Method for producing resin composition (w), method for manufacturing molded article, resin composition (w), and molded article

Abstract

To provide a method for producing a resin composition (W), a method for manufacturing a molded article, a resin composition (W), and a molded article, which can achieve both appearance with a more naturally spread texture pattern and physical properties.SOLUTION: A method for producing a resin composition that comprises a resin composition (X) containing a polycarbonate resin (A) having a specific structure, a specific thermoplastic resin composition (Y) and a specific pigment component, the method involving mixing the components in a solid state at or below a specific temperature.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a resin composition (W), a method for producing a molded article, the resin composition (W), and the molded article. [Background technology]

[0002] Automotive interior and exterior parts are decorated with various finishes, such as jet black, metallic, and woodgrain, in order to enhance their design. Examples of methods for producing resin molded products with flowing patterns, such as woodgrain and marble patterns, include film in-mold molding. This molding method involves injection molding a film with a pre-printed pattern sandwiched between an injection mold, thereby transferring the pattern to the surface of the resin molded product. However, the need for a patterned film poses challenges in terms of production cost and efficiency. Therefore, a technique for producing marbled patterns using only injection molding has been proposed.

[0003] As a method for manufacturing patterned parts, a method has been proposed in which two different colored materials are filled in different cylinders and then injected through a common side gate to obtain molded products with non-uniform colors and flow patterns (Patent Document 1). Also, a method has been proposed in which a thermoplastic colored resin is mixed in a molten state with a polycarbonate resin to obtain a glittering resin composition (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-183060 [Patent Document 2] Japanese Patent Publication No. 2020-117627 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the manufacturing method described in Patent Document 1 requires the preparation of an injection molding machine with at least two or more cylinders, which limits the injection molding machine that can be used, resulting in manufacturing cost issues. Furthermore, it is necessary to design a mold structure with multiple gates, which can become very complex depending on the mold cost and part shape. Furthermore, the composition described in Patent Document 2 sometimes suffers from problems such as insufficient flow patterns due to mixing in a molten state, resulting in poor appearance. Furthermore, when a pigment with low hiding power is used in the composition formulation described in the examples, problems such as streaky appearance problems can occur on the surface of molded products.

[0006] The present invention has been made in consideration of the above-mentioned problems, and aims to provide a method for producing a resin composition (W) that can achieve both an appearance with a more natural texture and a wide range of physical properties, a method for producing a molded article, the resin composition (W), and the molded article. [Means for solving the problem]

[0007] As a result of extensive research to solve the above problems, the present inventors have found that in a method for producing a resin composition containing a resin composition (X) containing a polycarbonate resin (A) having a specific structure, a specific thermoplastic resin composition (Y), and a specific pigment component, by mixing these in a solid state at a specific temperature or below, a resin composition (W) can be obtained that is free from appearance defects and has excellent pattern appearance and physical properties, and have arrived at the present invention as described below. That is, the present invention is as follows.

[0008] [1] A method for producing a resin composition (W) containing a polycarbonate resin composition (X) and a thermoplastic resin composition (Y), comprising: The polycarbonate resin composition (X) contains a polycarbonate resin (A) containing, as a part of its structure, a structural unit derived from a dihydroxy compound represented by the following formula (1): the thermoplastic resin composition (Y) is incompatible with the polycarbonate resin (A) and has a glass transition temperature of 70°C or higher and lower than 150°C; the resin composition (W) contains at least one dye and / or pigment, the content of aluminum derived from the dye and / or pigment in the resin composition (W) is 0.1 parts by mass or less, based on 100 parts by mass of the resin composition (W); A method for producing a resin composition (W), comprising a step of mixing the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) in a solid state at a temperature equal to or lower than the lower of the glass transition temperatures of the polycarbonate resin composition (X) and the thermoplastic resin composition (Y), which is −20°C or lower.

[0009] [ka]

[0010] [2] The method for producing the resin composition (W) according to [1], wherein the thermoplastic resin composition (Y) contains the dye and / or pigment. [3] The method for producing the resin composition (W) according to [2], wherein the resin composition (W) contains 5 to 90 parts by weight of the dye and / or pigment per 100 parts by weight of the thermoplastic resin composition (Y).

[0011] [4] The method for producing the resin composition (W) according to any one of [1] to [3], wherein the polycarbonate resin (A) further contains a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heterocyclic dihydroxy compound. [5] The method for producing a resin composition (W) according to any one of [1] to [4], wherein the ratio of structural units derived from the dihydroxy compound represented by formula (1) in the polycarbonate resin (A) is 25 to 95 mol % based on all structural units derived from hydroxy compounds.

[0012] [6] The method for producing a resin composition (W) according to any one of [1] to [5], wherein the content of the polycarbonate resin composition (X) is 70 to 99.99 parts by weight per 100 parts by weight of the total of the resin compositions (W). [7] The method for producing a resin composition (W) according to any one of [1] to [6], wherein the content of the thermoplastic resin composition (Y) is 0.01 to 10 parts by weight per 100 parts by weight of the total of the resin compositions.

[0013] [8] The method for producing a resin composition (W) according to any one of [1] to [7], wherein the polycarbonate resin (A) has a total light transmittance of 70% or more at a thickness of 1 mm. [9] The method for producing a polycarbonate resin composition (W) according to any one of [1] to [8], wherein the polycarbonate resin composition (X) further contains an elastomer (C) having a core-shell structure.

[0014]

[10] The method for producing a resin composition (W) according to any one of [1] to [9], wherein the impact strength retention rate of the resin composition (W) is 80% or more relative to the Charpy impact strength of the polycarbonate resin composition (X) alone.

[11] A method for producing a molded article made of a resin composition (W) obtained by the production method according to any one of [1] to

[10] , wherein the color tones of the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) are different, and the molded article has a non-uniform color tone and a flow pattern.

[0015]

[12] The method for producing a molded article according to

[11] , wherein the resin composition (W) is charged into an injection molding machine and molded at a temperature of glass transition temperature (Tg) of the polycarbonate resin composition (X) + 70°C to Tg + 170°C.

[0016]

[13] A polycarbonate resin composition (X) containing a polycarbonate resin (A) having a structural unit derived from a dihydroxy compound represented by the following formula (1) as part of its structure; a thermoplastic resin composition (Y) that is incompatible with the polycarbonate resin (A) and has a glass transition temperature of 70°C or higher but lower than 150°C; A resin composition containing at least one dye and / or pigment, A resin composition (W) in which the amount of aluminum derived from a dye and / or a pigment contained in the resin composition is 0.1 parts by weight or less.

[0017] [ka]

[0018]

[14] A molded article comprising the resin composition (W) according to

[13] , wherein the color tones of the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) are different, and the molded article has a non-uniform color tone and a flow pattern. [Effects of the Invention]

[0019] According to the method for producing the resin composition (W) of the present invention, a resin composition (W) excellent in appearance, color tone, and physical properties can be obtained, and therefore it is possible to provide a resin composition and a molded article that can be applied to a wide range of fields, such as the injection molding fields of electric and electronic parts, automobile interior and exterior parts, and further, building material applications. DETAILED DESCRIPTION OF THE INVENTION

[0020] The following describes in detail the embodiments of the present invention. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to the following content as long as it does not exceed the gist of the present invention.

[0021] In this specification, the term "structural unit" refers to a partial structure constituting a resin, a specific partial structure contained in a repeating unit structure, and a specific partial structure contained in a repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a partial structure sandwiched between a polymerization reactive group present at the terminal portion of a polymer and a linking group adjacent to the polymerization reactive group. More specifically, in the case of a polycarbonate resin, a carbonyl group is the linking group, and a partial structure sandwiched between adjacent carbonyl groups is referred to as a structural unit.

[0022] [Polycarbonate resin composition (X)] The polycarbonate resin composition (X) used in the present invention contains at least the polycarbonate resin (A) described below. The content of the polycarbonate resin composition (X) in the resin composition (W) is not particularly limited, but is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more, based on 100 parts by mass of the total of the resin composition (W). On the other hand, it is preferably 99.99 parts by mass or less, more preferably 99.95 parts by mass or less. When the polycarbonate resin composition (X) is between the above-mentioned lower limit and the above-mentioned upper limit, the impact resistance and rigidity of the resulting resin composition (W) are not reduced.

[0023] <Polycarbonate resin (A)> The polycarbonate resin (A) contained in the polycarbonate resin composition (X) contains, as part of its structure, at least a structural unit (hereinafter sometimes referred to as "structural unit (1)") derived from a dihydroxy compound represented by the following formula (1) (hereinafter sometimes referred to as "dihydroxy compound (1)"):

[0024] [ka]

[0025] Dihydroxy compounds (1) include isosorbide, isomannide, and isoided, which are stereoisomers. Among these dihydroxy compounds, isosorbide, which is abundant and easily available, and is obtained by dehydration condensation of sorbitol produced from various starches, is most preferred in terms of availability, ease of production, and moldability. These hydroxy compounds (1) may be used singly or in combination of two or more. When the above-mentioned isosorbide, isomannide, or isoidet is used as the dihydroxy compound (1), the structural unit derived from these dihydroxy compounds (1) is a structural unit represented by the following formula (1a).

[0026] [ka]

[0027] The polycarbonate resin (A) in the present invention preferably contains, in addition to the structural unit (1), a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heterocyclic dihydroxy compound, and more specifically, preferably has any structural unit selected from the group consisting of structural units derived from dihydroxy compounds represented by the following formulas (2) to (5):

[0028] Hereinafter, the dihydroxy compounds represented by formulas (2), (3), (4), and (5) may be referred to as "dihydroxy compound (2)," "dihydroxy compound (3)," "dihydroxy compound (4)," and "dihydroxy compound (5)," respectively, and the structural units derived from dihydroxy compounds (2), (3), (4), and (5) may be referred to as "structural unit (2)," "structural unit (3)," "structural unit (4)," and "structural unit (5)," respectively.

[0029] Dihydroxy compounds (2): HO-R1-OH (2) (In formula (2), R1 represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.) Dihydroxy compounds (3): HO-CH2-R2-CH2-OH (3) (In formula (3), R2 represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.) Dihydroxy compounds (4): H-(O-R3)p-OH (4) (In formula (4), R3 represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 2 to 100.) Dihydroxy compounds (5): HO-R4-OH (5) (In formula (5), R4 represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a group having a substituted or unsubstituted acetal ring.)

[0030] Among the dihydroxy compounds (2) to (5), it is particularly preferred that they contain structural units derived from an aliphatic dihydroxy compound, and among these, it is particularly preferred that they contain structural units derived from an alicyclic dihydroxy compound, which can impart flexibility to the resulting polycarbonate resin (A).

[0031] (aliphatic dihydroxy compounds) Examples of the aliphatic dihydroxy compound include dihydroxy compounds represented by the formula (5) in which R4 is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. Examples of such aliphatic dihydroxy compounds include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, and hydrogenated dioleyl glycol. The above-mentioned exemplified compounds are only examples of aliphatic dihydroxy compounds that can be used in the present invention, and the present invention is not limited to these. These aliphatic dihydroxy compounds may be used alone or in combination of two or more.

[0032] (alicyclic dihydroxy compounds) The alicyclic dihydroxy compound is not particularly limited, but typically includes compounds having a 5-membered ring structure or a 6-membered ring structure. When the alicyclic dihydroxy compound has a 5-membered ring structure or a 6-membered ring structure, the resulting polycarbonate resin (A) may have high heat resistance. The 6-membered ring structure may be fixed into a chair or boat shape by a covalent bond. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. If the carbon number is too large, heat resistance will be high, but synthesis will tend to be difficult, purification will be complicated, and costs will tend to be high. The smaller the carbon number, the easier it will be to purify and obtain.

