Polycarbonate resin composition, molded article thereof, and impact resistance improver for polycarbonate resin

Abstract

To provide a polycarbonate resin composition excellent in impact resistance, low-temperature impact resistance, and heat resistance.SOLUTION: The polycarbonate resin composition contains: a polycarbonate resin (A); and a polycarbonate copolymer (B) which contains a carbonate structural unit (X) derived from an aliphatic dihydroxy compound (1) represented by the following formula (1) and a carbonate structural unit (Y) derived from a spiroglycol represented by the following formula (2) in a total amount of 95 mass% or more in 100 mass% of all carbonate structural units.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition, more particularly to a polycarbonate resin composition having excellent impact resistance, low-temperature impact resistance, and heat resistance, and a molded article thereof. The present invention also relates to an impact modifier for polycarbonate resin, which is blended with such a polycarbonate resin composition and has excellent handleability. [Background technology]

[0002] Polycarbonate resin has excellent mechanical strength, electrical properties, transparency, etc., and is widely used as an engineering plastic in various fields such as electrical and electronic equipment and automobiles. In recent years, in these application fields, molded products have become thinner, smaller, and lighter, and further improvements in the performance of molding materials are being demanded.

[0003] On the other hand, concerns about global warming due to the depletion of petroleum resources and increased carbon dioxide emissions have led to a demand for the development of plastics made from carbon-neutral plant-derived monomers. In this context, polycarbonate resins produced using the plant-derived raw material isosorbide (hereinafter sometimes referred to as "ISB") have been developed in recent years and are beginning to be used in automotive parts, optical applications, and as a glass replacement (see, for example, Patent Documents 1 and 2).

[0004] However, conventional polycarbonate resins made from isosorbide have not been found to be sufficiently excellent in impact resistance and low-temperature impact resistance to meet the recent demands for thinner, smaller, and lighter molded articles.

[0005] Patent Document 3 discloses a polycarbonate resin that uses a compound produced from plant-derived raw materials and has excellent flexibility, color, and thermal stability, and a polycarbonate resin composition that uses the polycarbonate resin as an impact modifier and has excellent impact resistance and heat resistance. Specifically, Patent Document 3 proposes a copolymer polycarbonate resin that uses polytrimethylene ether glycol (hereinafter sometimes abbreviated as "PO3G") and isosorbide. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2004 / 111106 [Patent Document 2] International Publication No. 2007 / 148604 [Patent Document 3] Patent Publication No. 2021-91900 Summary of the Invention [Problem to be solved by the invention]

[0007] Although the copolymer polycarbonate resin of Patent Document 3 has excellent flexibility, the high content of polytrimethylene ether glycol copolymerized in it lowers the glass transition temperature to below room temperature, making the pellets prone to fusing together. Although the problem of fusing tends to be improved by increasing the molecular weight, there is a risk that the resin will fusing and become difficult to handle in high-temperature environments in summer or when stored for long periods of time.

[0008] An object of the present invention is to provide a polycarbonate resin composition and a molded article thereof that are excellent in impact resistance, low-temperature impact resistance, and heat resistance, and an impact modifier for polycarbonate resins that is suitable for use in such a polycarbonate resin composition and has excellent handleability. [Means for solving the problem]

[0009] The present inventors have found that a polycarbonate copolymer containing carbonate structural units derived from a specific aliphatic dihydroxy compound and carbonate structural units derived from a spiroglycol is easy to handle as an impact modifier for polycarbonate resins, and that the use of this polycarbonate copolymer results in a polycarbonate resin composition that meets the above-mentioned objectives.

[0010] The gist of the present invention is summarized as follows [1] to

[22] .

[0011] [1] A polycarbonate resin composition comprising a polycarbonate resin (A) and a polycarbonate copolymer (B) different from the polycarbonate resin (A), which contains carbonate structural units (X) derived from an aliphatic dihydroxy compound (1) represented by the following formula (1) and carbonate structural units (Y) derived from a spiroglycol represented by the following formula (2) in a total amount of 95 mass% or more relative to 100 mass% of all carbonate structural units:

[0012] [ka]

[0013] (In formula (1), X and Y are different from each other and each independently represent a single bond or a divalent linking group having 1 to 15 carbon atoms, 0 to 6 oxygen atoms, and 2 to 30 hydrogen atoms and not having a cyclic structure. n is an integer of 2 to 100.)

[0014] [ka]

[0015] [2] The polycarbonate resin composition according to [1], wherein the polycarbonate resin (A) contains, per 100 mol% of all carbonate structural units, 10 mol% or more of carbonate structural units derived from a dihydroxy compound having a bonding structure represented by the following formula (3) (provided that no hydrogen atom is bonded to the oxygen atom in formula (3)):

[0016] [ka]

[0017] [3] The polycarbonate resin composition according to [1] or [2], wherein the polycarbonate resin (A) contains 10 mol % or more of carbonate structural units derived from an aromatic dihydroxy compound represented by the following formula (4) per 100 mol % of all carbonate structural units:

[0018] [ka]

[0019] (In formula (4), Z 1 is a single bond, -O-, -S-, -SO2-, -CR 5 R 6 -(However, R 5 and R 6 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 5 and R 6 The alkyl groups may be bonded to each other to form a ring. 1 ~R 4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0020] [4] The polycarbonate resin composition according to [2], wherein the polycarbonate resin (A) contains a carbonate structural unit derived from a dihydroxy compound represented by the following formula (5):

[0021] [ka]

[0022] [5] The polycarbonate resin composition according to [3], wherein the polycarbonate resin (A) contains a carbonate structural unit derived from 2,2-bis(4-hydroxyphenyl)propane represented by the following formula (6):

[0023] [ka]

[0024] [6] The polycarbonate resin composition according to [4], wherein the polycarbonate resin (A) contains 30 mol % or more of carbonate structural units derived from the dihydroxy compound represented by the formula (5) in 100 mol % of all carbonate structural units.

[0025] [7] The polycarbonate resin composition according to any one of [1] to [6], wherein the polycarbonate resin (A) is contained in an amount of 70 to 99 mass% and the polycarbonate copolymer (B) is contained in an amount of 1 to 30 mass% relative to 100 mass% of the total of the polycarbonate resin (A) and the polycarbonate copolymer (B).

[0026] [8] The polycarbonate resin composition according to any one of [1] to [8], wherein the polycarbonate copolymer (B) contains 30% by mass or more and 90% by mass or less of the carbonate structural units (X) in 100% by mass of all carbonate structural units.

[0027] [9] The polycarbonate resin composition according to any one of [1] to [8], wherein the aliphatic dihydroxy compound (1) has a number average molecular weight of 400 or more and 10,000 or less.

[0028]

[10] The polycarbonate resin composition according to any one of [1] to [9], wherein the aliphatic dihydroxy compound (1) is an aliphatic dihydroxy compound represented by the following formula (1A):

[0029] [ka]

[0030] (In formula (1A), n has the same meaning as in formula (1).)

[0031]

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

[10] , wherein the polycarbonate copolymer (B) contains 10% by mass or more and 70% by mass or less of the carbonate structural units (Y) relative to 100% by mass of all carbonate structural units.

[0032]

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

[11] , which has a high-temperature glass transition temperature of 90°C or higher.

[0033]

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

[12] , which has a notched Izod impact strength at 23°C measured in accordance with ASTM D256 of 100 J / m or more.

[0034]

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

[13] , which has a notched Izod impact strength of 100 J / m or more at −20° C. as measured in accordance with ASTM D256.

[0035]

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

[14] , which has a viscosity average molecular weight of 15,000 or more.

[0036]

[16] A molded article using the polycarbonate resin composition according to any one of [1] to

[15] .

[0037]

[17] A molded article for automobile interiors, which is made using the polycarbonate resin composition according to any one of [1] to

[15] .

[0038]

[18] An impact resistance improver for polycarbonate resin, comprising a polycarbonate copolymer (B) containing a total of 95 mass% or more of carbonate structural units (X) derived from an aliphatic dihydroxy compound (1) represented by the following formula (1) and carbonate structural units (Y) derived from a spiroglycol represented by the following formula (2), based on 100 mass% of all carbonate structural units:

[0039] [ka]

[0040] (In formula (1), X and Y are different from each other and each independently represent a single bond or a divalent linking group having 1 to 15 carbon atoms, 0 to 6 oxygen atoms, and 2 to 30 hydrogen atoms and not having a cyclic structure. n is an integer of 2 to 100.)

