of screw]. The polycarbonate resin passing through the extruder was then passed through a screen type filter (made of SUS316) with an opening of 10 μm while still in a molten state to filter out foreign substances. After that, the polycarbonate resin was discharged from the die in a strand shape, water-cooled and solidified, and then pelletized with a rotary cutter to obtain a polycarbonate resin with a molar ratio of ISB / CHDM of 70 / 30 mol%. In Table-1, the obtained polycarbonate resins were respectively designated as "(A-1)". recorded.

[0138] The extruder had three vacuum vent ports, where residual low molecular components in the resin were devolatilized and removed. 2000 weight ppm of water was added to the resin in front of the second vent, and water injection devolatilization was carried out. In front of the third vent, Irganox1010, AS2112, and E-275 were added to 100 parts by weight of the polycarbonate resin in amounts of 0.1 part by weight, 0.05 part by weight, and 0 .3 part by weight, respectively. Thus, ISB / CHDM copolymer polycarbonate resin pellets were obtained. 0.65 weight ppm of phosphorous acid (0.24 weight ppm as the amount of phosphorus atoms) was added to the polycarbonate resin as a catalyst deactivator. The phosphorous acid was added as follows. Pellets of the polycarbonate resin obtained in Production Example 1 were sprayed with an ethanol solution of phosphorous acid and a masterbatch mixed therewith was prepared, and the first of the extruder From the front of the vent port (on the resin supply port side of the extruder), the masterbatch was supplied so as to be 1 part by weight with respect to 100 parts by weight of the polycarbonate resin in the extruder. A polycarbonate resin (A-2) was obtained in the same manner except that the reduced viscosity was changed to 0.42 dL / g or more and 0.45 dL / g or less.

[0139] [Production Example 2 Polycarbonate Resin (A-2)] ISB / CHDM Except for changing the reduced viscosity to 0.42 dL / g or more and 0.45 dL / g or less, A polycarbonate resin (A-2) was obtained in the same manner.

[0140] [Production Example 3 Polycarbonate Resin (B-1)] ISB / CHDM Except for changing the molar ratio to ISB / CHDM = 0.500 / 0.500 and the reduced viscosity to 0.50 dL / g or more and 0.53 dL / g or less, a polycarbonate resin (B-1) was obtained in the same manner. A polycarbonate resin (B-1) was obtained.

[0141] [Production Example 4 Polycarbonate Resin (B-2)] ISB / CHDM Except for changing the molar ratio to ISB / CHDM = 0.500 / 0.500 and the reduced viscosity to 0.60 dL / g or more and 0.63 dL / g or less, a polycarbonate resin (B-2) was obtained in the same manner. A polycarbonate resin (B-2) was obtained.

[0142] [Raw Materials Used in Examples and Comparative Examples] The abbreviations of the compounds used in the following examples and comparative examples are as follows. [Polycarbonate Resin (A)] As polycarbonate resins containing structural units derived from isosorbide, the following A-1, A- 2, B-1, B-2. A-1: Using isosorbide as the diol component, 1,4-cyclohexanedimethanol (mol ratio = 70:30), and diphenyl carbonate as the dicarboxylic acid component, the reduced viscosity A polycarbonate resin obtained by the melt polymerization method such that the degree is 0.45 or more and less than 0.50 dL / g. Glass transition temperature 122 °C. Reduced viscosity 0.48 dL / g. A-2: Using isosorbide as the diol component, 1,4-cyclohexanedimethanol (molar ratio = 70:30), and diphenyl carbonate as the dicarboxylic acid component, a polycarbonate resin obtained by the melt polymerization method such that the reduced viscosity is 0.40 or more and 0.45 dL / g or less. Glass transition temperature 122 °C. Reduced viscosity 0.44 dL / g. [Polycarbonate resin (B)] B-1: Using isosorbide as the diol component, 1,4-cyclohexanedimethanol (molar ratio = 50:50), and diphenyl carbonate as the dicarboxylic acid component, a polycarbonate resin obtained by the melt polymerization method such that the reduced viscosity is 0.50 dL / g or more and 0.53 dL / g or less. Glass transition temperature 100 °C. Reduced viscosity 0.51 dL / g. B-2: Using isosorbide as the diol component, 1,4-cyclohexanedimethanol (molar ratio = 50:50), and diphenyl carbonate as the dicarboxylic acid component, a polycarbonate resin obtained by the melt polymerization method such that the reduced viscosity is 0.600 dL / g or more and 0.630 dL / g or less. Glass transition temperature 100 °C. Reduced viscosity 0.61 dL / g.