[0033] (Dihydroxy compounds (2) and (3)) Specific examples of the alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure include the dihydroxy compounds (2) and (3) described above. Examples of the alicyclic dihydroxy compound represented by the formula (3) include cyclohexane dimethanols, tricyclodecane dimethanols, pentacyclopentadecanedimethanols, decalin dimethanols, tricyclotetradecane dimethanols, norbornane dimethanols, adamantane dimethanols, etc. Examples of the alicyclic dihydroxy compound represented by the formula (2) include cyclohexane diols, tricyclotetradecane diols, norbornane diols, adamantane diols, etc.

[0034] Cyclohexanedimethanols, which are alicyclic dihydroxy compounds represented by the formula (3), include various isomers in which R2 in the formula (3) is represented by the following formula (3a) (wherein R5 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.) Specific examples of such isomers include 1,2-cyclohexadimethanol, 1,3-cyclohexadimethanol, and 1,4-cyclohexanedimethanol.

[0035] [ka]

[0036] Furthermore, tricyclomethanol or pentacyclopentadecanedimethanol, which is an alicyclic dihydroxy compound represented by the formula (3), includes various isomers in which R2 in the formula (3) is represented by the following formula (3b) (wherein n represents 0 or 1):

[0037] [ka]

[0038] Furthermore, decalin dimethanols and tricyclotetradecane dimethanols, which are alicyclic dihydroxy compounds represented by the formula (3), include various isomers in which R2 in the formula (3) is represented by the following formula (3c) (wherein m represents 0 or 1). Specific examples of such isomers include 2,6-decalin dimethanol, 1,5-decalin dimethanol, and 2,3-decalin dimethanol.

[0039] [ka]

[0040] Norbornane dimethanols, which are alicyclic dihydroxy compounds represented by the formula (3), include various isomers in which R2 in the formula (3) is represented by the following formula (3d). Specific examples of such isomers include 2,3-norbornane dimethanol and 2,5-norbornane dimethanol.

[0041] [ka]

[0042] Furthermore, the adamantane dimethanol, which is an alicyclic dihydroxy compound represented by the formula (3), includes various isomers in which R2 in the formula (3) is represented by the following formula (3e), such as 1,3-adamantanedimethanol.

[0043] [ka]

[0044] Furthermore, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the formula (2), encompasses various isomers represented by the following formula (2a) in which R1 in the formula (2) represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples of such isomers include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol.

[0045] [ka]

[0046] Furthermore, tricyclodecanediols and pentacyclopentadecanediols, which are alicyclic dihydroxy compounds represented by the formula (2), include various isomers in which R1 in the formula (2) is represented by the following general formula (2b) (wherein n represents 0 or 1):

[0047] [ka]

[0048] Furthermore, decalindiols and tricyclotetradecanediols, which are alicyclic dihydroxy compounds represented by the formula (2), include various isomers in which R1 in the formula (2) is represented by the following general formula (2c) (wherein m represents 0 or 1). Specific examples of such isomers include 2,6-decalindiol, 1,5-decalindiol, and 2,3-decalindiol.

[0049] [ka]

[0050] Furthermore, norbornanediols, which are alicyclic dihydroxy compounds represented by the formula (2), include various isomers in which R1 in the formula (2) is represented by the following general formula (2d).Specific examples of such isomers include 2,3-norbornanediol and 2,5-norbornanediol.

[0051] The norbornanediol, which is an alicyclic dihydroxy compound represented by the formula (2), includes various isomers in which R1 in the formula (2) is represented by the following general formula (2d). Specific examples of such isomers include 2,3-norbornanediol and 2,5-norbornanediol.

[0052] [ka]

[0053] Adamantanediols, which are alicyclic dihydroxy compounds represented by the formula (2), include various isomers in which R1 in the formula (2) is represented by the following formula (2e). Specific examples of such isomers include 1,3-adamantanediol.

[0054] [ka]

[0055] Among the specific examples of the alicyclic dihydroxy compounds described above, cyclohexanedimethanols, tricyclodecane dimethanols, adamantanediols, and pentacyclopentadecanedimethanols are preferred, and from the viewpoints of availability and ease of handling, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are particularly preferred. The above-mentioned exemplary compounds are merely examples of alicyclic dihydroxy compounds that can be used in the present invention, and the present invention is not limited to these. These alicyclic dihydroxy compounds may be used alone or in combination of two or more.

[0056] (Dihydroxy compound (4): Polyoxyalkylene dihydroxy compound) The polyoxyalkylene dihydroxy compound, which is a dihydroxy compound represented by the formula (4), is a compound having a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, in R3. p is an integer of 2 to 100, preferably 2 to 50, more preferably 6 to 30, and even more preferably 12 to 15. Specific examples of polyoxyalkylene dihydroxy compounds, which are dihydroxy compounds represented by the formula (4), include, but are not limited to, diethylene glycol, triethylene glycol, and polyethylene glycol (molecular weight 150 to 4000). As the dihydroxy compound represented by the formula (4), polyethylene glycol having a molecular weight of 300 to 2000 is preferred, and polyethylene glycol having a molecular weight of 600 to 1500 is particularly preferred. These may be used alone or in combination of two or more depending on the required performance of the resulting polycarbonate resin (A). The above-mentioned exemplary compounds are merely examples of polyoxyalkylene dihydroxy compounds that can be used in the present invention, and the present invention is not limited to these. These polyoxyalkylene dihydroxy compounds may be used alone or in combination of two or more.

[0057] (Dihydroxy Compound (5): Dihydroxy Compound Having an Alkylene Group or a Group Having an Acetal Ring) The dihydroxy compound represented by the formula (5) is a dihydroxy compound having, in R4, a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, or a group having a substituted or unsubstituted acetal ring. When the alkylene group in R4 has a substituent, examples of the substituent include an alkyl group having 1 to 5 carbon atoms. Furthermore, when the group having an acetal ring in R4 has a substituent, examples of the substituent include an alkyl group having 1 to 3 carbon atoms.

[0058] Among the dihydroxy compounds (5), examples of dihydroxy compounds in which R4 is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms include, but are not limited to, propanediols such as 1,3-propanediol and 1,2-propanediol, butanediols such as 1,4-butanediol and 1,3-butanediol, heptanediols such as 1,5-heptanediol, and hexanediols such as 1,6-hexanediol. Of these, hexanediols are preferred. The above-mentioned exemplified compounds are only examples of aliphatic dihydroxy compounds that can be used in the present invention, and the present invention is not limited to these. These aliphatic dihydroxy compounds may be used alone or in combination of two or more.

[0059] Furthermore, the dihydroxy compound in which R4 is a group having a substituted or unsubstituted acetal ring is not particularly limited, but among them, dihydroxy compounds having a spiro structure as represented by the following formula (8) or formula (9) are preferred, and dihydroxy compounds having a multi-ring structure as represented by the following formula (8) are particularly preferred.

[0060] [ka]

[0061] Among these dihydroxy compounds, 1,3-propanediol and 1,6-hexanediol are preferred as the dihydroxy compound (5) from the viewpoints of availability, ease of handling, high reactivity during polymerization, and the color of the resulting polycarbonate resin (A). From the viewpoint of heat resistance, dihydroxy compounds having a group with an acetal ring are preferred, and in particular, those having a multi-ring structure such as that represented by the above formula (8) are preferred. These may be used alone or in combination of two or more, depending on the required performance of the resulting polycarbonate resin (A).

[0062] When the polycarbonate resin (A) has structural units derived from the dihydroxy compounds represented by the above (2) to (5), the molar ratio of the structural unit (1) and the total of the structural units (2) to (5) can be selected at any ratio. By adjusting the molar ratio, impact strength (for example, notched Charpy impact strength) may be improved, and further, a desired glass transition temperature may be obtained for the polycarbonate resin (A).

[0063] The proportion of the structural unit (1) in the polycarbonate resin (A) is preferably 25 mol % to 95 mol %, more preferably 30 mol % to 90 mol %, and even more preferably 40 mol % to 80 mol %, based on all structural units derived from hydroxy compounds. By ensuring that the proportion of the structural unit (1) in the polycarbonate resin (A) of the present invention is within the above range, the polycarbonate resin can exhibit excellent heat resistance and mechanical properties (tensile strength, flexural strength, impact resistance, and heat resistance).

[0064] (Other dihydroxy compounds) The polycarbonate resin (A) may further contain structural units derived from other dihydroxy compounds in addition to the structural units (1) and (2) to (5). Examples of other dihydroxy compounds include aromatic dihydroxy compounds.

[0065] Examples of aromatic dihydroxy compounds include substituted or unsubstituted bisphenol compounds, specifically bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, and 1,1-bis(4-hydroxyphenyl)hexane. Bisphenol compounds without a substituent on the aromatic ring, such as bisphenols, 2,2-bis(4-hydroxyphenyl)hexane, 3,3-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclopentane, and 1,1-bis(4-hydroxyphenyl)cyclohexane; bisphenol compounds with an aryl group as a substituent on the aromatic ring, such as bis(3-phenyl-4-hydroxyphenyl)methane, 1,1-bis(3-phenyl-4-hydroxyphenyl)ethane, 1,1-bis(3-phenyl-4-hydroxyphenyl)propane, and 2,2-bis(3-phenyl-4-hydroxyphenyl)propane;Bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, bis(4-hydroxy-3-ethylphenyl)methane, 1,1-bis(4-hydroxy-3-ethylphenyl)ethane, 1,1-bis( 4-hydroxy-3-ethylphenyl)propane, 2,2-bis(4-hydroxy-3-ethylphenyl)propane, 1,1-bis(4-hydroxy-3-ethylphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(4-hydroxy-3-(sec-butyl)phenyl)propane, bis(4-hydroxy-3,5-dimethylphenyl)methane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl) bisphenol compounds having alkyl groups as substituents on the aromatic ring, such as 2,2-bis(4-hydroxy-3,5-dimethylphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, bis(4-hydroxy-3,6-dimethylphenyl)methane, 1,1-bis(4-hydroxy-3,6-dimethylphenyl)ethane, 2,2-bis(4-hydroxy-3,6-dimethylphenyl)propane, bis(4-hydroxy-2,3,5-trimethylphenyl)methane, 1,1-bis(4-hydroxy-2,3,5-trimethylphenyl)ethane, 2,2-bis(4-hydroxy-2,3,5-trimethylphenyl)propane, bis(4-hydroxy-2,3,5-trimethylphenyl)phenylmethane, 1,1-bis(4-hydroxy-2,3,5-trimethylphenyl)phenylethane, and 1,1-bis(4-hydroxy-2,3,5-trimethylphenyl)cyclohexane;Bisphenol compounds in which the divalent group linking the aromatic rings has an aryl group as a substituent, such as bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-phenylpropane, bis(4-hydroxyphenyl)diphenylmethane, and bis(4-hydroxyphenyl)dibenzylmethane; bisphenol compounds in which the aromatic rings are linked by an ether bond, such as 4,4'-dihydroxydiphenyl ether and 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl ether; phenol compounds; bisphenol compounds in which aromatic rings are linked by sulfone bonds, such as 4,4'-dihydroxydiphenyl sulfone and 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfone; bisphenol compounds in which aromatic rings are linked by sulfide bonds, such as 4,4'-dihydroxydiphenyl sulfide and 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide, and the like, with 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as "bisphenol A") being preferred;

[0066] In the polycarbonate resin (A), the content of the structural units derived from the aromatic dihydroxy compound is preferably 0 mol% or more and less than 1 mol%, more preferably 0 mol% or more and less than 0.8 mol%, and even more preferably 0 mol% or more and less than 0.5 mol%, relative to all structural units derived from dihydroxy compounds contained in the polycarbonate resin (A) of the present invention. By including structural units derived from aromatic dihydroxy compounds in the polycarbonate resin (A), improvements in heat resistance, surface impact resistance, moldability, etc. can be expected, but if the content of structural units derived from aromatic dihydroxy compounds is too high, there is a risk of significant coloration.