[0041] [ka]

[0042]

[19] The impact resistance improver for polycarbonate resins according to

[18] , wherein the polycarbonate copolymer (B) contains 30% by mass or more and 90% by mass or less of the carbonate structural units (X) relative to 100% by mass of all carbonate structural units.

[0043]

[20] The impact resistance improver for polycarbonate resins according to

[18] or

[19] , wherein the aliphatic dihydroxy compound (1) has a number average molecular weight of 400 or more and 10,000 or less.

[0044]

[21] The impact resistance improver for polycarbonate resins according to any one of

[18] to

[21] , wherein the aliphatic dihydroxy compound (1) is an aliphatic dihydroxy compound represented by the following formula (1A):

[0045] [ka]

[0046] (In formula (1A), n has the same meaning as in formula (1).)

[0047]

[22] The impact resistance improver for polycarbonate resins according to any one of

[18] to

[20] , wherein the polycarbonate copolymer (B) contains 10% by mass or more and 70% by mass or less of the carbonate structural units (Y) relative to 100% by mass of all carbonate structural units. [Effects of the Invention]

[0048] The polycarbonate resin composition of the present invention can provide a molded article having excellent impact resistance, low-temperature impact resistance, and heat resistance. The impact modifier for polycarbonate resins of the present invention is free from the problem of fusion between pellets and is easy to handle. Furthermore, by blending this impact modifier for polycarbonate resins with polycarbonate resins, it is possible to provide polycarbonate resin compositions and molded articles thereof that are excellent in impact resistance, low-temperature impact resistance, and heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0049] The present invention will be described in detail below with reference to embodiments and examples, but the present invention should not be construed as being limited to the embodiments and examples shown below. In this specification, unless otherwise specified, the symbol "to" is used to mean that the numerical values before and after it are included as the lower limit and upper limit.

[0050] [Polycarbonate resin composition] The polycarbonate resin composition of the present invention comprises a polycarbonate resin (A) and a polycarbonate copolymer (B) (hereinafter sometimes referred to as "polycarbonate copolymer (B) of the present invention") that is different from the polycarbonate resin (A) and contains carbonate structural units (X) derived from an aliphatic dihydroxy compound (1) represented by the following formula (1) and carbonate structural units (Y) derived from a spiroglycol represented by the following formula (2) in a total amount of 95 mass% or more, relative to 100 mass% of all carbonate structural units.

[0051] [ka]

[0052] (In formula (1), X and Y are different from each other and each independently represent a single bond or a divalent linking group having 1 to 15 carbon atoms, 0 to 6 oxygen atoms, and 2 to 30 hydrogen atoms and not having a cyclic structure. n is an integer of 2 to 100.)

[0053] [ka]

[0054] [Polycarbonate copolymer (B)] First, the polycarbonate copolymer (B) of the present invention will be described. The polycarbonate copolymer (B) of the present invention is a polycarbonate copolymer (B) containing carbonate structural units (X) derived from the aliphatic dihydroxy compound (1) represented by the formula (1) above and carbonate structural units (Y) derived from the spiroglycol represented by the formula (2) above in a total amount of 95 mass% or more, based on 100 mass% of all carbonate structural units.

[0055] <Aliphatic dihydroxy compounds (1)> The aliphatic dihydroxy compound (1) that serves as a raw material for the carbonate structural unit (X) is an aliphatic dihydroxy compound represented by the following formula (1).

[0056] [ka]

[0057] (In formula (1), X and Y are different from each other and each independently represent a single bond or a divalent linking group having 1 to 15 carbon atoms, 0 to 6 oxygen atoms, and 2 to 30 hydrogen atoms and not having a cyclic structure. n is an integer of 2 to 100.)

[0058] From the viewpoint of low-temperature impact resistance, X in the above formula (1) is preferably a divalent linking group having no cyclic structure and consisting of 1 to 15 carbon atoms, 1 to 6 oxygen atoms, and 2 to 30 hydrogen atoms, and more preferably an alkylene ether group consisting of an alkylene group having 2 to 10 carbon atoms and one oxygen atom. Y in the formula (1) is preferably a divalent linking group having no cyclic structure and consisting of 1 to 15 carbon atoms, 0 to 6 oxygen atoms, and 2 to 30 hydrogen atoms, and more preferably an alkylene group having 2 to 10 carbon atoms.

[0059] From the viewpoint of ease of polymerization, the aliphatic dihydroxy compound (1) is preferably polytrimethylene ether glycol (PO3G), which is an aliphatic dihydroxy compound represented by the following formula (1A).

[0060] [ka]

[0061] (In formula (1A), n has the same meaning as in formula (1).)

[0062] In this case, it is preferable to use PO3G with a biomass content of 100%, which is synthesized by condensing 1,3-propanediol produced from plant-derived raw materials. Whether PO3G or other substances are produced from plant-derived resources can be determined by, for example, radiocarbon ( 14 This can be confirmed by measuring the concentration of C).

[0063] The number average molecular weight of the aliphatic dihydroxy compound (1) such as PO3G is preferably 400 or more and 10,000 or less. The lower limit of the number average molecular weight of the aliphatic dihydroxy compound (1) such as PO3G is more preferably 420 or more, and even more preferably 450 or more. The upper limit of the number average molecular weight of PO3G is more preferably 7,000 or less, and even more preferably 3,000 or less. Therefore, n in the above formulas (1) and (1A) is preferably a number that satisfies this number average molecular weight.

[0064] In the polycarbonate resin composition of the present invention, the carbonate structural units (X) derived from the aliphatic dihydroxy compound (1) such as PO3G form soft segments, and the carbonate structural units (Y) derived from the spiroglycol form hard segments, thereby exhibiting flexibility, heat resistance, and fusion resistance. When the number-average molecular weight of the aliphatic dihydroxy compound (1) such as PO3G is at least the lower limit, soft segments and hard segments are easily formed, and flexibility, heat resistance, and fusion resistance tend to be easily achieved. When the number-average molecular weight of the aliphatic dihydroxy compound (1) such as PO3G is at most the upper limit, compatibility with the dihydroxy compound (2) is good, and the problem of unsuccessful polymerization can be prevented.

[0065] The number average molecular weight of the aliphatic dihydroxy compound (1) is 1 It can be calculated by a measurement method using H-NMR, a method of determining from the hydroxyl value of the terminal group, or the like.

[0066] <Spiroglycol> The raw material for the carbonate structural unit (Y) of the polycarbonate copolymer (B) of the present invention is a spiro glycol represented by the following formula (2).

[0067] [ka]

[0068] Spiro glycol (SPG) represented by the above formula (2) is preferred from the viewpoints of its crystallinity, heat resistance, flexibility, and resistance to fusion.

[0069] <Content of carbonate structural units (X) and carbonate structural units (Y)> The carbonate structural unit (X) and the carbonate structural unit (Y) in the polycarbonate copolymer (B) of the present invention are contained in the polycarbonate copolymer (B).

[0070] In the polycarbonate copolymer (B) of the present invention, the total content of the carbonate structural units (X) and the carbonate structural units (Y) is 95% by mass or more, based on 100% by mass of all carbonate structural units. By containing the carbonate structural units (X) and the carbonate structural units (Y) in a total content of 95% by mass or more, the polycarbonate copolymer (B) of the present invention can sufficiently achieve the effects of improving impact resistance and low-temperature impact resistance, and fusion resistance. From this perspective, the content of the carbonate structural units (X) and the carbonate structural units (Y) in the polycarbonate copolymer (B) of the present invention is preferably 97% by mass or more, more preferably 98 to 100% by mass.

[0071] The content of the carbonate structural unit (Y) in 100% by mass of all carbonate structural units in the polycarbonate copolymer (B) of the present invention (hereinafter, the contents of carbonate structural units such as the carbonate structural unit (X) and the carbonate structural unit (Y) in the polycarbonate copolymer (B) are all expressed as mass percentages relative to 100% by mass of all carbonate structural units in the polycarbonate copolymer (B)) is preferably 10% by mass or more and 70% by mass or less, and the content of the carbonate structural unit (X) is preferably 30% by mass or more and 90% by mass or less. By containing 10% by mass or more and 70% by mass or less of the carbonate structural unit (Y) and 30% by mass or more and 90% by mass or less of the carbonate structural unit (X), the polycarbonate copolymer (B) of the present invention becomes excellent in the effects of improving impact resistance and low-temperature impact resistance and in the resistance to fusion.