[0143] [Elastomer (B) having a core-shell structure] · Acrylic-styrene rubber, manufactured by Kaneka Corporation.

[0144] [Example 1] Mix the polycarbonate resin (A-1) and the polycarbonate resin (B-1) so as to have the composition shown in Table-1, and use a twin-screw extruder (TEX- manufactured by Japan Steel Works, Ltd.) having one vent port ​​​​​​​​​​​Using (33), it was extruded in a strand shape so that the resin temperature at the outlet became 250 °C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. After cooling and solidifying, it was pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1.

[0145] [Example 2] Polycarbonate resin (A-1), polycarbonate resin (B-1), and an elastomer having a (C) core-shell structure were mixed to obtain the composition shown in Table-1. Using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. having one vent port, it was extruded in a strand shape so that the resin temperature at the outlet became 250 °C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. Shown.

[0146] [Example 3] Polycarbonate resin (A-1) and polycarbonate resin (B-2) were mixed to obtain the composition shown in Table-1. Using a twin-screw extruder (TEX- 33) manufactured by Japan Steel Works, Ltd. having one vent port, it was extruded in a strand shape so that the resin temperature at the outlet became 250 °C, cooled with water and solidified, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1.

[0147] [Example 4] Polycarbonate resin (A-1) and polycarbonate Resin (B-2) and an elastomer having a core-shell structure (C) were mixed, and using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. having one vent port, the resin temperature at the outlet was set to 250 °C and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 ℃ and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 ℃ and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 ℃ and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 .

[0148] [Comparative Example 1] Polycarbonate resin (A-2) and polycarbonate resin (B-1) were mixed to have the composition shown in Table-1, and using a twin-screw extruder (TEX- 33) manufactured by Japan Steel Works, Ltd. having one vent port, the resin temperature at the outlet was set to 250°C and extruded in a strand form, cooled with water solidified, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 solidified, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 solidified, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 solidified, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1

[0149] [Comparative Example 2] Polycarbonate resin (A-2), polycarbonate resin (B-1), and an elastomer having a core-shell structure (C) were mixed to have the composition shown in Table-1, and using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. having one vent port, the resin temperature at the outlet was set to 250 °C and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 °C and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 °C and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 °C and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 °C and extruded in a strand form, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1 .

[0150] [Comparative Example 3] The polycarbonate resin (A-2) and polycarbonate were mixed to have the composition shown in Table-1 resin (B-2), and using a twin-screw extruder (TEX- 33) manufactured by Japan Steel Works, Ltd. with one vent port, it was extruded in a strand form so that the resin temperature at the outlet became 250°C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1.

[0151] [Comparative Example 4] The polycarbonate resin (A-2), polycarbonate resin (B-2), and an elastomer having a (C) core-shell structure were mixed to have the composition shown in Table-1, and using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. with one vent port, it was extruded in a strand form so that the resin temperature at the outlet became 250 °C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1

[0152] [Comparative Example 5] Using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. with one vent port, the polycarbonate resin (A-1) was extruded in a strand form so that the resin temperature at the outlet became 250°C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. ​​​​​​It was controlled as follows. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1.

[0153] [Comparative Example 6] Using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. having one vent port, the polycarbonate resin (A-2) was extruded in a strand form so that the resin temperature at the outlet became 250°C. After cooling and solidifying with water and then pelletizing with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. It was extruded in a strand form so that the resin temperature at the outlet became 250°C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. It was controlled as follows. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1.

[0154] [Comparative Example 7] Using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. having one vent port, the polycarbonate resin (B-1) was extruded in a strand form so that the resin temperature at the outlet became 250°C. After cooling and solidifying with water and then pelletizing with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. It was extruded in a strand form so that the resin temperature at the outlet became 250°C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. It was controlled as follows. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1.