[0067] The above-mentioned other hydroxy compounds may be used singly or in combination of two or more.

[0068] (carbonate diester) The polycarbonate resin (A) in the present invention can be obtained by polycondensing a dihydroxy compound including the dihydroxy compound of the present invention described above and a carbonate diester as raw materials through an ester exchange reaction. The carbonic acid diester used is usually one represented by the following general formula (6): These carbonic acid diesters may be used alone or in combination of two or more.

[0069] [ka]

[0070] In the above formula (6), A1 and A2 are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group. Examples of the carbonate diester represented by the above formula (6) include diphenyl carbonate, substituted diphenyl carbonates such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, among which diphenyl carbonate and substituted diphenyl carbonates are preferred, and diphenyl carbonate is particularly preferred. Note that the carbonate diester may contain impurities such as chloride ions, which may inhibit the polymerization reaction or deteriorate the hue of the resulting polycarbonate resin (A). Therefore, it is preferable to use a diester purified by distillation or the like, as necessary.

[0071] The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably 0.95 to 1.10, even more preferably 0.96 to 1.10, and particularly preferably 0.98 to 1.04, relative to the total amount of dihydroxy compounds used in the melt polymerization. If this molar ratio is less than 0.90, the number of terminal hydroxyl groups in the produced polycarbonate resin (A) will increase, resulting in a deterioration in the thermal stability of the polymer, which may lead to discoloration when the thermoplastic resin composition is molded, a decrease in the rate of the transesterification reaction, or an inability to obtain a desired high molecular weight product.

[0072] Furthermore, if this molar ratio is greater than 1.20, the transesterification reaction rate will decrease under the same conditions, and the amount of residual carbonate diester in the polycarbonate resin (A) of the desired molecular weight will increase, which may absorb ultraviolet light and deteriorate the light resistance of the polycarbonate resin (A), which is undesirable. The concentration of residual carbonate diester in the polycarbonate resin (A) of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and most preferably 30 ppm by weight or less. However, in reality, the polycarbonate resin (A) may contain unreacted carbonate diester, and the lower limit of the concentration of unreacted carbonate diester in the polycarbonate resin (A) is usually 1 ppm by weight.

[0073] (Transesterification catalyst) The polycarbonate resin (A) of the present invention can be produced by transesterification of a dihydroxy compound containing the dihydroxy compound (1) with a carbonate diester represented by the formula (6), as described above. More specifically, it can be obtained by transesterification and removing by-products such as monohydroxy compounds from the reaction system. In this case, melt polymerization is usually carried out by transesterification in the presence of a transesterification catalyst.

[0074] Examples of transesterification catalysts (hereinafter sometimes referred to as "catalysts") that can be used in producing the polycarbonate resin (A) of the present invention include basic compounds such as metal compounds of Group 1 or 2 (hereinafter simply referred to as "Group 1" and "Group 2") in the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds. Among these, Group 1 metal compounds and / or Group 2 metal compounds are preferably used.

[0075] It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with the Group 1 metal compound and / or Group 2 metal compound as an auxiliary. However, it is particularly preferable to use only the Group 1 metal compound and / or Group 2 metal compound. The Group 1 metal compound and / or Group 2 metal compound is usually used in the form of a hydroxide or a salt such as a carbonate, carboxylate, or phenolate. From the viewpoints of availability and ease of handling, the hydroxide, carbonate, or acetate is preferred, and from the viewpoints of color and polymerization activity, the acetate is preferred.

[0076] Examples of the Group 2 metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, strontium hydrogencarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and stearate. Among these, magnesium compounds, calcium compounds, and barium compounds are preferred, and magnesium compounds and / or calcium compounds are more preferred.

[0077] Examples of the basic boron compound include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, and butyltriphenyl boron.

[0078] Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0079] Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimelylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenyl hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0080] Examples of the amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

[0081] Among these, it is preferable to use at least one metal compound selected from the group consisting of Group 2 metal compounds and lithium compounds as a catalyst, in order to provide the resulting polycarbonate resin (A) with excellent various physical properties such as transparency, hue, and light resistance. In order to provide the polycarbonate resin (A) with particularly excellent transparency, color, and light resistance, the catalyst is preferably at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds.

[0082] The catalyst usage fee, in the case of a Group 1 metal compound / or Group 2 metal compound, when all dihydroxy compounds to be subjected to the reaction are used, particularly when a magnesium compound and / or a calcium compound is used, is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and particularly preferably 0.7 μmol or more, calculated as metal, per mole of all dihydroxy compounds to be subjected to the reaction. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2.0 μmol.

[0083] If the amount of catalyst used is too small, the polymerization activity required to produce a polycarbonate resin (A) of the desired molecular weight may not be obtained, and sufficient fracture energy may not be obtained.On the other hand, if the amount of catalyst used is too large, not only may the color of the resulting polycarbonate resin (A) deteriorate, but by-products may be generated, resulting in a decrease in fluidity and increased gel generation, which may cause brittle fracture, making it difficult to produce a polycarbonate resin (A) of the desired quality.

[0084] <Method for producing polycarbonate resin (A)> The polycarbonate resin (A) in the present invention is obtained by melt-polymerizing a dihydroxy compound including the dihydroxy compound (1) with a carbonic acid diester through a transesterification reaction. It is preferable that the dihydroxy compound and the carbonic acid diester, which are raw materials, are uniformly mixed before the transesterification reaction.

[0085] The mixing temperature is usually 80°C or higher, preferably 90°C or higher, with the upper limit being usually 250°C or lower, preferably 200°C or lower, and more preferably 150°C or lower. Of these, a temperature of 100°C or higher and 120°C or lower is preferred. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often resulting in problems such as solidification. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a deterioration in the hue of the resulting polycarbonate resin (A) and possibly adversely affecting its light resistance.

[0086] Furthermore, the operation of mixing the dihydroxy compound and the carbonic acid diester is preferably carried out in an atmosphere with an oxygen concentration of 10% by volume or less, preferably 0.0001 to 10% by volume, more preferably 0.0001 to 5% by volume, and particularly preferably 0.0001 to 1% by volume, from the viewpoint of preventing deterioration in the hue of the resulting polycarbonate resin (A).

[0087] The polycarbonate resin (A) of the present invention is preferably produced by melt polymerization in multiple stages using a catalyst and multiple reactors. The reason for carrying out melt polymerization in multiple reactors is that melt polymerization is preferred. The reason for carrying out melt polymerization in multiple reactors is that, in the early stages of the melt polymerization reaction, the reaction solution contains a large amount of monomer, so it is important to maintain the required polymerization rate while suppressing the evaporation of monomer. In the later stages of the melt polymerization reaction, it is important to sufficiently distill off the by-product monohydroxy compound in order to shift the equilibrium toward polymerization. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use multiple reactors arranged in series. As mentioned above, the number of reactors should be at least two, but from the viewpoint of production efficiency, it is three or more, preferably three to five, and particularly preferably four.

[0088] The reaction may be carried out in a batch system, a continuous system, or a combination of a batch system and a continuous system. Furthermore, the use of a reflux condenser in a polymerization reactor is effective in suppressing the amount of monomer distilled, and this effect is particularly significant in a reactor in the early stages of polymerization where a large amount of unreacted monomer components is present. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the monomer used. Typically, the temperature of the solvent introduced into the reflux condenser at the inlet of the reflux condenser is 45 to 180°C, preferably 80 to 150°C, and particularly preferably 100 to 130°C. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount decreases and its effectiveness decreases. If the temperature is too low, the efficiency of distilling off the monohydroxy compound that should be distilled off tends to decrease. As the refrigerant, hot water, steam, heat transfer oil, etc. are used, with steam and heat transfer oil being preferred.

[0089] In order to maintain an appropriate polymerization rate and suppress distillation of the monomer while not impairing the hue, thermal stability, light resistance, etc. of the polycarbonate resin (A) finally obtained, it is important to select the type and amount of the catalyst described above. In producing the polycarbonate resin (A) of the present invention, if there are two or more reactors, the reactors may have a plurality of reaction stages with different conditions, or the temperature and pressure may be changed continuously.

[0090] In the production of the polycarbonate resin (A) of the present invention, the catalyst can be added to a raw material preparation tank or a raw material storage tank, or can be added directly to the reactor. From the viewpoints of supply stability and control of melt polymerization, however, a catalyst supply line is installed midway along the raw material line before supply to the reactor, and the catalyst is preferably supplied in the form of an aqueous solution.

[0091] As for polymerization conditions, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stages of polymerization, and then increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the later stages of polymerization. However, it is important to appropriately select the jacket temperature, internal temperature, and pressure in the reaction system at each molecular weight stage from the viewpoint of the hue and light resistance of the resulting polycarbonate resin (A). For example, if either the temperature or pressure is changed too quickly before the polymerization reaction reaches a predetermined value, unreacted monomers will be distilled off, upsetting the molar ratio of the dihydroxy compound and the carbonate diester. This may result in a decrease in the polymerization rate or failure to obtain a polymer with the desired molecular weight or terminal groups, which may ultimately prevent the objectives of the present invention from being achieved.

[0092] If the temperature of the transesterification reaction is too low, productivity will decrease and the heat history of the product will increase, while if it is too high, not only will it cause the monomer to volatilize but it may also promote decomposition and discoloration of the polycarbonate resin (A).

[0093] In the production of the polycarbonate resin (A) of the present invention, the transesterification reaction of a dihydroxy compound, including the dihydroxy compound (1), with a carbonate diester in the presence of a catalyst is typically carried out in two or more stages. Specifically, the first-stage transesterification temperature (hereinafter sometimes referred to as "internal temperature") is preferably 140°C or higher, more preferably 150°C or higher, even more preferably 180°C or higher, and even more preferably 200°C or higher. The first-stage transesterification temperature is preferably 270°C or lower, more preferably 240°C or lower, even more preferably 230°C or lower, and even more preferably 220°C or lower. The residence time in the first-stage transesterification reaction is typically 0.1 to 10 hours, preferably 0.5 to 3 hours. The first-stage transesterification reaction is carried out while distilling off the generated monohydroxy compound from the reaction system. From the second stage onwards, the transesterification reaction temperature is increased and the transesterification reaction is carried out usually at a temperature of 210 to 270°C, preferably 220 to 250°C. Simultaneously, while removing the monohydroxy compound generated from the reaction system, the pressure of the reaction system is gradually reduced from the pressure of the first stage, and the polycondensation reaction is carried out usually for 0.1 to 10 hours, preferably 0.5 to 6 hours, particularly preferably 1 to 3 hours, so that the pressure of the reaction system finally becomes 200 Pa or less.

[0094] If the transesterification reaction temperature is too high, the color of the molded product may deteriorate and the product may be prone to brittle fracture. If the transesterification reaction temperature is too low, the target molecular weight may not increase, and the molecular weight distribution may become broad, resulting in poor impact strength. If the residence time of the transesterification reaction is too long, the product may be prone to brittle fracture. If the residence time is too short, the target molecular weight may not increase, resulting in poor impact strength.