[0072] From the viewpoint of the effect of improving impact resistance and low-temperature impact resistance, the content of the carbonate structural unit (X) in the polycarbonate copolymer (B) of the present invention is more preferably 40% by mass or more, even more preferably 45% by mass, particularly preferably 50% by mass or more, and especially preferably 55% by mass or more, and the content of the carbonate structural unit (Y) is more preferably 60% by mass or less, even more preferably 55% by mass or less, particularly preferably 50% by mass or less, and especially preferably 45% by mass or less. Furthermore, from the viewpoints of heat resistance and fusion resistance, the content of the carbonate structural unit (X) is more preferably 85% by mass or less, even more preferably 83% by mass or less, particularly preferably 80% by mass or less, and especially preferably 77% by mass or less, and the content of the carbonate structural unit (Y) is more preferably 15% by mass or more, even more preferably 17% by mass or more, particularly preferably 20% by mass or more, and especially preferably 23% by mass or more.

[0073] The polycarbonate copolymer (B) of the present invention may contain only one type of aliphatic dihydroxy compound (1) constituting the carbonate structural unit (X), or two or more types of aliphatic dihydroxy compounds (1). That is, the polycarbonate copolymer (B) may contain carbonate structural units (X) derived from two or more types of aliphatic dihydroxy compounds (1).

[0074] The content of each carbonate structural unit (X) and (Y) in the polycarbonate copolymer (B) of the present invention can be determined as the proportion of each dihydroxy compound, i.e., the aliphatic dihydroxy compound (1) and spiroglycol, in the total dihydroxy compounds used in the production of the polycarbonate copolymer (B) of the present invention. The same applies to the other carbonate structural units described below. The content of each carbonate structural unit (X) and (Y) in the polycarbonate copolymer (B) (the proportion of each dihydroxy compound in the total dihydroxy compounds from which the carbonate structural units of the polycarbonate copolymer (B) are derived, i.e., the proportion of the aliphatic dihydroxy compound (1) and spiroglycol) is 1 It can be determined by measuring H-NMR.

[0075] <Other carbonate structural units> The polycarbonate copolymer (B) of the present invention may contain other carbonate structural units than the carbonate structural unit (X) and the carbonate structural unit (Y), i.e., carbonate structural units derived from aromatic or aliphatic dihydroxy compounds other than the aliphatic dihydroxy compound (1) and spiroglycol, within the scope of not impairing the object of the present invention. However, when the polycarbonate copolymer (B) of the present invention contains other carbonate structural units, the content of other carbonate structural units in the polycarbonate copolymer (B) is 5% by mass or less, preferably 2% by mass or less, and it is most preferred that the polycarbonate copolymer (B) contains no other carbonate structural units.

[0076] The polycarbonate copolymer (B) of the present invention may contain only one type of other carbonate structural unit, or may contain two or more types.

[0077] [Method for producing polycarbonate copolymer (B)] The polycarbonate copolymer (B) of the present invention can be produced by a conventionally known polymerization method, and the polymerization method is not particularly limited. Examples of the polymerization method include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among these, the melt transesterification and interfacial polymerization methods are preferred, and the melt transesterification method is more preferred. Below, particularly preferred methods among these methods will be specifically explained.

[0078] (melt transesterification method) In the melt transesterification method, for example, a transesterification reaction is carried out between a carbonate ester and a raw material dihydroxy compound.

[0079] By using a raw material dihydroxy compound containing an aliphatic dihydroxy compound (1) and a spiroglycol, a polycarbonate copolymer (B) containing a carbonate structural unit (X) and a carbonate structural unit (Y) can be produced. When producing the polycarbonate copolymer (B) containing the above-mentioned other carbonate structural units, one or more of the other dihydroxy compounds may be further used together with the aliphatic dihydroxy compound (1) and spiro glycol.

[0080] The carbonate ester may be, for example, a compound represented by the following formula (7), and examples thereof include aryl carbonates, dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0081] [ka]

[0082] In the above formula (7), R 11 and R 12 each independently represents an alkyl group, an aryl group, or an arylalkyl group having 1 to 30 carbon atoms, which may have a substituent. Below, R 11 and R 12 However, when the group is an alkyl group or an arylalkyl group, it is called a dialkyl carbonate, and when the group is an aryl group, it is called a diaryl carbonate. Among them, from the viewpoint of reactivity with dihydroxy compounds, R 11 and R 12 are preferably both optionally substituted aryl groups, and more preferably diaryl carbonate represented by the following formula (8).

[0083] [ka]

[0084] In the above formula (8), R 13 and R 14 are each independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. p and q are each independently an integer of 0 to 5.

[0085] Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), bis(4-methylphenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-fluorophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(2,4-difluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, bis(2-nitrophenyl)carbonate, bis(methylsalicylphenyl)carbonate, and diaryl carbonates which may have a substituent such as ditolyl carbonate. Of these, diphenyl carbonate is preferred. These carbonate esters can be used alone or in combination of two or more.

[0086] The carbonate ester may be substituted with a dicarboxylic acid or dicarboxylic acid ester, preferably in an amount of 50 mol % or less, more preferably 30 mol % or less. Typical dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

[0087] The ratio of the starting dihydroxy compound to the carbonate ester may be any ratio as long as the desired polycarbonate resin is obtained. When polymerizing the carbonate ester with the dihydroxy compound, it is preferable to use a slightly smaller amount or a slightly larger amount than the starting dihydroxy compound. That is, the amount of the carbonate ester is preferably 0.95 to 1.30 times (molar ratio), more preferably 0.98 to 1.20 times (molar ratio), relative to the amount of the dihydroxy compound. If this molar ratio is too small, the resulting polycarbonate resin will have many terminal OH groups, which tends to deteriorate the thermal stability of the resin.If this molar ratio is too large, the transesterification reaction rate will decrease, making it difficult to produce a polycarbonate resin with the desired molecular weight, or the amount of carbonate ester remaining in the resin will increase, which may cause an odor during molding or when the molded product is made.

[0088] When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination as an auxiliary. The transesterification catalyst may be used alone or in any combination of two or more in any ratio.

[0089] In the melt transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 300°C. The pressure during the reaction is not particularly limited, but is usually reduced to 2 mmHg or less. Specifically, the melt polycondensation reaction may be carried out under the above conditions while removing by-products.

[0090] In the presence of an alkali catalyst, the polycarbonate copolymer (B) of the present invention is significantly affected by thermal history and oxidation, leading to a deterioration in color. Therefore, the reaction temperature is preferably 300°C or lower. In addition, to prevent oxygen leakage from the equipment due to excessive pressure reduction, it is preferable to select reduced pressure conditions with a lower limit of approximately 0.05 mmHg.

[0091] The reaction can be carried out in either a batch or continuous manner. When the reaction is carried out in a batch manner, the order in which the reaction substrates (reaction raw materials), catalyst, additives, etc. are mixed can be any order as long as the desired polycarbonate resin can be obtained, and an appropriate order can be set as desired.

[0092] In the melt transesterification method, a catalyst deactivator may be used as needed. As the catalyst deactivator, any compound that neutralizes the transesterification catalyst can be used. Examples of such a catalyst deactivator include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc. The catalyst deactivator may be used alone or in any combination of two or more in any ratio.

[0093] The amount of catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, and usually 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less, relative to the transesterification catalyst. The amount of the catalyst deactivator used is usually 1 ppm or more and 1000 ppm or less, preferably 500 ppm or less, based on the polycarbonate resin.

[0094] [Physical properties of polycarbonate copolymer (B)] <Melting point peak temperature of polycarbonate copolymer (B)> The melting peak temperature of the polycarbonate copolymer (B) of the present invention is not particularly limited, but the melting peak temperature, determined by heating the polycarbonate copolymer (B) of the present invention at a heating rate of 20°C / min using a differential scanning calorimeter, measuring the calorific value, and taking the temperature at the apex of the melting peak, is preferably 40°C or higher, more preferably 80°C or higher, and even more preferably 130°C or higher. A melting peak temperature above the above lower limit is preferred because of excellent resistance to fusion. From the viewpoint of moldability, the upper limit of the melting peak temperature of the polycarbonate copolymer (B) of the present invention is preferably 350°C or lower, more preferably 300°C or lower, and even more preferably 260°C or lower. When the polycarbonate copolymer (B) of the present invention has a plurality of melting peak temperatures, it is preferred that at least the higher melting peak temperature is within the above range. The melting point peak temperature of the polycarbonate copolymer (B) of the present invention is specifically measured by the method described in the Examples section below.