[0155] [Comparative Example 8] Using a twin-screw extruder (TEX-33) manufactured by Japan Steel Works, Ltd. having one vent port, the polycarbonate resin (B-2) was extruded in a strand form so that the resin temperature at the outlet became 250°C. After cooling and solidifying with water and then pelletizing with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. It was extruded in a strand form so that the resin temperature at the outlet became 250°C, cooled and solidified with water, and then pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump and controlled so that the pressure at the vent port became 500 Pa. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1. It was controlled as follows. The results of evaluating the obtained polycarbonate resin composition are shown in Table-1.

[0156]

Table 1

[0157] As shown in Table 1, the resin compositions of Examples 1 to 4 containing polycarbonate resin (A-1) and polycarbonate resin (B) are resin compositions that achieve both moldability and a balance of various physical properties. In particular, they were excellent in the effects of improving heat aging resistance, chemical resistance, and the appearance of molded products. In contrast, Comparative Examples 1 to 4 containing polycarbonate resin (A-2) and polycarbonate resin (B ) were inferior in heat aging resistance and chemical resistance. Comparative Example 5 containing only polycarbonate resin (A-1) was inferior in the appearance of molded products. Comparative Example 6 containing only polycarbonate resin (A-2) was inferior in heat aging resistance, chemical resistance, and the appearance of molded products. Comparative Examples 6 and 7 containing only polycarbonate resin (B) were inferior in heat resistance. From these results, it can be understood that a resin composition containing a polycarbonate resin (A) having a reduced viscosity within a specific range and a polycarbonate resin (B) having a reduced viscosity satisfying specific conditions exhibits the effects of improving heat aging resistance, chemical resistance, and the appearance of molded products, and being excellent in heat resistance. ​

Claims

1. A polycarbonate resin composition comprising a polycarbonate resin (A) and a polycarbonate resin (B), both the polycarbonate resin (A) and the polycarbonate resin (B) have a structural unit (a) derived from a dihydroxy compound represented by the following formula (1), the content ratio of the structural unit (a) in the polycarbonate resin (A) is 60 mol% or more based on the structural units derived from all dihydroxy compounds in the polycarbonate resin (A), and the content ratio of the structural unit (a) in the polycarbonate resin (B) is less than 60 mol% based on the structural units derived from all dihydroxy compounds in the polycarbonate resin (B), the reduced viscosity of the polycarbonate resin (A) is 0.45 dL / g or more and less than 0.50 dL / g, the reduced viscosity of the polycarbonate resin (B) is equal to or higher than the reduced viscosity of the polycarbonate resin (A), the structural units derived from dihydroxy compounds other than the structural unit (a) derived from the dihydroxy compound represented by formula (1) of the polycarbonate resin (A) and the polycarbonate resin (B) are structural units derived from 1,4-cyclohexanedimethanol, the content of the polycarbonate resin (A) is 60 parts by weight or more and 95 parts by weight or less based on a total of 100 parts by weight of the polycarbonate resin composition, the weight ratio of the polycarbonate resin (A) to the polycarbonate resin (B) (the polycarbonate resin (A) / the polycarbonate resin (B)) is 65 / 36 to 95 / 5, A polycarbonate resin composition. 【Chemical 1】

2. The polycarbonate resin composition according to claim 1, wherein the reduced viscosity of the polycarbonate resin (B) is 0.45 dL / g or more and less than 0.55 dL / g.

3. The polycarbonate resin composition according to claim 1, wherein the reduced viscosity of the polycarbonate resin (B) is 0.55 dL / g or more and 0.65 dL / g or less.

4. Furthermore, the polycarbonate resin composition according to any one of claims 1 to 3, further comprising an elastomer (C) having a core-shell structure.

5. The polycarbonate resin composition according to claim 4, wherein the content of the elastomer (C) having a core-shell structure is 0.1 to 20 parts by weight based on a total of 100 parts by weight of the polycarbonate resin composition.

6. A molded article formed by molding the polycarbonate resin composition according to any one of claims 1 to 5.

7. The molded article according to claim 6, which is a component for an automobile.

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