[0095] From the viewpoint of effective utilization of resources, it is preferable that the by-produced hydroxy compound is purified as necessary and then reused as a raw material for carbonic acid diesters and various bisphenol compounds. In particular, to suppress coloration, heat aging, or discoloration of the polycarbonate resin (A) and obtain a good polycarbonate resin (A) with high impact strength, it is preferable that the maximum temperature inside the reactor during all reaction stages is less than 255° C., more preferably 250° C. or less, and particularly 225 to 245° C. In addition, in order to prevent a decrease in the polymerization rate in the latter half of the polymerization reaction and to minimize thermal degradation of the polycarbonate resin (A) due to thermal history, it is preferable to use a horizontal reactor with excellent plug flow properties and interface renewal properties in the final stage of the reaction.

[0096] In addition, in order to obtain a polycarbonate resin (A) with high impact strength and a high molecular weight, the polymerization temperature may be increased as much as possible and the polymerization time may be prolonged. However, in this case, foreign matter and discoloration may occur in the polycarbonate resin (A), making it more susceptible to brittle fracture. Therefore, in order to achieve both high impact strength and reduced susceptibility to brittle fracture, it is preferable to keep the polymerization temperature low, use a highly active catalyst to shorten the polymerization time, and adjust the pressure of the reaction system appropriately. Furthermore, in order to reduce susceptibility to brittle fracture, it is also preferable to remove foreign matter and discoloration generated in the reaction system using a filter or the like during the reaction or at the final stage of the reaction.

[0097] When polycarbonate resin (A) is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonate diester represented by formula (6), phenol and substituted phenols are inevitably produced as by-products and remain in the polycarbonate resin (A). However, because phenol and substituted phenols also contain aromatic rings, they absorb ultraviolet light, which can not only deteriorate lightfastness but also cause molding cycles. After a typical batch reaction, polycarbonate resin (A) contains 1,000 ppm by weight or more of aromatic monohydroxy compounds with aromatic rings, such as by-product phenols. From the perspective of lightfastness and odor reduction, it is preferable to use a horizontal reactor or an extruder equipped with a vacuum vent that has excellent devolatilization capabilities to reduce the content of aromatic monohydroxy compounds in polycarbonate resin (A) to preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and especially 300 ppm by weight or less. However, it is difficult to completely remove aromatic monohydroxy compounds industrially, and the lower limit of the content of aromatic monohydroxy compounds in the polycarbonate resin (A) is usually 1 ppm by weight. Depending on the raw material used, these aromatic monohydroxy compounds may naturally have a substituent, such as an alkyl group having 5 or less carbon atoms.

[0098] Furthermore, Group 1 metals, particularly lithium, sodium, potassium, and cesium, and particularly sodium, potassium, and cesium, may be mixed in not only from the catalyst used but also from raw materials or reaction equipment. If these metals are contained in large amounts in the polycarbonate resin (A), this may adversely affect the color tone. Therefore, the total content of these compounds in the polycarbonate resin (A) of the present invention is preferably as low as possible, and the amount of metal in the polycarbonate resin (A) is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, and more preferably 0.7 ppm by weight or less.

[0099] The amount of metal in the polycarbonate resin (A) can be measured by various conventionally known methods. For example, the metal in the polycarbonate resin (A) can be recovered by wet ashing or the like, and then the amount can be measured by atomic emission, atomic absorption, inductively coupled plasma (ICP), or the like. After the polycarbonate resin (A) of the present invention is melt-polymerized as described above, it is usually cooled and solidified, and then pelletized using a rotary cutter or the like.

[0100] The pelletizing method is not limited, and examples include a method in which the polycarbonate resin (A) is withdrawn in a molten state from the final polymerization reactor, cooled and solidified in the form of strands, and pelletized; a method in which the resin is supplied in a molten state from the final polymerization reactor to a single-screw or twin-screw extruder, melt-extruded, and then cooled and solidified to pelletize; and a method in which the resin is withdrawn in a molten state from the final polymerization reactor, cooled and solidified in the form of strands, and once pelletized, is again supplied to a single-screw or twin-screw extruder, melt-extruded, and then cooled and solidified to pelletize.

[0101] At this time, residual monomers may be removed under reduced pressure in the extruder, and commonly known additives such as a heat stabilizer, a neutralizing agent, an ultraviolet absorber, a mold release agent, a colorant, an antistatic agent, a lubricant, a plasticizer, a compatibilizer, and a flame retardant may be added and kneaded. The melt-kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin (A), but is usually 150 to 300°C, preferably 200 to 270°C, and more preferably 230 to 260°C. If the melt-kneading temperature is lower than 150°C, the melting temperature of the polycarbonate resin (A) becomes high, which increases the load on the extruder and reduces productivity. If the temperature is higher than 300°C, the polycarbonate undergoes severe thermal degradation, which can lead to a decrease in mechanical strength due to a decrease in molecular weight, coloration, gas generation, the generation of foreign matter, and even discoloration. It is preferable to install a filter in the extruder or at the extruder outlet to remove the foreign matter and discoloration.

[0102] The size (mesh size) of the filter for removing foreign matter is usually 400 μm or less, preferably 200 μm or less, and particularly preferably 100 μm or less, with the goal of achieving a filtration accuracy of removing 99% or more of the foreign matter. If the filter mesh size is excessively large, foreign matter or discoloration may not be removed properly, which may cause brittle fracture when the polycarbonate resin (A) is molded. The filter mesh size can also be adjusted depending on the intended use of the thermoplastic resin composition of the present invention. For example, when used in foam applications, the filter mesh size is preferably 40 μm or less, and more preferably 10 μm or less, due to the need to eliminate defects.

[0103] Furthermore, a plurality of the filters may be arranged in series, or a filtration device in which a plurality of leaf disk type polymer filters are stacked may be used. Furthermore, when cooling and pelletizing the melt-extruded polycarbonate resin (A), it is preferable to use a cooling method such as air cooling or cooling. The air used for air cooling is preferably air that has been previously purified of foreign matter using a HEPA filter (preferably a filter specified in JIS Z8112) or the like to prevent re-adhesion of foreign matter in the air. It is more preferable to carry out the cooling in a clean room with a cleanliness level higher than Class 7, or even more preferably Class 6, as defined in JIS B 9920 (2002). When using water cooling, it is preferable to remove metals from the water using an ion exchange resin or the like, and then use water from which foreign matter has been removed using a filter. The mesh size of the filter used can vary, but a filter with a mesh size of 0.1 to 0.45 μm is preferred.

[0104] When the polycarbonate resin (A) used in the present invention is produced by melt polymerization, one or more phosphoric acid compounds and / or phosphorous acid compounds may be added during polymerization to prevent discoloration. The phosphoric acid compound is preferably one or more trialkyl phosphates such as trimethyl phosphate and triethyl phosphate. These are preferably added in an amount of 0.0001 mol % to 0.005 mol %, more preferably 0.0003 mol % to 0.003 mol %, based on the hydroxy compound to be reacted. If the amount of phosphoric acid compound added is less than the lower limit, the coloration prevention effect is small, while if it is more than the upper limit, transparency may be reduced or, conversely, coloration may be promoted or heat resistance may be reduced.

[0105] The phosphorous acid compound may be selected from the following heat stabilizers. In particular, one or more of the following are suitable: trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol % to 0.005 mol %, more preferably 0.0003 mol % to 0.003 mol %, based on the total amount of dihydroxy compounds used in the reaction. Addition of a phosphorous acid compound below the lower limit results in a reduced coloration prevention effect. Addition of a phosphorous acid compound above the lower limit may result in a decrease in transparency, or may even promote coloration or reduce heat resistance.

[0106] The phosphoric acid compound and the phosphorous acid compound can be added in combination, but in that case, the amount added, in total, of the phosphoric acid compound and the phosphorous acid compound is preferably 0.0001 mol % to 0.005 mol %, more preferably 0.0003 mol % to 0.003 mol % of all dihydroxy compounds to be reacted. If the amount added is less than the lower limit, the coloring prevention effect is small, and if it is more than the upper limit, it may cause a decrease in transparency or, conversely, promote coloring or reduce heat resistance.

[0107] The phosphoric acid compound and the phosphorous acid compound can be added in combination, but in that case, the amount added, in total, of the phosphoric acid compound and the phosphorous acid compound is preferably 0.0001 mol % to 0.005 mol %, more preferably 0.0003 mol % to 0.003 mol % of all dihydroxy compounds to be reacted. If the amount added is less than the lower limit, the coloring prevention effect is small, and if it is more than the upper limit, it may cause a decrease in transparency or, conversely, promote coloring or reduce heat resistance.

[0108] The polycarbonate resin (A) thus produced may contain one or more heat-stable compounds to prevent a decrease in molecular weight or deterioration in color during molding or the like. Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylene bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and 2,2-methylene bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite. Examples of suitable phosphate diphosphates include (4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinate tetrakis(2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and dimethyl benzenephosphonate are preferably used.

[0109] Such a heat stabilizer can be added in addition to the amount added during melt polymerization. That is, after a polycarbonate resin (A) is obtained by adding an appropriate amount of a phosphorous acid compound or a phosphoric acid compound, by adding a phosphorous acid compound by the method described below, it is possible to add a larger amount of heat stabilizer without causing a decrease in transparency, coloration, and heat resistance during polymerization, and to prevent deterioration of color. The content of these heat stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 parts by weight, and even more preferably 0.001 to 0.2 parts by weight, relative to 100 parts by weight of the polycarbonate resin (A).

[0110] From the viewpoint of further improving mechanical strength, the content of the polycarbonate resin (A) in the polycarbonate resin composition (X) is not particularly limited, but is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, and even more preferably 80 parts by weight or more, relative to 100 parts by weight of the polycarbonate resin composition (X). On the other hand, it is preferably 99 parts by weight or less, more preferably 97 parts by weight or less, and even more preferably 95 parts by weight or less. The higher the content of the polycarbonate resin (A), the lower the content tends to be, while the lower the heat resistance and elastic modulus tend to be. The polycarbonate resin (A) may be used singly, or two or more types having different types of structural units derived from other dihydroxy compounds, copolymerization ratios, physical properties, etc. may be mixed and used.

[0111] <Physical properties of polycarbonate resin (A)> Preferred physical properties of the polycarbonate resin (A) of the present invention are shown below. (glass transition temperature) The glass transition temperature (Tg) of the polycarbonate resin (A) of the present invention is preferably less than 155°C. If the glass transition temperature of the polycarbonate resin (A) is too high, exceeding this range, the resin may be prone to coloration, making it difficult to improve impact strength. In this case, it is necessary to set the mold temperature high when transferring the shape of the mold surface to the molded article during molding. This may limit the temperature regulators that can be selected or may worsen the transferability of the mold surface.

[0112] The glass transition temperature of the polycarbonate resin (A) of the present invention is more preferably lower than 145°C, and even more preferably lower than 135°C. The glass transition temperature of the polycarbonate resin (A) of the present invention is usually 90°C or higher, and preferably 95°C or higher. Methods for adjusting the glass transition temperature of the polycarbonate resin (A) of the present invention to less than 155°C include reducing the proportion of the structural unit (1) in the polycarbonate resin (A), selecting an alicyclic dihydroxy compound with low heat resistance as the dihydroxy compound used in producing the polycarbonate resin (A), and reducing the proportion of structural units derived from aromatic dihydroxylated products such as bisphenol compounds in the polycarbonate resin (A). The glass transition temperature (Tg) of the polycarbonate resin (A) is measured in accordance with JIS K7121 (1987) using a differential scanning calorimeter (DSC 6220 manufactured by SII NanoTechnology Inc.).