[0095] <Molecular weight of polycarbonate copolymer (B)> The molecular weight of the polycarbonate copolymer (B) of the present invention is preferably 15,000 or more and 150,000 or less in terms of viscosity average molecular weight (Mv) calculated from the solution viscosity. If the viscosity average molecular weight (Mv) is equal to or more than the above lower limit, the impact resistance improving effect is favorable, and if the viscosity average molecular weight (Mv) is equal to or less than the above upper limit, the moldability of the polycarbonate resin composition of the present invention tends to be favorable, and therefore, it is favorable. From this viewpoint, the viscosity average molecular weight (Mv) of the polycarbonate copolymer (B) of the present invention is more preferably 20,000 or more, even more preferably 30,000 or more, and more preferably 120,000 or less, even more preferably 100,000 or less.

[0096] The viscosity average molecular weight (Mv) of the polycarbonate copolymer (B) of the present invention can be determined by measuring the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at 20°C using chloroform as a solvent with an Ubbelohde viscometer, and then calculating the viscosity average molecular weight (Mv) using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv0.83 The intrinsic viscosity (limiting viscosity) [η] is the value calculated from the specific viscosity [ηsp] measured at each solution concentration [C] (g / dL) using the following formula:

[0097]

number

[0098] <Glass transition temperature of polycarbonate copolymer (B)> The glass transition temperature of the polycarbonate copolymer (B) of the present invention is not particularly limited, but the glass transition temperature of the polycarbonate copolymer (B) of the present invention, determined by heating at a heating rate of 20°C / min and measuring the calorific value using a differential scanning calorimeter, is preferably 30°C or lower, more preferably 20°C or lower, and even more preferably 10°C or lower. If the glass transition temperature is below the above upper limit, the effect of improving low-temperature impact resistance is excellent. There is no particular limit to the lower limit of the glass transition temperature of the polycarbonate copolymer (B) of the present invention, but it is usually -100°C or higher. When the polycarbonate copolymer (B) of the present invention has a plurality of glass transition temperatures, it is preferred that at least the lower glass transition temperature is within the above range.

[0099] [Polycarbonate resin (A)] Next, the polycarbonate resin (A) used in the present invention will be described. The polycarbonate resin (A) used in the present invention (hereinafter sometimes referred to as "polycarbonate resin (A) of the present invention") is not particularly limited as long as it is a polycarbonate resin different from the polycarbonate copolymer (B) of the present invention, and examples thereof include those having carbonate structural units derived from a dihydroxy compound described below.

[0100] <Dihydroxy compound having a bond structure represented by formula (3)> An example of a suitable embodiment of the polycarbonate resin (A) of the present invention is one containing a carbonate structural unit derived from a dihydroxy compound having a bonding structure represented by the following formula (3) (provided that no hydrogen atoms are bonded to the oxygen atoms in formula (3)). When the polycarbonate resin (A) contains a carbonate structural unit derived from a dihydroxy compound having a bonding structure represented by the following formula (3) (provided that no hydrogen atoms are bonded to the oxygen atoms in formula (3)), the polycarbonate resin has excellent heat resistance and is therefore preferred.

[0101] [ka]

[0102] Examples of dihydroxy compounds having a bond structure represented by the above formula (3) include 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-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, and 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene. compounds having an aromatic group on a side chain and an ether group bonded to an aromatic group on the main chain, such as fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene; oxyalkylene glycols exemplified by diethylene glycol, triethylene glycol, and tetraethylene glycol;Bis[4-(2-hydroxyethoxy)phenyl]methane, bis[4-(2-hydroxyethoxy)phenyl]diphenylmethane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]ethane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]-1-phenylethane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)-3-methylphenyl]propane, 2,2-bis[3,5-dimethyl-4-(2-hydroxyethoxy)phenyl]propane, 1,1-bis[ 4-(2-hydroxyethoxy)phenyl]-3,3,5-trimethylcyclohexane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,4-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,3-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 2,2-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]propane, 2,2-bis[(2-hydroxyethoxy)-3-isopropylphenyl]propane, 2,2-bis[3-tert-butyl-4-(2- bis(hydroxyalkoxy)phenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]butane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]-4-methylpentane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]octane, 1,1-bis[4-(2-hydroxyethoxy)phenyl]decane, 2,2-bis[3-bromo-4-(2-hydroxyethoxy)phenyl]propane, 2,2-bis[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl]propane, etc. aryl)alkanes; bis(hydroxyalkoxyaryl)cycloalkanes such as 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 1,1-bis[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl]cyclohexane, and 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclopentane; dihydroxyalkoxydiaryl ethers such as 4,4'-bis(2-hydroxyethoxy)diphenyl ether and 4,4'-bis(2-hydroxyethoxy)-3,3'-dimethyldiphenyl ether;Bishydroxyalkoxyaryl sulfides such as 4,4'-bis(2-hydroxyethoxyphenyl) sulfide and 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl] sulfide; bishydroxyalkoxyaryl sulfoxides such as 4,4'-bis(2-hydroxyethoxyphenyl) sulfoxide and 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl] sulfoxide; bishydroxyalkoxyaryl sulfones such as 4,4'-bis(2-hydroxyethoxyphenyl) sulfone and 4,4'-bis[4-(2-dihydroxyethoxy)-3-methylphenyl] sulfone; 1,4-bishydroxyethoxybenzene, 1,3-bishydroxyethoxybenzene, 1,2-bishydroxy Examples of suitable dihydroxy compounds include ethoxybenzene, 1,3-bis[2-[4-(2-hydroxyethoxy)phenyl]propyl]benzene, 1,4-bis[2-[4-(2-hydroxyethoxy)phenyl]propyl]benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, 1,3-bis[4-(2-hydroxyethoxy)phenyl]-5,7-dimethyladamantane, and dihydroxy compounds having a heterocyclic group, such as those represented by the following formula (5): and spiro glycols such as 2-(5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl)-2-methylpropan-1-ol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane. These may be used alone or in combination of two or more. Among these, the dihydroxy compound represented by the following formula (5) is preferred.

[0103] [ka]

[0104] Examples of the dihydroxy compound represented by the above formula (5) include isosorbide, isomannide, and isoidet, which are stereoisomers. These may be used alone or in combination of two or more. Of these dihydroxy compounds, isosorbide, which is obtained by dehydration condensation of sorbitol produced from various starches, which are abundant and easily available as a resource, is most preferred in terms of availability, ease of production, heat resistance, and moldability.

[0105] In this embodiment, the content of carbonate structural units derived from a dihydroxy compound having a bond structure represented by the above formula (3), such as isosorbide, contained in the polycarbonate resin (A) is, from the viewpoint of more effectively obtaining the above-mentioned effects provided by including carbonate structural units derived from the dihydroxy compound, preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to 100 mol% of all carbonate structural units, and this content may be 100 mol%.

[0106] From the viewpoint of impact resistance and heat resistance, the polycarbonate resin (A) containing carbonate structural units derived from isosorbide preferably contains 40 to 80 mol % of carbonate structural units derived from isosorbide and 20 to 60 mol % of carbonate structural units derived from an alicyclic dihydroxy compound described below, such as 1,4-cyclohexanedimethanol.

[0107] The content of carbonate structural units derived from dihydroxy compounds having a bond structure represented by the formula (3), such as isosorbide, contained in the polycarbonate resin (A), and the content of carbonate structural units derived from alicyclic dihydroxy compounds, such as 1,4-cyclohexanedimethanol, which will be described later, are determined by the following formula: 1 It can be determined by measuring H-NMR.

[0108] <Aromatic dihydroxy compound represented by formula (4)> Another preferred embodiment of the polycarbonate resin (A) of the present invention is one containing a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following formula (4): When the polycarbonate resin (A) contains a carbonate structural unit derived from an aromatic dihydroxy compound represented by the following formula (4), it is preferable because it has excellent heat resistance.

[0109] [ka]

[0110] (In formula (4), Z 1 is a single bond, -O-, -S-, -SO2-, -CR 5 R 6 -(However, R 5 and R 6 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 5 and R 6 The alkyl groups may be bonded to each other to form a ring. 1 ~R 4 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0111] In the above formula (4), Z 1 is a single bond, -O-, -S-, -SO2-, -CR 5 R 6 - represents. -CR 5 R 6 -R 5 and R 6 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0112] R 5 and R 6 Specific examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include: Methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl; Methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group, methylnonadecyl group; Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group, dimethyloctadecyl group; Trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; Ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group; Butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group etc.