[0113] (reduced viscosity) The molecular weight of polycarbonate resin (A) can be expressed by reduced viscosity, and the higher the reduced viscosity, the higher the molecular weight. The reduced viscosity of polycarbonate resin (A) is measured using an Ubbelohde viscometer at a temperature of 20.0°C ± 0.1°C, with the polycarbonate resin concentration precisely adjusted to 0.6 g / dL using methylene chloride as a solvent.

[0114] From the viewpoints of improving the fluidity during molding, thereby improving the molding cycle in, for example, injection molding, and also reducing distortion of the molded body and preventing thermal deformation, the reduced viscosity of the polycarbonate resin (A) is preferably 2.0 dL / g or less, more preferably 1.7 dL / g or less, and even more preferably 1.4 dL / g or less.

[0115] (Total light transmittance) The total light transmittance of the polycarbonate resin (A) at a thickness of 1 mm is preferably 70% or more, more preferably 80%, and even more preferably 85% or more. When the total light transmittance is within the above range, the polycarbonate resin (X) can exhibit a wide range of total light transmittances by using colorants and additives. Details of the method for measuring the total light transmittance are described in the Examples section.

[0116] <Elastomer with a core-shell structure (C)> The polycarbonate resin composition (X) of the present invention preferably contains an elastomer (C) having a core-shell structure. The "elastomer having a core-shell structure" is composed of a core (core layer) and one or more layers (shell layers) covering it. The elastomer having a core-shell structure is a core-shell graft copolymer in which a copolymerizable monomer component is graft copolymerized with the core layer as the shell layer.

[0117] The difference in average refractive index between the polycarbonate resin (A) of the present invention and the elastomer (C) having a core-shell structure (i.e., "average refractive index of polycarbonate resin (A)" - "average refractive index of elastomer (C) having a core-shell structure") is preferably 0.2 or less. It is more preferably 0.15 or less, and even more preferably 0.10 or less. When the difference in average refractive index between the polycarbonate resin (A) and the elastomer (C) having a core-shell structure is within the above range, the transparency of the polycarbonate resin composition (X) and its molded article is further improved.

[0118] The average refractive index of the polycarbonate resin (A) and the elastomer (C) having a core-shell structure is measured and calculated using the following method. Based on JIS K7142:2008, the refractive index of a measurement sample of the polycarbonate resin and impact strength modifier molded to a thickness of 100 μm is measured. The measurement is performed using, for example, an Abbe refractometer manufactured by Atago Co., Ltd., using the sodium D line (589 nm) as a light source, and at a temperature of 23°C.

[0119] 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 graft copolymerized as the shell layer. The core-shell graft copolymer may be produced by any of the following methods: bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The copolymerization method may be either single-stage grafting or multi-stage grafting. However, in the second aspect of the present invention, commercially available core-shell elastomers can usually be used as they are. Examples of commercially available core-shell elastomers are listed below.

[0120] The elastomer (C) having a core-shell structure is not particularly limited, but is preferably an acrylic-styrene rubber having a core-shell structure, which provides a molded article of the polycarbonate resin composition with a good balance of heat aging resistance, chemical resistance, moldability, molded article appearance, and heat resistance.

[0121] The polymer component forming the core layer typically has a glass transition temperature of 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower. Specific examples of polymer components forming the core layer include polybutadiene, polyisoprene, polyalkyl acrylates such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone rubbers such as polyorganosiloxane rubber, butadiene-acrylic composites, IPN (Interpenetrating Polymer Network) composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene copolymers, ethylene-α-olefin copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-acrylic copolymers, and fluororubbers. These may be used alone or in combination. Among these, polybutadiene, polyalkyl acrylate, polyorganosiloxane, a composite of polyorganosiloxane and polyalkyl acrylate, and butadiene-styrene copolymer are preferred in terms of mechanical properties and surface appearance.

[0122] Specific examples of the monomer component constituting the shell layer that can be graft-copolymerized with the polymer component of the core layer include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and anhydrides thereof (e.g., maleic anhydride, etc.); and the like. 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)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferred, with (meth)acrylic acid ester compounds being more preferred. Specific examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate. Among these, methyl (meth)acrylate and ethyl (meth)acrylate, which are relatively easily available, are preferred, with methyl (meth)acrylate being more preferred. Here, "(meth)acrylic" collectively refers to "acrylic" and "methacrylic."

[0123] The core-shell elastomer (C) is particularly preferably a core-shell graft copolymer, which comprises a core layer made of at least one polymer component selected from polybutadiene-containing rubber, polybutylacrylate-containing rubber, polyorganosiloxane rubber, and an IPN-type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, and a shell layer formed by graft copolymerization of a (meth)acrylic acid ester around the core layer. The core-shell graft copolymer preferably contains 40% by weight or more of the polymer component of the core layer, more preferably 60% by weight or more. The shell layer preferably contains 10% by weight or more of the (meth)acrylic acid ester component.

[0124] Preferred examples of these core-shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, and methyl methacrylate-(acrylic-silicone complex) copolymer.

[0125] Examples of such core-shell type graft copolymers include "Paraloid (registered trademark) EXL2602," "Paraloid (registered trademark) EXL2603," "Paraloid (registered trademark) EXL2655," "Paraloid (registered trademark) EXL2690," "Paraloid (registered trademark) EXL2311," "Paraloid (registered trademark) EXL2313," "Paraloid (registered trademark) EXL2315," "Paraloid (registered trademark) KM330," "Paraloid (registered trademark) KM336P," and "Paraloid (registered trademark) KCZ201," all manufactured by Dow Chemical Japan Co., Ltd. Examples include "Metablen (registered trademark) C-223A," "Metablen (registered trademark) E-901," "Metablen (registered trademark) S-2001," "Metablen (registered trademark) W-450A," and "Metablen (registered trademark) SRK-200" manufactured by Ryo Rayon Co., Ltd., and "Kane Ace (registered trademark) M-511," "Kane Ace (registered trademark) M-600," "Kane Ace (registered trademark) M-400," "Kane Ace (registered trademark) M-580," "Kane Ace (registered trademark) M-590," "Kane Ace (registered trademark) M-591," and "Kane Ace (registered trademark) MR-01" manufactured by Kaneka Corporation. The elastomer (C) having a core-shell structure such as these core-shell type graft copolymers may be used alone or in combination of two or more.

[0126] The content of the elastomer (C) having a core-shell structure in the polycarbonate resin composition (X) of the present invention is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and most preferably 5 parts by mass or more, based on 100 parts by mass of the total of the polycarbonate resin (A) and the elastomer (C) having a core-shell structure. On the other hand, it is more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and most preferably 25 parts by mass or less. By having the content of the elastomer (C) having a core-shell structure at or above the lower limit, improved surface impact resistance and impact resistance are achieved. On the other hand, by having the content of the elastomer (C) having a core-shell structure at or below the upper limit, poor appearance and reduced heat resistance of the resulting molded article can be suppressed.

[0127] <Ultraviolet absorber (D)> The polycarbonate resin composition (X) of the present invention preferably contains an ultraviolet absorber (D). The ultraviolet absorber (D) is not particularly limited as long as it is a compound capable of absorbing ultraviolet light. In the present embodiment, examples of the compound capable of absorbing ultraviolet light include organic compounds and inorganic compounds. Among these, organic compounds are preferred because they can easily ensure affinity with polycarbonate resins and are easily dispersed uniformly.

[0128] The molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is usually 200 or more, or 250 or more. It is also usually 600 or less, preferably 450 or less, and more preferably 400 or less. By having the molecular weight at least the lower limit, it is possible to suppress a decrease in ultraviolet resistance performance over long-term use. By having the molecular weight at most the upper limit, it is possible to suppress a decrease in transparency of the resin composition over long-term use.

[0129] Preferred examples of the ultraviolet absorber (D) include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, and oxalic acid anilide compounds. Of these, benzotriazole compounds, hydroxybenzophenone compounds, and malonic acid ester compounds are preferably used. These may be used alone or in combination of two or more.

[0130] More specific examples of the benzotriazole-based compound include 2-(2'-hydroxy-3'-methyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-t-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, methyl-3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate, and 2-(2'-hydroxy-3'-methyl-5'-t-octylphenyl)benzotriazole (manufactured by Shipro Chemical Co., Ltd., SEESORB709).

[0131] Examples of the hydroxybenzophenone compounds include 2,2'-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone.

[0132] Examples of the malonic acid ester compounds include 2-(1-arylalkylidene)malonic acid esters and tetraethyl-2,2'-(1,4-phenylene-dimethylidene)-bismalonate.

[0133] Examples of the triazine compounds include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol (manufactured by BASF, Tinuvin 1577ED).

[0134] Examples of the cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenylacrylate, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, etc. Examples of the oxalic acid anilide compounds include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan, Sanduvor VSU), etc.

[0135] The content of the ultraviolet absorber (D) is preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, and even more preferably 0.1 parts by weight or more, per 100 parts by weight of the polycarbonate resin (A). On the other hand, it is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and even more preferably 1 part by weight or less. By having the content of the ultraviolet absorber be equal to or greater than the lower limit, the effect of improving weather resistance due to the inclusion of the ultraviolet absorber can be more effectively achieved. On the other hand, by having the content of the ultraviolet absorber be equal to or less than the upper limit, the occurrence of poor appearance due to bleed-out of the ultraviolet absorber can be suppressed.

[0136] <Light stabilizer (E)> The polycarbonate resin composition (X) of the present invention preferably contains a light stabilizer (E). The light stabilizer (E) is not particularly limited as long as it is a compound capable of preventing oxidative degradation due to light. Examples of the light stabilizer (E) used in the polycarbonate resin composition (X) of the present invention include bis(2,2,6,6-tetramethyl-4-piperidyl)carbonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1,-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6, Examples of hindered amines include 6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)diphenylmethane-p,p'-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)benzene-1,3-disulfonate, bis(2,2,6,6-tetramethyl-4-piperidyl)phenylphosphite, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)=1,2,3,4-butanetetracarboxylate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)=1,2,3,4-butanetetracarboxylate. Commercially available products include LA-57, LA-52, and LA-63P manufactured by ADEKA Corporation. These agents may be used alone or in combination of two or more.

[0137] The content of the light stabilizer (E) is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, per 100 parts by weight of the polycarbonate resin (A). On the other hand, it is preferably 3 parts by weight or less, more preferably 1 part by weight or less, and particularly preferably 0.5 parts by weight. By having the content of the light stabilizer (E) equal to or greater than the lower limit, the weather resistance of the resulting polycarbonate resin composition (X) is further improved. On the other hand, by having the content of the light stabilizer (E) equal to or less than the upper limit, the occurrence of deposits on the mold during injection molding can be prevented, and the surface appearance of the resulting product can be improved.

[0138] <Other additives> The polycarbonate resin composition (X) of the present invention may contain various well-known additives as long as they do not impair the object of the present invention. Examples of such additives include impact modifiers, antioxidants, heat stabilizers, fillers, neutralizing agents, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, crosslinking agents, crosslinking aids, metal deactivators, molecular weight modifiers, antibacterial agents, antifungal agents, fluorescent brighteners, and light diffusing agents such as organic and inorganic diffusing agents. Furthermore, other resins may be mixed as long as they do not impair the effect of the present invention.

[0139] (antioxidant) As the antioxidant, a general antioxidant used in resins can be used. From the viewpoints of oxidation stability, thermal stability, and good jet black coloring, phosphite-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants are preferred. As the antioxidant, one type of compound may be used, or two or more types of compounds may be used in combination.

[0140] When an antioxidant is added to the polycarbonate resin composition (X) of the present invention, the amount added is preferably 0.001 part by weight or more, more preferably 0.002 part by weight or more, and even more preferably 0.005 part by weight or more, and is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and even more preferably 2 parts by weight or less, based on 100 parts by weight of component (A) in the polycarbonate resin composition. If the amount of antioxidant added is more than 5 parts by weight, the mold may be contaminated during molding, and molded products with excellent surface appearance may not be obtained, whereas if the amount is less than 0.001 part by weight, sufficient improvement in weather resistance tests tends not to be obtained.

[0141] (Phosphite antioxidant) Examples of the phosphite antioxidant include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite. Among these, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are preferably used.

[0142] (sulfur-based antioxidant) Examples of the sulfur-based antioxidants include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl]sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, and 1,1'-thiobis(2-naphthol). Among these, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred. These compounds may be used alone or in combination of two or more.

[0143] (phenolic antioxidant) Examples of the phenol-based antioxidant include triethylene glycol-bis[3(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzyl Examples of compounds include benzophenone, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, 2,6-di-tert-butyl-p-cresol, and 2,6-di-tert-butyl-4-ethylphenol.

[0144] Among these compounds, aromatic monohydroxy compounds substituted with one or more alkyl groups having 5 or more carbon atoms are preferred. Specifically, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc. are preferred, with pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] being more preferred. These compounds may be used alone or in combination of two or more.

[0145] (coloring agent) Examples of colorants for the polycarbonate resin composition (X) include organic pigments, organic pigments, and organic face washes such as organic dyes. Examples of inorganic pigments include carbon black; and oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black. Examples of organic dyes and pigments such as organic pigments and organic dyes include phthalocyanine dyes and pigments; condensed polycyclic dyes and pigments such as azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone; anthraquinone, perinone, perylene, methine, quinoline, heterocyclic, and methyl dyes and pigments; etc. These colorants may be used alone or in combination of two or more. Among the inorganic pigments, organic pigments, and organic dyes and pigments such as organic dyes, inorganic pigments are preferred. By using an inorganic pigment as a colorant, the molded product can maintain its image clarity for a long period of time even when used outdoors.

[0146] (inorganic filler) The polycarbonate resin composition (X) of the present invention may also contain an inorganic filler. The amount of inorganic filler blended is usually 1 part by weight or more and 100 parts by weight or less, and preferably 3 parts by weight or more and 50 parts by weight or less, per 100 parts by weight of the polycarbonate resin. If the amount of inorganic filler blended is too small, the reinforcing effect is reduced, and if the amount is too large, the appearance tends to deteriorate.

[0147] Examples of inorganic fillers include glass fiber, milled glass fiber, glass flakes, glass beads, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, calcium silicates such as wollastonite, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whiskers, etc. Among these, glass fibrous fillers, glass powder fillers, glass flake fillers, carbon fibrous fillers, carbon powder fillers, carbon flake fillers, various whiskers, and talc are preferred. More preferred are glass fiber, glass flakes, milled glass fiber, carbon fiber, wollastonite, and talc.

[0148] <Physical Properties of Polycarbonate Resin Composition (X)> Preferred physical properties of the polycarbonate resin composition (X) of the present invention are shown below. (glass transition temperature) The glass transition temperature (Tg) of the polycarbonate resin composition (X) of the present invention is preferably less than 155°C. If the glass transition temperature of the polycarbonate resin composition (X) is too high, exceeding this range, the composition may be prone to coloration, making it difficult to improve impact strength. In this case, it is necessary to set the mold temperature high when transferring the shape of the mold surface to the molded article during molding. This may limit the temperature regulators that can be selected or may worsen the transferability of the mold surface.

[0149] The glass transition temperature of the polycarbonate resin composition (X) of the present invention is more preferably lower than 145°C, and even more preferably lower than 135°C. The glass transition temperature of the polycarbonate resin composition (X) of the present invention is usually 90°C or higher, and preferably 95°C or higher. Methods for adjusting the glass transition temperature of the polycarbonate resin composition (X) of the present invention to less than 155°C include reducing the proportion of the structural unit (1) in the polycarbonate resin composition (X), selecting an alicyclic dihydroxy compound with low heat resistance as the dihydroxy compound used in producing the polycarbonate resin composition (X), and reducing the proportion of structural units derived from aromatic dihydroxylated products such as bisphenol compounds in the polycarbonate resin composition (X). The glass transition temperature (Tg) of the polycarbonate resin composition (X) is measured in accordance with JIS K7121 (1987) using a differential scanning calorimeter (DSC 6220 manufactured by SII NanoTechnology Inc.).

[0150] <Thermoplastic resin composition (Y)> The thermoplastic resin composition (Y) in the present invention is incompatible with the polycarbonate resin (A) and has a glass transition temperature of 70°C or higher but lower than 150°C. The content of the thermoplastic resin composition (Y) in the resin composition (W) is not particularly limited, but is preferably 0.01 parts by mass or higher, more preferably 0.05 parts by mass or higher, and even more preferably 0.1 parts by mass or higher, based on 100 parts by mass of the total resin composition (W). On the other hand, it is preferably 10 parts by mass or lower, more preferably 8 parts by mass or lower, and even more preferably 5 parts by mass or lower. By setting the content of the thermoplastic resin composition (Y) at or above the lower limit, a molded article having a more excellent ink painting-like expanse and flowing pattern can be obtained. On the other hand, by setting the content of the thermoplastic resin composition (Y) at or below the upper limit, the appearance of the obtained molded article can be prevented from being poor and the impact resistance can be prevented from being reduced.

[0151] The thermoplastic resin composition (Y) of the present invention contains a thermoplastic resin (B). The thermoplastic resin (B) is not particularly limited, but examples thereof include polyester resin, acrylic resin, polycarbonate resin, polypropylene resin, acrylonitrile-styrene resin, etc. Among them, polyester resin, acrylic resin, and polycarbonate resin are preferred, and polyester resin and polycarbonate resin are more preferred.

[0152] The thermoplastic resin composition (Y) used in the present invention preferably contains a dye and / or pigment as described below. By mixing the thermoplastic resin composition (Y) in advance in the form of a masterbatch containing a dye and / or pigment, it becomes easier to obtain a molded article having a flow pattern with a desired color tone that is different from the color tone of the polycarbonate resin composition (X) and the thermoplastic resin composition (Y).

[0153] (additives) The thermoplastic resin composition (Y) of the present invention may contain various well-known additives as long as they do not impair the object of the present invention. Examples of such additives include impact modifiers, antioxidants, light stabilizers, UV absorbers, heat stabilizers, fillers, neutralizing agents, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, crosslinking agents, crosslinking aids, metal deactivators, molecular weight modifiers, antibacterial agents, antifungal agents, fluorescent brighteners, and light diffusing agents such as organic diffusing agents and inorganic diffusing agents. Furthermore, other resins may be mixed as long as they do not impair the effect of the present invention.

[0154] <Physical Properties of Thermoplastic Resin Composition (Y)> (glass transition temperature) The thermoplastic resin composition (Y) used in the present invention has a glass transition temperature (Tg) of 70°C or higher but lower than 150°C. If the glass transition temperature is outside this range, the resin composition may have poor appearance or may have a spread reminiscent of an ink painting, resulting in an excellent flow pattern. The glass transition temperature is more preferably 72°C or higher, and even more preferably 74°C or higher. On the other hand, it is more preferably lower than 148°C, and even more preferably lower than 146°C.

[0155] (refractive index) The refractive index of the thermoplastic resin composition (Y) used in the present invention at a wavelength of 589 nm is not particularly limited, but is preferably 1.45 to 1.65, and more preferably 1.50 to 1.60. The difference in refractive index at a wavelength of 589 nm between the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) is preferably 0.01 to 0.12, more preferably 0.02 to 0.11, and even more preferably 0.03 to 0.10. By keeping the refractive index within this range, a molded article having better color development and flow pattern can be obtained.

[0156] <Dyes and / or pigments> The resin composition (W) of the present invention contains at least one dye and / or pigment, which may include inorganic pigments, organic pigments, and organic face washes such as organic dyes.

[0157] Examples of inorganic pigments include carbon black; and oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black. Examples of organic dyes and pigments such as organic pigments and organic dyes include phthalocyanine dyes and pigments; condensed polycyclic dyes and pigments such as azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, and quinophthalone; anthraquinone, perinone, perylene, methine, quinoline, heterocyclic, and methyl dyes and pigments; etc. These colorants may be used alone or in combination of two or more. Among the inorganic pigments, organic pigments, and organic dyes and pigments such as organic dyes, inorganic pigments are preferred. By using an inorganic pigment as a colorant, the molded product can maintain its image clarity for a long period of time even when used outdoors.

[0158] As described above, the dye and / or pigment in the present invention is preferably contained in the thermoplastic resin composition (Y). The content of the dye and / or pigment in the thermoplastic resin composition (Y) is not particularly limited, but is preferably 5 to 90 mass %, more preferably 6 to 85 mass %, and even more preferably 7 to 80 mass %, based on 100 mass % of the thermoplastic resin composition (Y). By keeping the content within the above range, a molded article having better color development and flow pattern can be obtained.

[0159] The dye and / or pigment may contain shiny metal particles. Examples include metals selected from the group consisting of aluminum, gold, silver, copper, nickel, and titanium, oxides of these metals, and inorganic particles coated with these metals. Examples of inorganic particles include glass and talc in the form of plates, chunks, powders, or spheres. Multiple types of shiny metal particles may be used in combination, and opacifying agents, dyes and pigments, and various other known and commonly used fillers may also be used in combination within the scope of the invention. On the other hand, when an aluminum pigment is contained, the content in the resin composition (W) is preferably 0.1 parts by mass or less, more preferably 0.05 or less, and even more preferably 0.01 or less, based on 100 parts by mass of the resin composition (W). When the content of the aluminum pigment in the resin composition is equal to or less than the upper limit, deterioration in the physical properties of the resin composition can be suppressed, and the influence of the color tone on the appearance of the molded product of the resin composition and poor appearance can be reduced.

[0160] <Method for producing polycarbonate resin composition (X)> The polycarbonate resin composition (X) used in the present invention can be produced, for example, by mechanically melt-kneading the above-mentioned components. Examples of melt-kneading machines that can be used here include single-screw extruders, twin-screw extruders, Brabender mixers, Banbury mixers, kneader blenders, and roll mills. Among these, twin-screw extruders are preferred, and the kneading is preferably carried out under reduced pressure from the viewpoint of distilling off residual phenol. In particular, the lower limit of the kneading temperature for the polycarbonate resin composition (X) is usually 100°C or higher, preferably 145°C or higher, and more preferably 160°C or higher. Meanwhile, the upper limit of the kneading temperature for the polycarbonate resin composition (X) is usually 350°C, preferably 300°C, and more preferably 250°C. During kneading, the components may be kneaded together, or a multi-stage kneading method may be used in which, after kneading any component, the remaining components are added and kneaded. The extruded kneaded product is preferably pelletized using a strand cutter or the like and appropriately dried before use.

[0161] <Method for producing thermoplastic resin composition (Y)> The resin composition (Y) of the present invention can be produced, for example, by mechanically melt-kneading the above-mentioned components. Examples of melt-kneaders that can be used here include a single-screw extruder, a twin-screw extruder, a lavender, a Banbury mixer, a kneader blender, and a roll mill.