[0113] In addition, R is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. 5 and R 6 may be bonded to each other to form a ring, and R 5 and R 6 Examples of the ring formed by bonding together include a cyclohexane ring, a cyclododecyl ring, and a 3,3,5-trimethylcyclohexane ring.

[0114] R 5 and R 6 Specific examples of the substituted or unsubstituted aryl group include, independently, a phenyl group, a tolyl group, a 4-methylphenyl group, a naphthyl group, and the like.

[0115] In formula (4), Z is selected from the viewpoint of impact resistance and heat resistance. 1 is preferably —C(CH3)CH3—, R 5 and R 6 are bonded to each other to form a ring, and more preferably -C(CH3)CH3-.

[0116] In formula (4), R 1 ~R 4 R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 ~R 4The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and the substituted or unsubstituted aryl group include R 5 ,R 6 Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and the substituted or unsubstituted aryl group include those exemplified above.

[0117] From the viewpoint of impact resistance and heat resistance, R 5 ,R 6 are each independently preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0118] Examples of the aromatic dihydroxy compound represented by formula (4) include 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, and 1,1-bis(4-hydroxyphenyl)cyclohexane.

[0119] Furthermore, examples of the aromatic dihydroxy compound include bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene.

[0120] In this embodiment, the content of carbonate structural units derived from an aromatic dihydroxy compound represented by the formula (4), such as bisphenol A, contained in the polycarbonate resin (A) is, from the viewpoint of more effectively obtaining the above-mentioned effects provided by including carbonate structural units derived from the aromatic dihydroxy compound, preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to 100 mol% of all carbonate structural units, and this content may be 100 mol%.

[0121] From the viewpoints of impact resistance and heat resistance, the aromatic dihydroxy compound represented by the formula (4) is preferably 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), which is an aromatic dihydroxy compound represented by the following formula (6): That is, as another example of a preferred embodiment, the polycarbonate resin (A) preferably contains carbonate structural units derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

[0122] [ka]

[0123] <Other dihydroxy compounds> The polycarbonate resin (A) of the present invention may contain one or more carbonate structural units derived from dihydroxy compounds other than the carbonate structural units derived from the dihydroxy compound having the bond structure represented by the formula (3) and the carbonate structural units derived from the aromatic dihydroxy compound represented by the formula (4). Examples of other dihydroxy compounds constituting carbonate structural units derived from other dihydroxy compounds that can be contained in the polycarbonate resin (A) of the present invention include the following.

[0124] (alicyclic dihydroxy compounds) The polycarbonate resin (A) of the present invention may contain a structural unit derived from an alicyclic dihydroxy compound as a carbonate structural unit derived from another dihydroxy compound. The alicyclic dihydroxy compound is not particularly limited, but specific examples include cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; cyclodecane dimethanols such as tricyclodecane dimethanol and pentacyclopentadecanedimethanol; adamantanediols, etc. Among these, from the viewpoints of ease of availability and ease of handling, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are preferred.

[0125] (aliphatic dihydroxy compounds) The polycarbonate resin (A) of the present invention may contain a structural unit derived from an aliphatic dihydroxy compound as a carbonate structural unit derived from another dihydroxy compound. Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, and 1,6-hexanediol.

[0126] These other dihydroxy compounds can be used singly or in combination of two or more.

[0127] The polycarbonate resin (A) of the present invention can be produced by the same method as that for the polycarbonate copolymer (B) of the present invention described above. Furthermore, commercially available products can also be used as the polycarbonate resin (A) of the present invention, and examples of commercially available polycarbonate resin (A) include polycarbonate resins (A1) to (A5) used in the examples described later.

[0128] [Polycarbonate resin (A) and polycarbonate copolymer (B) content ratio] The polycarbonate resin composition of the present invention preferably contains 70 to 99 mass% of the polycarbonate resin (A) and 1 to 30 mass% of the polycarbonate copolymer (B) of the present invention, based on a total of 100 mass% of the polycarbonate resin (A) and the polycarbonate copolymer (B) of the present invention, more preferably 70 to 97 mass% of the polycarbonate resin (A) and 3 to 30 mass% of the polycarbonate copolymer (B), and even more preferably 80 to 95 mass% of the polycarbonate resin (A) and 5 to 20 mass% of the polycarbonate copolymer (B). When the content of polycarbonate resin (A) is equal to or less than the above upper limit and the content of polycarbonate copolymer (B) is equal to or greater than the above lower limit, the effect of improving impact resistance and low-temperature impact resistance by containing polycarbonate copolymer (B) can be effectively obtained. However, if the content of polycarbonate copolymer (B) is excessively high, the heat resistance and elastic modulus of the resulting polycarbonate resin composition tend to decrease, so it is preferable that the content of polycarbonate resin (A) is equal to or greater than the above lower limit and the content of polycarbonate copolymer (B) is equal to or less than the above upper limit.

[0129] The polycarbonate resin composition of the present invention may contain only one type of polycarbonate resin (A), or may contain two or more types of polycarbonate resins that differ in the type, composition, physical properties, etc. of carbonate structural units. Similarly, the polycarbonate copolymer (B) of the present invention may contain only one type, or may contain two or more types that differ in the type, composition, physical properties, etc. of carbonate structural units.

[0130] [Other ingredients] The polycarbonate resin composition of the present invention may contain other components in addition to the polycarbonate resin (A) and polycarbonate copolymer (B) of the present invention, as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins, various resin additives, etc.

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

[0132] Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; styrene-based resins such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; and polymethacrylate resin. The other resins may be contained either alone or in any combination and ratio of two or more.

[0133] [Method for producing polycarbonate resin composition] The polycarbonate resin composition of the present invention can be produced by mixing the polycarbonate resin (A) of the present invention with the polycarbonate copolymer (B) of the present invention. There are no particular limitations on the method for mixing, and examples thereof include the following methods 1) to 4). 1) A method of melt-kneading a polycarbonate resin (A) and a polycarbonate copolymer (B); 2) A method of melt-kneading a molten polycarbonate resin (A) and a molten polycarbonate copolymer (B); 3) A method in which the polycarbonate resin (A) and the polycarbonate copolymer (B) are mixed in a solution state; 4) A method of dry-blending a polycarbonate resin (A) and a polycarbonate copolymer (B); Each method will be explained below.

[0134] 1) A method of melt-kneading a polycarbonate resin (A) and a polycarbonate copolymer (B); Pellets or granules of polycarbonate resin (A) and pellets or granules of polycarbonate copolymer (B) are melt-kneaded using a mixing device such as a kneader, twin-screw extruder, single-screw extruder, etc. Pellets or granules of polycarbonate resin (A) and pellets or granules of polycarbonate copolymer (B) may be mixed in advance in a solid state and then kneaded, or one of them may be melted first in the mixing device, and the other polycarbonate resin may be added thereto and kneaded. The kneading temperature is not particularly limited, but is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 230°C or higher. Also, 320°C or lower is preferred, and 300°C or lower is particularly preferred. A low kneading temperature is undesirable because the polycarbonate resin (A) and the polycarbonate copolymer (B) are not mixed completely, which can result in variations in impact resistance and heat resistance when a molded product is produced. Also, a too high kneading temperature is undesirable because it can deteriorate the color tone of the polycarbonate resin composition.

[0135] 2) A method of melt-kneading a molten polycarbonate resin (A) and a molten polycarbonate copolymer (B); The molten polycarbonate resin (A) and the molten polycarbonate copolymer (B) are mixed using a mixing device such as a stirring tank, static mixer, kneader, twin-screw extruder, single-screw extruder, etc. In this case, if the polycarbonate resin is obtained by melt polymerization, it may be introduced into the mixing device in a molten state without being cooled and solidified.