[0162] [Method for producing resin composition (W)] The method for producing a resin composition of the present invention includes a step of mixing a polycarbonate resin composition (X) and a thermoplastic resin composition (Y) in a solid state at a temperature equal to or lower than the lower of the glass transition temperatures of the polycarbonate resin composition (X) and the thermoplastic resin composition (Y), whichever is lower. In other words, a polycarbonate resin composition (X) and a thermoplastic resin composition (Y) having different color tones can be mixed, for example, by adding pellets of each resin composition to a polyethylene bag and shaking them by hand to dry blend them. A mixer or other mixing machine may also be used.

[0163] By mixing the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) in a solid state (pellet state) at a temperature of −20° C. or less, whichever is the lower of the glass transition temperatures of the polycarbonate resin composition (X) and the thermoplastic resin composition (Y), the pellets are prevented from fusing together while maintaining the solid state, and the pellets can be effectively dispersed, thereby forming a superior ink painting-style pattern. On the other hand, when mixing in a molten state, the composition is dispersed in a molten state, which makes it difficult to form a pattern with an excellent ink painting look due to over-dispersion, and a good appearance cannot be obtained.

[0164] [Physical properties of resin composition (W)] (Impact strength retention rate) The resin composition (W) in the present invention preferably has an impact strength retention of 80% or more relative to the Charpy impact strength of the polycarbonate resin composition (X) alone, as measured by the method described below. If the impact strength retention is within the above range, the impact resistance of the resin composition can be maintained. From the same viewpoint, 85% or more is more preferable, and 90% or more is even more preferable.

[0165] (compatibility) In order to form an excellent flowing pattern with a broadness reminiscent of ink painting, it is preferable that the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) are not completely compatible with each other. From this viewpoint, it is preferable that the resin composition (W) in the present invention has two or more waveforms showing glass transition temperatures among the waveforms of the glass transition temperature measurement obtained by DSC measurement described below.

[0166] [Method for molding resin composition (W) and molded products] The resin composition (W) of the present invention can be processed into various molded articles by molding methods such as injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, etc.), extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding. The shape of the molded article is not particularly limited, and examples include sheets, films, plates, particles, lumps, fibers, rods, porous bodies, and foams, with sheets, films, and plates being preferred. The molded film can also be stretched uniaxially or biaxially. Examples of stretching methods include roll methods, tenter methods, and tubular methods.

[0167] When the resin composition (W) of the present invention is molded by injection molding, the resin composition (W) is preferably placed in an injection molding machine and molded at a temperature of Tg + 70°C to Tg + 170°C relative to the glass transition temperature of the polycarbonate resin composition (X). More preferably, it is Tg + 90°C to Tg + 150°C. Molding within the above range can suppress the effects of decomposition and coloration due to thermal history, which can lead to poor appearance and reduced physical properties, and can produce molded products with better ink painting-like patterns.

[0168] [Hue Difference] In a molded article obtained by molding the resin composition of the present invention, the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) preferably have different color tones, and have a non-uniform color tone and a flow pattern. Specifically, the difference in color tone between the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) preferably falls within the following range. The color difference can be expressed as either a color difference ΔE* or a color difference ΔL*. When expressed as a color difference ΔE*, ΔE* is preferably 0.5 or more, more preferably 3.0 or more, and even more preferably ΔE* is 10.0 or more. When expressed as a color difference ΔL*, ΔL* is preferably 5.0 or more, more preferably 10.0 or more, and even more preferably 20.0 or more. Details of the method for measuring the color difference (color difference) are described in the Examples section.

[0169] [Application] The uses of the molded articles obtained by molding the resin composition (W) of the present invention are not particularly limited, and examples thereof include the fields of injection molding for electric / electronic parts, automobile parts, etc., the fields of films and sheets, the fields of bottles and containers where heat resistance is required, and further the fields of building materials. [Example]

[0170] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded.

[0171] In the following, the physical properties and characteristics of resin compositions, molded articles, etc. were evaluated by the following methods. [Test specimen preparation method and various evaluations] <Method for preparing test specimens for evaluating physical properties> Pellets of resin composition (W) obtained in each example and comparative example were dried for 10 hours at 90 to 100°C under a nitrogen atmosphere. Next, the dried pellets of resin composition (W) were fed into an injection molding machine (J75EII model, manufactured by The Japan Steel Works, Ltd.) and molded into injection-molded specimens (width 100 mm × length 100 mm × thickness 2 mm) and ISO test specimens for evaluating mechanical properties under conditions of a resin temperature of 240°C and a molding cycle of 40 seconds (mold temperature: 80°C). The total light transmittance of the polycarbonate resin (A) was measured using an injection-molded piece (width 100 mm×length 100 mm×thickness 1 mm) prepared in the same manner as above.

[0172] <Pattern appearance evaluation, poor appearance> The appearance of the injection molded pieces prepared above was evaluated according to the following criteria. (Pattern appearance evaluation) ·Uneven color ○: When the test piece was visually inspected, the overall appearance was non-uniform in color. △: When the test piece is visually inspected, there is a non-uniform color in part of the appearance of the test piece. ×: When the test piece was visually inspected, the overall appearance was a single color. Flow pattern formation ○: When the test piece is visually inspected, it has a spread reminiscent of an ink painting and has an excellent flow pattern. △: When the test piece was visually inspected, a flow pattern was formed but was blurred. ×: When the test piece is visually inspected, the pattern is broken and not continuous.

[0173] (poor appearance) ◯: The test piece was visually inspected and found to be in good condition with no defects in the molded appearance. △: Visual inspection of the test piece revealed peeling of the surface layer near the gate, indicating a defect. ×: When the test piece was visually inspected, streaky defects in appearance were observed, indicating defects.

[0174] <Glass Transition Temperatures (°C) of Polycarbonate Resin Composition (X), Thermoplastic Resin Composition (Y), and Polycarbonate Resin (A)> The glass transition temperatures (Tg) of the polycarbonate resin composition (X), the thermoplastic resin composition (Y) and the polycarbonate resin (A) were measured using a differential scanning calorimeter DSC6220 manufactured by SII NanoTechnology Inc. Approximately 10 mg of the resin sample was placed in an aluminum pan manufactured by the same company, sealed, and heated from 30°C to 200°C at a heating rate of 10°C / min under a nitrogen gas flow of 50 mL / min. After holding the temperature for 3 minutes, the sample was cooled to 30°C at a rate of 10°C / min. The sample was then heated again to 200°C at a rate of 20°C / min. From the DSC data obtained in the second heating run, the extrapolated glass transition onset temperature was determined, which is 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 greatest. This was taken as the glass transition temperature.

[0175] <compatibility> The resin compositions (W) obtained in each of the Examples and Comparative Examples were subjected to DSC measurement as described above, and the number of waveforms indicating the glass transition temperature was recorded from the waveforms obtained for the glass transition temperature measurement. Here, "compatibility" refers to the property of mixing multiple substances without separating when they are mixed. Since complete incompatibility is preferred for forming an excellent flowing pattern with a broad, ink-painting-like appearance, it is preferable for the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) to have two or more waveforms indicating the glass transition temperature when mixed. When the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) are compatible with each other, it can be confirmed by the fact that they show a single waveform of the glass transition temperature.

[0176] <Charpy impact test> The ISO test specimen for evaluating mechanical properties obtained above was notched with a notch tip radius of 0.25R, and the Charpy impact strength was measured in accordance with ISO 179. The Charpy impact retention (%) of resin composition (W) obtained by mixing thermoplastic resin composition (Y) with polycarbonate resin composition (X) relative to polycarbonate resin composition (X) was evaluated.

[0177] <Total light transmittance measurement> Measurement was carried out using an injection-molded piece (100 mm wide x 100 mm long x 1 mm thick) of the polycarbonate resin (A) obtained above. The total light transmittance was evaluated using a haze meter NDH-7000II manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS K7361-1 and ISO13468-1, using a D65 light source / 10-degree viewing angle light source transmission method.

[0178] <Color difference (ΔE*, ΔL*)> Measurements were carried out using the injection-molded specimens (100mm wide x 100mm long x 2mm thick) obtained above. In accordance with JIS Z8722, a spectrophotometer (Konica Minolta CM-5) was used to measure the color values ​​L*, a*, and b* using the D65 light source reflection method (specular reflection excluded), and the color difference was calculated using the following formula: ΔL* = L1* - L2* Δa*=a1*-a2* Δb*=b1*-b2* ΔE*=[ (ΔL*) 2 +(Δa*) 2 +(Δb *) 2 ] 1 / 2

[0179] [raw materials] The abbreviations for compounds used in the following examples are as follows: (Polycarbonate resin (A)) A-1: Isosorbide / 1,4-cyclohexanedimethanol = 50 / 50 mol% copolymer polycarbonate (Mitsubishi Chemical Corporation: Durabio, refractive index: 1.50, glass transition temperature: 100°C, total light transmittance (thickness 1 mm): 92%, reduced viscosity: 0.61 dL / g) A-2: Isosorbide / 1,4-cyclohexanedimethanol = 70 / 30 mol% copolymer polycarbonate (Mitsubishi Chemical Corporation: Durabio, refractive index: 1.50, glass transition temperature: 122 °C, total light transmittance (thickness 1 mm): 92%, reduced viscosity: 0.44 dL / g)

[0180] (Thermoplastic resin (B)) B-1: Acrylic resin (Mitsubishi Chemical Corporation: ACRYPET VH001) B-2: Acrylonitrile styrene resin (Techno UMG Co., Ltd.: Sunrex SAN-C) B-3: Isosorbide / 1,4-cyclohexanedimethanol = 90 / 10 mol% copolymer polycarbonate resin (Mitsubishi Chemical Corporation: Durabio)

[0181] (Thermoplastic resin composition (Y)) Y-1: Polyester resin pigment masterbatch (OK Chemical Co., Ltd.: PYA-T1038, glass transition temperature: 75°C, refractive index (589nm): 1.58, titanium dioxide concentration: 15%) Y-2: Acrylic resin pigment masterbatch (glass transition temperature: 70°C, refractive index (589nm): 1.49, titanium dioxide concentration: 20%) Y-3: Polycarbonate resin pigment masterbatch (manufactured by Resinocolor Kogyo Co., Ltd., PC-TT3045-A, glass transition temperature: 145°C, refractive index (589 nm): 1.58, titanium oxide concentration: 50%) Y-4: Acrylonitrile styrene resin pigment masterbatch (glass transition temperature: 108°C, refractive index (589nm): 1.57, titanium dioxide concentration: 20%) Y-5: Isosorbide / 1,4-cyclohexanedimethanol = 90 / 10 mol% copolymer polycarbonate pigment masterbatch (glass transition temperature: 149°C, refractive index (589 nm): 1.50, titanium dioxide concentration: 10%) Y-6: Polyolefin resin pigment masterbatch (OK Chemical Co., Ltd.: PYP-WH-55, glass transition temperature: -20°C, refractive index (589nm): 1.49, titanium dioxide concentration: 15%) Y-7: Acrylonitrile styrene resin pigment masterbatch (MHF-A-20CB50 manufactured by Resinocolor Kogyo Co., Ltd., glass transition temperature: 108°C, refractive index (589 nm): 1.50, aluminum concentration: 50 wt%)

[0182] (Elastomer with a core-shell structure (C)) C-1: Butadiene-methyl methacrylate-styrene copolymer (Dow Chemical Company, Paraloid EXL2690) (core layer: butadiene-styrene copolymer, shell layer: graft polymer of methyl methacrylate)

[0183] (Ultraviolet absorber (D)) D-1: UV absorber (Shipro Chemical Co., Ltd., SEESORB709)

[0184] (Light stabilizer (E)) E-1: Light stabilizer (ADEKA Corporation, LA-52)

[0185] (Pigment (F)) F-1: Pigment (manufactured by Tioxide: TIOXIDE (registered trademark) R-TC30)

[0186] [Example 1] Polycarbonate resin (A-1), polycarbonate resin (A-2), ultraviolet absorber (D-1), and light stabilizer (E-1) were mixed to obtain the composition shown in Table 1. The mixture was extruded into strands using a twin-screw extruder (LABOTEX 30HSS-32) equipped with one vent port (manufactured by The Japan Steel Works, Ltd.) so that the outlet resin temperature reached 250°C. The mixture was then cooled and solidified with water, and pelletized using a rotary cutter. The vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa to obtain polycarbonate resin composition (X). The polycarbonate resin composition (X) and thermoplastic resin composition (Y-1) obtained to obtain the composition shown in Table 1 were placed in a polyethylene bag at room temperature (25°C) and mixed by hand shaking. The resulting resin composition was evaluated, and the results are shown in Table 1.