[0136] 3) A method in which the polycarbonate resin (A) and the polycarbonate copolymer (B) are mixed in a solution state; In this method, the polycarbonate resin (A) and the polycarbonate copolymer (B) are dissolved in an appropriate solvent to form a solution, mixed in the solution state, and then isolated as a polycarbonate resin composition. Suitable solvents include aliphatic hydrocarbons such as hexane and n-heptane; chlorinated aliphatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, and 1,2-dichloroethylene; aromatic hydrocarbons such as benzene, toluene, and xylene; and substituted aromatic hydrocarbons such as nitrobenzene and acetophenone. Among these, chlorinated hydrocarbons such as chloroform are preferred. These solvents can be used alone or in combination with other solvents. Examples of the mixing device include a stirring tank, a static mixer, etc. The mixing temperature is not particularly limited as long as the polycarbonate resin (A) and the polycarbonate copolymer (B) are dissolved, and the mixing is usually carried out at a temperature equal to or lower than the boiling point of the solvent used.

[0137] 4) A method of dry-blending a polycarbonate resin (A) and a polycarbonate copolymer (B); This method involves dry blending pellets or granules of polycarbonate resin (A) with pellets or granules of polycarbonate copolymer (B) using a tumbler, super mixer, Henschel mixer, Nauta mixer or the like.

[0138] Among the above methods 1) to 4), methods 1) and 2) in which the polycarbonate resin (A) and the polycarbonate copolymer (B) are melt-kneaded, and method 4) in which the polycarbonate resin (A) and the polycarbonate copolymer (B) are dry-blended are preferred. In producing the polycarbonate resin composition, in any of the above methods, pigments, dyes, mold release agents, heat stabilizers, etc. may be added as appropriate within the range that does not impair the object of the present invention.

[0139] [Glass transition temperature of polycarbonate resin composition] There are no particular restrictions on the glass transition temperature of the polycarbonate resin composition of the present invention, but the polycarbonate resin composition of the present invention preferably has a higher-temperature glass transition temperature of 90°C or higher, more preferably 92°C or higher, and even more preferably 115°C or higher, as determined by heating at a heating rate of 20°C / min using a differential scanning calorimeter and measuring the calorific value. This higher-temperature glass transition temperature reflects the glass transition temperature of the polycarbonate resin (A) of the present invention, and a glass transition temperature of 90°C or higher indicates excellent heat resistance. There are no particular restrictions on the upper limit of the glass transition temperature of the polycarbonate resin composition of the present invention, but it is usually 200°C or lower.

[0140] [Izod impact strength of polycarbonate resin composition] Although there are no particular limitations, the polycarbonate resin composition of the present invention preferably has a notched Izod impact strength at 23°C measured in accordance with ASTM D256 of 100 J / m or more, more preferably 200 J / m or more, and more preferably 250 J / m or more. Polycarbonate resin compositions having an Izod impact strength at 23°C equal to or greater than the above lower limit have excellent impact resistance and are therefore preferred.

[0141] Furthermore, although there are no particular limitations, the polycarbonate resin composition of the present invention preferably has a notched Izod impact strength at -20°C measured in accordance with ASTM D256 of 100 J / m or more, more preferably 110 J / m or more, and preferably 140 J / m or more. Polycarbonate resin compositions having an Izod impact strength at -20°C equal to or greater than the above lower limit have excellent impact resistance and are therefore preferred.

[0142] The Izod impact test of the polycarbonate resin composition is carried out by using a test piece of the polycarbonate resin composition having a thickness of 3.2 mm, a length of 53.5 mm and a width of 12.7 mm, according to the method described in the Examples section below.

[0143] [Molecular weight of polycarbonate resin composition] The molecular weight of the polycarbonate resin composition of the present invention is preferably 15,000 or more, in terms of viscosity average molecular weight (Mv) calculated from the solution viscosity. A viscosity average molecular weight (Mv) of at least the above lower limit is preferred because the mechanical properties of the polycarbonate resin composition of the present invention are good. On the other hand, the upper limit of the viscosity average molecular weight of the polycarbonate resin composition of the present invention is preferably 30,000 or less, because the fluidity of the polycarbonate resin composition of the present invention is good. From this perspective, the viscosity average molecular weight (Mv) of the polycarbonate resin composition of the present invention is more preferably 16,000 to 28,000, and even more preferably 17,000 to 25,000.

[0144] The viscosity average molecular weight (Mv) of the polycarbonate resin composition of the present invention can be determined by measuring the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at 20°C using methylene chloride as a solvent with an Ubbelohde viscometer, and then calculating the viscosity average molecular weight (Mv) using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 The intrinsic viscosity (η) is as described above.

[0145] [Molded body] The molded article of the present invention uses the polycarbonate resin composition of the present invention and is produced by molding the polycarbonate resin composition of the present invention. To produce the molded article of the present invention from the polycarbonate resin composition of the present invention, a conventional extruder or injection molding machine is used.

[0146] The molding temperature when molding the polycarbonate resin composition of the present invention is preferably 200°C or higher, more preferably 220°C or higher, and most preferably 230°C or higher. It is also preferably 350°C or lower, particularly preferably 320°C or lower. If the molding temperature is too low, the melt viscosity may increase, the fluidity may decrease, and moldability may decrease. If the molding temperature is too high, the polycarbonate resin composition may become discolored, and the color tone of the resulting molded article may also deteriorate, which is undesirable.

[0147] When injection molding or extrusion molding is carried out, pigments, dyes, mold release agents, heat stabilizers, etc. may be added to the polycarbonate resin composition of the present invention as appropriate within the range that does not impair the object of the present invention.

[0148] [Injection molded products] To produce an injection-molded article from the polycarbonate resin composition of the present invention, a conventional injection molding machine is used.

[0149] When an injection molding machine or the like is used, the mold temperature is preferably 150°C or lower, more preferably 130°C or lower. Also, it is preferably 30°C or higher, particularly preferably 50°C or higher. If the mold temperature is too high, the cooling time during molding must be extended, which may lengthen the production cycle of molded articles and reduce productivity. If the mold temperature is too low, the melt viscosity of the polycarbonate resin composition may become too high, making it impossible to obtain uniform molded articles and causing problems such as unevenness on the surface of the molded articles, which is undesirable.

[0150] [Extrusion molding] To produce an extrusion molded article from the polycarbonate resin composition of the present invention, a conventional extrusion molding machine is used. The extrusion molding machine is generally equipped with a T-die, a round die, or the like, and extrusion molded articles of various shapes can be obtained. Examples of extrusion molded articles include sheets, films, plates, tubes, pipes, and the like. Among these, sheets and films are preferred.

[0151] The extrusion molded article of the polycarbonate resin composition of the present invention may be laminated on one or both sides of the extrusion molded article with a hard coat layer to improve adhesion, paintability, and printability, or may be heat-laminated on one or both sides of the extrusion molded article with a film for improving weather resistance and / or scratch resistance. Furthermore, the surface may be subjected to a graining process or a semi-transparent or opaque process.

[0152] [Application] Molded articles of the polycarbonate resin composition of the present invention can be used in a variety of fields, including buildings, vehicles, electrical and electronic equipment, machinery, and the like. In particular, the molded article of the present invention is suitable as an automobile interior or exterior molded article, especially as an automobile interior molded article, due to its excellent impact resistance, low-temperature impact resistance, and heat resistance.

[0153] Examples of automotive interior and exterior parts to which the molded article of the present invention can be applied include, but are not limited to, automotive exterior parts such as fenders, bumpers, fascias, door panels, side garnishes, pillars, radiator grilles, side protectors, side moldings, rear protectors, rear moldings, various spoilers, bonnets, roof panels, trunk lids, detachable tops, window reflectors, mirror housings, and outer door handles, as well as instrument panels, center console panels, meter parts, various switches, car navigation parts, car audio-visual parts, and automobile computer parts.

[0154] [Impact modifier for polycarbonate resin] The impact resistance improver for polycarbonate resin of the present invention comprises a polycarbonate copolymer (B) containing a total of 95 mass% or more of carbonate structural units (X) derived from an aliphatic dihydroxy compound (1) represented by the following formula (1) and carbonate structural units (Y) derived from a spiroglycol represented by the following formula (2), based on 100 mass% of all carbonate structural units.

[0155] That is, the impact modifier for polycarbonate resins of the present invention comprises the above-mentioned polycarbonate copolymer (B) of the present invention, and the preferred embodiments of the impact modifier for polycarbonate resins of the present invention are also applicable to the preferred embodiments of the polycarbonate copolymer (B) of the present invention. The impact modifier for polycarbonate resin of the present invention is used by being blended with a polycarbonate resin, preferably the above-mentioned polycarbonate resin (A) of the present invention, as an impact modifier for improving the impact resistance and low-temperature impact resistance of the polycarbonate resin. [Example]

[0156] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to the following examples. The physical properties of the polycarbonate resins obtained in the following Examples and Comparative Examples were evaluated by the following methods.