[0187] [Example 2] A resin composition was obtained in the same manner as in Example 1, except that an elastomer (C-1) having a core-shell structure was further used in addition to the polycarbonate resin composition (X) and the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0188] [Example 3] A resin composition was obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0189] [Example 4] A resin composition was obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0190] [Example 5] Polycarbonate resin composition (X) was obtained in the same manner as in Example 2. Thermoplastic resin (B-1) and pigment (F-1) were mixed to obtain the composition shown in Table 2, and the mixture was extruded into strands using a twin-screw extruder (LABOTEX30HSS-32) equipped with one vent, manufactured by The Japan Steel Works, Ltd., so that the outlet resin temperature was 230°C. The mixture was cooled and solidified with water, and then pelletized using a rotary cutter to obtain thermoplastic resin composition (Y-2). The polycarbonate resin composition (X) and thermoplastic resin composition (Y-2) obtained to obtain the composition shown in Table 1 were placed in a polyethylene bag, and the resulting resin composition was mixed by shaking by hand. The results of the evaluation of the resulting resin composition are shown in Table 1.

[0191] [Example 6] A resin composition was obtained in the same manner as in Example 1, except that the thermoplastic resin composition (Y-3) was used and the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0192] [Example 7] A resin composition was obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0193] [Example 8] Polycarbonate resin composition (X) was obtained in the same manner as in Example 2. Thermoplastic resin (B-2) and pigment (F-1) were mixed to obtain the composition shown in Table 2, and the mixture was extruded into strands using a twin-screw extruder (LABOTEX 30HSS-32) equipped with one vent, manufactured by The Japan Steel Works, Ltd., so that the outlet resin temperature was 230°C. The mixture was cooled and solidified with water, and then pelletized using a rotary cutter to obtain thermoplastic resin composition (Y-4). The polycarbonate resin composition (X) and thermoplastic resin composition (Y-4) obtained to obtain the composition shown in Table 1 were placed in a polyethylene bag, and the resulting resin composition was mixed by shaking by hand. The results of the evaluation of the resulting resin composition are shown in Table 1.

[0194] [Comparative Example 1] Polycarbonate resin composition (X) was obtained in the same manner as in Example 2. Thermoplastic resin (B-3) and pigment (F-1) were mixed to obtain the composition shown in Table 2, and extruded into strands using a twin-screw extruder (LABOTEX 30HSS-32) equipped with one vent port (manufactured by The Japan Steel Works, Ltd.) so that the outlet resin temperature reached 250°C. The extruded strands were cooled and solidified with water, and then pelletized using a rotary cutter. The vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to 500 Pa to obtain thermoplastic resin composition (Y-5). The polycarbonate resin composition (X) and thermoplastic resin composition (Y-5) obtained to obtain the composition shown in Table 1 were placed in a polyethylene bag, and the resulting resin composition was mixed by shaking by hand. The results of the evaluation of the resulting resin composition are shown in Table 1.

[0195] Comparative Example 2 A resin composition was obtained in the same manner as in Example 1, except that the thermoplastic resin composition (Y-6) was used and the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0196] Comparative Example 3 A resin composition was obtained in the same manner as in Example 1, except that the thermoplastic resin composition (Y-7) was used and the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0197] Comparative Example 4 Polycarbonate resin (A-1), polycarbonate resin (A-2), core-shell rubber (C-1), ultraviolet absorber (D-1), and light stabilizer (E-1) were mixed to obtain the composition shown in Table 1, and the mixture was extruded into strands using a twin-screw extruder (LABOTEX30HSS-32) equipped with one vent, manufactured by The Japan Steel Works, Ltd., so that the outlet resin temperature reached 250°C. The mixture was then cooled and solidified with water, and pelletized using a rotary cutter. The vent was connected to a vacuum pump, and the pressure at the vent was controlled to 500 Pa, yielding polycarbonate resin composition (X). The obtained polycarbonate resin composition (X) and thermoplastic resin composition (Y-3) were mixed to obtain the composition shown in Table 1, and extruded into strands using a twin-screw extruder (LABOTEX30HSS-32) equipped with one vent port manufactured by The Japan Steel Works, Ltd., so that the outlet resin temperature was 250°C. After cooling and solidifying with water, the extruded strands were pelletized using 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 500 Pa, to obtain a resin composition. The results for the obtained resin composition are shown in Table 1.

[0198] Comparative Example 5 Polycarbonate resin (A-1), polycarbonate resin (A-2), core-shell rubber (C-1), ultraviolet absorber (D-1), and light stabilizer (E-1) were mixed to obtain the composition shown in Table 1, and the mixture was extruded into strands using a twin-screw extruder (LABOTEX30HSS-32) equipped with one vent, manufactured by The Japan Steel Works, Ltd., so that the outlet resin temperature reached 250°C. The mixture was then cooled and solidified with water, and pelletized using a rotary cutter. The vent was connected to a vacuum pump, and the pressure at the vent was controlled to 500 Pa, yielding polycarbonate resin composition (X). Thermoplastic resin (B-1) and pigment (F-1) were mixed to obtain the composition shown in Table 2. The mixture was extruded into strands using a twin-screw extruder (LABOTEX 30HSS-32) equipped with one vent, manufactured by The Japan Steel Works, Ltd., so that the outlet resin temperature reached 230°C. The mixture was then cooled and solidified with water, and pelletized using a rotary cutter to obtain thermoplastic resin composition (Y-2). The resulting polycarbonate resin composition (X) and thermoplastic resin composition (Y-2) were mixed to obtain the composition shown in Table 1. The mixture was extruded into strands using a twin-screw extruder (LABOTEX 30HSS-32) equipped with one vent, manufactured by The Japan Steel Works, Ltd., so that the outlet resin temperature reached 250°C. The mixture was then cooled and solidified with water, and pelletized using a rotary cutter. The vent was connected to a vacuum pump, and the pressure at the vent was controlled to 500 Pa to obtain a resin composition. The results for the resulting resin composition are shown in Table 1.

[0199] Comparative Example 6 A resin composition was obtained in the same manner as in Comparative Example 4, except that the formulation was changed as shown in Table 1. The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0200] [Table 1]

[0201] [Table 2]

[0202] From the above results, it was found that molded articles having excellent ink painting-like patterns with non-uniform colors could be obtained in Examples 1 to 8, and no defects in appearance were observed on the surface of the molded articles. Furthermore, it was revealed that even when the thermoplastic resin (Y) was mixed, there was no decrease in impact resistance and the articles exhibited good mechanical properties. On the other hand, in Comparative Example 1, due to good compatibility, it was not possible to obtain a molded product with a non-uniform color and an excellent ink painting-like pattern. In Comparative Example 2, due to poor compatibility, the appearance was non-uniform in color, but the pattern was not connected but rather interrupted. In Comparative Example 3, due to the inclusion of aluminum particles, the molded product had a poor streaky appearance and was partially non-uniform in color, making it impossible to obtain an excellent appearance, and a decrease in impact resistance was also confirmed. Furthermore, in Comparative Examples 4 to 6, due to mixing in a molten state, the appearance was uniform in color and the formation of a pattern was not confirmed.

Claims

1. A method for producing a resin composition (W) containing a polycarbonate resin composition (X) and a thermoplastic resin composition (Y), comprising: The polycarbonate resin composition (X) contains a polycarbonate resin (A) containing, as a part of its structure, a structural unit derived from a dihydroxy compound represented by the following formula (1): the thermoplastic resin composition (Y) is incompatible with the polycarbonate resin (A) and has a glass transition temperature of 70°C or higher and lower than 150°C; the resin composition (W) contains at least one dye and / or pigment, the content of aluminum derived from the dye and / or pigment in the resin composition (W) is 0.1 parts by mass or less, based on 100 parts by mass of the resin composition (W); a step of mixing the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) in a solid state at a temperature equal to or lower than the lower of the glass transition temperatures of the polycarbonate resin composition (X) and the thermoplastic resin composition (Y), which is −20° C. or lower. 【Chemical 1】

2. The method for producing a resin composition (W) according to claim 1, wherein the thermoplastic resin composition (Y) contains the dye and / or pigment.

3. The method for producing a resin composition (W) according to claim 2, wherein the dye and / or pigment is contained in an amount of 5 to 90 parts by weight per 100 parts by weight of the thermoplastic resin composition (Y).

4. 3. The method for producing a resin composition (W) according to claim 1 or 2, wherein the polycarbonate resin (A) further contains a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a heterocyclic dihydroxy compound.

5. 3. The method for producing resin composition (W) according to claim 1 or 2, wherein the ratio of structural units derived from the dihydroxy compound represented by formula (1) in the polycarbonate resin (A) is 25 to 95 mol % based on all structural units derived from hydroxy compounds.

6. The method for producing a resin composition (W) according to claim 1 or 2, wherein the content of the polycarbonate resin composition (X) is 70 to 99.99 parts by weight per 100 parts by weight of the total of the resin compositions (W).

7. The method for producing a resin composition (W) according to claim 1 or 2, wherein the content of the thermoplastic resin composition (Y) is 0.01 to 10 parts by weight per 100 parts by weight of the total of the resin compositions.

8. The method for producing a resin composition (W) according to claim 1 or 2, wherein the polycarbonate resin (A) has a total light transmittance of 70% or more at a thickness of 1 mm.

9. 3. The method for producing a polycarbonate resin composition (W) according to claim 1 or 2, wherein the polycarbonate resin composition (X) further contains an elastomer (C) having a core-shell structure.

10. 3. The method for producing resin composition (W) according to claim 1 or 2, wherein the impact strength retention rate of said resin composition (W) is 80% or more relative to the Charpy impact strength of said polycarbonate resin composition (X) alone.

11. 3. A method for producing a molded article made of a resin composition (W) obtained by the production method according to claim 1 or 2, wherein the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) have different color tones, and the molded article has a non-uniform color tone and a flow pattern.

12. The method for producing a molded article according to claim 11, wherein the resin composition (W) is charged into an injection molding machine and molded at a glass transition temperature (Tg) of the polycarbonate resin composition (X) + 70°C to Tg + 170°C.

13. a polycarbonate resin composition (X) containing a polycarbonate resin (A) having a structural unit derived from a dihydroxy compound represented by the following formula (1) as part of its structure; a thermoplastic resin composition (Y) that is incompatible with the polycarbonate resin (A) and has a glass transition temperature of 70°C or higher but lower than 150°C; A resin composition comprising at least one dye and / or pigment, A resin composition (W) in which the amount of aluminum derived from the dye and / or pigment contained in the resin composition is 0.1 parts by weight or less. 【Chemistry 2】

14. A molded article comprising the resin composition (W) according to claim 13, wherein the polycarbonate resin composition (X) and the thermoplastic resin composition (Y) have different color tones, and the molded article has a non-uniform color tone and a flow pattern.

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