[0157] (1) Viscosity average molecular weight (Mv) The polycarbonate resin was dissolved in methylene chloride (concentration 6.0 g / L), and the intrinsic viscosity (limiting viscosity) [η] (unit: dL / g) at 20°C was determined using an Ubbelohde viscosity tube (manufactured by Moritomo Rika Kogyo Co., Ltd.), and the viscosity average molecular weight (Mv) was calculated using Schnell's viscosity formula (the following formula). η = 1.23 × 10 -4 Mv 0.83 For PC(B1), PC(B2), PC(B3), and PC(B4) described below, measurements were performed in chloroform instead of methylene chloride, and the viscosity average molecular weight (Mv) was calculated using the above formula.

[0158] (2) Glass transition temperature (Tg) and melting point peak temperature (Tm) Measurements were performed using a differential scanning calorimeter (DSC6220, manufactured by SII). The resulting polycarbonate resin was used as the measurement sample without drying. An aluminum sample pan containing approximately 10 mg of the measurement sample was heated from 30°C to 300°C at a heating rate of 20°C / min with a nitrogen gas flow rate of 50 mL / min, and then cooled to -120°C at a heating rate of 40°C / min. The pan was then heated again to 300°C at a heating rate of 20°C / min. The differential scanning calorimetry curve obtained in the second temperature rise was analyzed as the measurement curve. The glass transition temperature (Tg) and melting peak temperature (Tm) were analyzed in accordance with JIS K7121-1987. The extrapolated glass transition onset temperature was determined as the temperature at the intersection of a straight line extending the low-temperature baseline toward the high-temperature side and a tangent drawn at the point where the gradient of the step-like change in the glass transition curve is maximum. This extrapolated glass transition temperature was designated the glass transition temperature (Tg). The peak melting point temperature (Tm) was designated as the peak of the melting point temperature.

[0159] (3) Izod impact strength Using a small injection molding machine (Shinko Selbic C, Mobile, Inc.), samples of the polycarbonate resin composition were molded under the cylinder and mold temperatures described in each example to obtain test specimens measuring 3.2 mm thick, 53.5 mm long, and 12.7 mm wide. According to ASTM D256, a notch was machined into each test specimen at a position 31.8 mm from the longitudinal edge, with a notch tip radius of 0.25 mm and a notch depth of 2.54 mm. Notched Izod impact strength values were measured five times at 23°C and -20°C using a Universal Impact Tester (Toyo Seiki Seisakusho, Ltd.), and the average values were calculated.

[0160] [raw materials] The compounds used in the following Examples and Comparative Examples are abbreviated as follows: The compounds used were manufactured by the following manufacturers. Of the following compounds, plant-derived raw materials were used for PO3G.

[0161] <Dihydroxy compounds> PO3G2700: Polytrimethylene ether glycol, number average molecular weight 2743 (manufactured by ALLESSA, trade name: VELVETOL) PO3G1000: Polytrimethylene ether glycol, number average molecular weight 1042 (manufactured by ALLESSA, trade name: VELVETOL) SPG: Spiroglycol (Mitsubishi Gas Chemical Company, Inc.)

[0162] <Carbonate ester> DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

[0163] <Polymerization catalyst> Calcium acetate monohydrate (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0164] [Production Examples 1 to 4: Production of Polycarbonate Copolymer (B)] The following are examples of the production of PC(B1), PC(B2), PC(B3), and PC(B4), which are the polycarbonate copolymer (B) of the present invention.

[0165] [Manufacturing example 1: PC(B1)] A raw material mixture was prepared by adding 81.70 g (approximately 0.0298 mol) of PO3G2700, 35.01 g (approximately 0.115 mol), 32.42 g (approximately 0.151 mol) of SPG, 32.42 g (approximately 0.151 mol) of DPC, and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst to a glass reactor having an internal volume of 570 mL and equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device, so that the calcium acetate monohydrate concentration was 100 μmol per 1 mol of the total dihydroxy compounds.

[0166] Next, the pressure inside the glass reactor was reduced to 1.3 to 4.0 kPa (10 to 30 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated five times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. The agitator was then rotated at 100 rpm. After stirring for 60 minutes, the temperature was increased to 240°C, and the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute over 40 minutes while distilling off phenol, which was a by-product of the oligomerization reaction of the dihydroxy compound and DPC inside the reactor.

[0167] Next, the pressure inside the reactor was maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. Thereafter, while maintaining the external temperature of the reactor at 240°C, the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute over 40 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was further reduced to 40 Pa (approximately 0.3 Torr), and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power.

[0168] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter. This polycarbonate resin contains 68.5 mass % of carbonate structural units (X) and 31.5 mass % of carbonate structural units (Y), and has a biomass content of 67.8 mass %.

[0169] The viscosity average molecular weight (Mv), glass transition temperature (Tg), and melting point peak temperature (Tm) of the polycarbonate resin thus obtained were measured. The results are shown in Table 1. In Table 1, the content ratios of the carbonate structural unit (X) and the carbonate structural unit (Y) are shown as values rounded off to the nearest whole number.

[0170] [Manufacturing example 2: PC(B2)] A raw material mixture was prepared by adding 70.03 g (approximately 0.0255 mol) of PO3G2700, 46.68 g (approximately 0.153 mol), 40.05 g (approximately 0.187 mol) of DPC, and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst such that the calcium acetate monohydrate was 100 μmol per 1 mol of the total dihydroxy compounds. The procedure described in Production Example 1 was repeated except that the external temperature of the reactor was raised to 250°C during the reduction in pressure from 13.3 kPa (100 Torr) to carry out the reaction. The obtained polycarbonate resin contained 58.2 mass % of carbonate structural units (X) and 41.8 mass % of carbonate structural units (Y), and had a biomass content of 57.7 mass %.

[0171] The viscosity average molecular weight (Mv), glass transition temperature (Tg), and melting point peak temperature (Tm) of the polycarbonate resin thus obtained were measured. The results are shown in Table 1.

[0172] [Manufacturing example 3: PC(B3)] A raw material mixture was prepared by adding 81.70 g (approximately 0.0784 mol) of PO3G1000, 35.01 g (approximately 0.115 mol), 43.30 g (approximately 0.202 mol) of SPG, and 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst to a 570 mL glass reactor equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device so that the calcium acetate monohydrate concentration was 100 μmol per 1 mol of the total dihydroxy compounds.

[0173] Next, the pressure inside the glass reactor was reduced to 1.3 to 4.0 kPa (10 to 30 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated five times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. Then, the agitator was rotated at 100 rpm, and the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute over 40 minutes while distilling off phenol, which was a by-product of the oligomerization reaction of the dihydroxy compound and DPC inside the reactor.

[0174] Next, the pressure inside the reactor was maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 240°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute over 40 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was then further reduced to 40 Pa (approximately 0.3 Torr), and the polycondensation reaction was carried out. The polycondensation reaction was terminated when the reactor's agitator reached a predetermined stirring power.

[0175] Next, the pressure inside the reactor was restored to 101.3 kPa absolute pressure with nitrogen, and then increased to 0.2 MPa gauge pressure. The polycarbonate resin was extracted in the form of strands from the bottom of the reactor, and the strand-like polycarbonate resin was obtained and then pelletized using a rotary cutter. This polycarbonate resin contains 68.8 mass % of carbonate structural units (X) and 31.2 mass % of carbonate structural units (Y), and has a biomass content of 67.0 mass %.

[0176] The viscosity average molecular weight (Mv), glass transition temperature (Tg), and melting point peak temperature (Tm) of the polycarbonate resin thus obtained were measured. The results are shown in Table 1.

[0177] [Manufacturing example 4: PC(B4)] A raw material mixture was prepared by adding 70.03 g (approximately 0.0672 mol) of PO3G1000, 46.68 g (approximately 0.153 mol), 49.38 g (approximately 0.231 mol) of DPC, and a 3.0 mass% aqueous solution of calcium acetate monohydrate as a catalyst so that the calcium acetate monohydrate was 100 μmol per 1 mol of the total dihydroxy compounds, and the procedure described in Production Example 3 was followed. The obtained polycarbonate resin contained 58.6 mass % of carbonate structural units (X) and 41.4 mass % of carbonate structural units (Y), and had a biomass content of 57.1 mass %.

[0178] The viscosity average molecular weight (Mv), glass transition temperature (Tg), and melting point peak temperature (Tm) of the polycarbonate resin thus obtained were measured. The results are shown in Table 1.

[0179] For PC(B1), PC(B2), PC(B3), and PC(B4), which are the polycarbonate copolymers (B) of the present invention obtained in Production Examples 1 to 4, 5 g of pellets were placed in an aluminum dish with a circular bottom, a diameter of 7 cm, and a height of 3 cm, and allowed to stand at room temperature for 1 day to check for fusion between the pellets. The results are also shown in Table 1.

[0180] [Table 1]

[0181] From Table 1, it can be seen that the polycarbonate copolymer (B) of the present invention, ie, the impact modifier for polycarbonate resin of the present invention, is free from the problem of fusion between pellets and has excellent handleability.

[0182] [Polycarbonate resin (A)] As the polycarbonate resin (A), those shown in Table 2 below were used. Furthermore, polymethyl methacrylate resin (PMMA) shown in Table 2 was used as a comparative resin.

[0183] [Table 2]

[0184] [Examples 1 to 11, Comparative Examples 1 to 7] PC (B1), PC (B2), PC (B3), and PC (B4) obtained in Production Examples 1 to 4 were dry-blended with the raw materials listed in Table 2 in the proportions (mass ratios) listed in Table 3. Izod test specimens were molded using a small injection molding machine (Shinko Cellbic C, Mobile, Inc.) under the molding conditions listed in Table 3. The viscosity average molecular weight (Mv), notched Izod impact strength, and glass transition temperature of the Izod test specimens thus obtained were measured. The results are shown in Table 3.

[0185] [Table 3]

[0186] As can be seen from Table 3, Comparative Examples 1 to 3, which contain only polycarbonate resin (A) without blending PC(B1), PC(B2), PC(B3), or PC(B4), which correspond to the impact resistance modifiers for polycarbonate resins of the present invention, and Comparative Example 4, which contains only PMMA, are inferior in impact resistance and low-temperature impact resistance. However, the polycarbonate resin compositions of Examples 1 to 11, which contain the polycarbonate resin (A) of Comparative Examples 1 to 3 blended with PC(B1), PC(B2), or PC(B3), which are the impact resistance modifiers for polycarbonate resins of the present invention, all maintain good heat resistance and exhibit significantly improved impact resistance and low-temperature impact resistance. These results demonstrate that the impact resistance improver for polycarbonate resins of the present invention has an excellent effect of improving the impact resistance of the polycarbonate resin (A). In Comparative Examples 5 to 7, in which the impact resistance modifier for polycarbonate resins of the present invention was blended with PMMA instead of polycarbonate resin (A), there was almost no difference in impact resistance, low-temperature impact resistance, or heat resistance compared to Comparative Example 4, in which the impact resistance modifier for polycarbonate resins of the present invention was not blended. This demonstrates that the impact resistance modifier for polycarbonate resins of the present invention is effective as an impact resistance modifier for polycarbonate resin (A).

Claims

1. A polycarbonate resin (A), a polycarbonate copolymer (B) different from the polycarbonate resin (A), which contains carbonate structural units (X) derived from an aliphatic dihydroxy compound (1) represented by the following formula (1) and carbonate structural units (Y) derived from a spiroglycol represented by the following formula (2) in a total amount of 95 mass% or more relative to 100 mass% of all carbonate structural units; A polycarbonate resin composition comprising: 【Chemical 1】 (In formula (1), X and Y are different from each other and each independently represent a single bond or a divalent linking group having 1 to 15 carbon atoms, 0 to 6 oxygen atoms, and 2 to 30 hydrogen atoms and not having a cyclic structure; and n is an integer of 2 to 100.) 【Chemistry 2】

2. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) contains, per 100 mol % of all carbonate structural units, 10 mol % or more of carbonate structural units derived from a dihydroxy compound having a bonding structure represented by the following formula (3) (provided that no hydrogen atom is bonded to the oxygen atom in formula (3)): 【Chemistry 3】

3. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) contains 10 mol % or more of carbonate structural units derived from an aromatic dihydroxy compound represented by the following formula (4) relative to 100 mol % of all carbonate structural units: 【Chemistry 4】 (In formula (4), Z １ represents a single bond, -O-, -S-, -SO ２ -, -CR ５ R ６ - (However, R ５ and R ６ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. ５ and R ６ The alkyl groups may be bonded to each other to form a ring. １ ~R ４ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

4. 3. The polycarbonate resin composition according to claim 2, wherein the polycarbonate resin (A) contains a carbonate structural unit derived from a dihydroxy compound represented by the following formula (5): 【Chemistry 5】

5. 4. The polycarbonate resin composition according to claim 3, wherein the polycarbonate resin (A) contains a carbonate structural unit derived from 2,2-bis(4-hydroxyphenyl)propane represented by the following formula (6): 【Chemistry 6】

6. 5. The polycarbonate resin composition according to claim 4, wherein the polycarbonate resin (A) contains 30 mol % or more of carbonate structural units derived from the dihydroxy compound represented by formula (5) based on 100 mol % of all carbonate structural units.

7. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) is contained in an amount of 70 to 99 mass% and the polycarbonate copolymer (B) is contained in an amount of 1 to 30 mass% based on a total of 100 mass% of the polycarbonate resin (A) and the polycarbonate copolymer (B).

8. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate copolymer (B) contains 30% by mass or more and 90% by mass or less of the carbonate structural units (X) based on 100% by mass of all carbonate structural units.

9. 2. The polycarbonate resin composition according to claim 1, wherein the aliphatic dihydroxy compound (1) has a number average molecular weight of 400 or more and 10,000 or less.

10. 2. The polycarbonate resin composition according to claim 1, wherein the aliphatic dihydroxy compound (1) is an aliphatic dihydroxy compound represented by the following formula (1A): 【Chemistry 7】 (In formula (1A), n has the same meaning as in formula (1) above.)

11. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate copolymer (B) contains 10% by mass or more and 70% by mass or less of the carbonate structural unit (Y) based on 100% by mass of all carbonate structural units.

12. 2. The polycarbonate resin composition according to claim 1, wherein the high-temperature glass transition temperature is 90°C or higher.

13. 2. The polycarbonate resin composition according to claim 1, which has a notched Izod impact strength at 23°C measured in accordance with ASTM D256 of 100 J / m or more.

14. 2. The polycarbonate resin composition according to claim 1, which has a notched Izod impact strength of 100 J / m or more at −20° C. as measured in accordance with ASTM D256.

15. 2. The polycarbonate resin composition according to claim 1, which has a viscosity average molecular weight of 15,000 or more.

16. A molded article using the polycarbonate resin composition according to any one of claims 1 to 15.

17. A molded article for automobile interiors, which uses the polycarbonate resin composition according to any one of claims 1 to 15.

18. An impact resistance improver for polycarbonate resins, comprising a polycarbonate copolymer (B) containing, in total, 95 mass% or more of carbonate structural units (X) derived from an aliphatic dihydroxy compound (1) represented by the following formula (1) and carbonate structural units (Y) derived from a spiroglycol represented by the following formula (2), based on 100 mass% of all carbonate structural units: 【Chemistry 8】 (In formula (1), X and Y are different from each other and each independently represent a single bond or a divalent linking group having 1 to 15 carbon atoms, 0 to 6 oxygen atoms, and 2 to 30 hydrogen atoms and not having a cyclic structure; and n is an integer of 2 to 100.) 【Chemistry 9】

19. 19. The impact resistance modifier for polycarbonate resins according to claim 18, wherein the polycarbonate copolymer (B) contains 30% by mass or more and 90% by mass or less of the carbonate structural units (X) based on 100% by mass of all carbonate structural units.

20. 19. The impact resistance modifier for polycarbonate resins according to claim 18, wherein the aliphatic dihydroxy compound (1) has a number average molecular weight of 400 or more and 10,000 or less.

21. 19. The impact resistance modifier for polycarbonate resins according to claim 18, wherein the aliphatic dihydroxy compound (1) is an aliphatic dihydroxy compound represented by the following formula (1A): 【Chemistry 10】 (In formula (1A), n has the same meaning as in formula (1) above.)

22. The impact resistance modifier for polycarbonate resins according to any one of claims 18 to 21, wherein the polycarbonate copolymer (B) contains 10% by mass or more and 70% by mass or less of the carbonate structural units (Y) based on 100% by mass of all carbonate structural units.

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