Polycarbonate resin composition and molded article

Abstract

The present invention provides a polycarbonate resin composition having good low-temperature impact resistance, durability, and flame retardancy. The present invention is a polycarbonate resin composition characterized in that, with respect to 100 parts by weight of a resin component composed of 10 to 90 parts by weight of (A) a polycarbonate-polydiorganosiloxane copolymer (A component) and 90 to 10 parts by weight of (B) a polycarbonate resin (B component), 0.5 to 7 parts by weight of (C) a phosphazene compound (C component) and 0.1 to 0.5 parts by weight of (D) a fluorine-containing anti-dripping agent (D component) are contained, the ratio of the viscosity-average molecular weight of the A component to the viscosity-average molecular weight of the B component (Mv(A component) / Mv(B component)) is 1 to 1.5, and the A component satisfies (i) to (ii) below. (i) is a polycarbonate-polydiorganosiloxane copolymer composed of a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3]. (ii) The viscosity-average molecular weight is 23,000 to 30,000.

Description

Technical Field

[0001] This invention relates to polycarbonate resin compositions and molded articles. More specifically, it relates to polycarbonate resin compositions and molded articles that improve low-temperature impact resistance, durability, and flame retardancy by incorporating phosphazene compounds and fluorinated anti-drip agents into a resin composition consisting of a polycarbonate-polydiorganosiloxane copolymer and a polycarbonate resin with a specific viscosity-average molecular weight ratio. Background Technology

[0002] Polycarbonate resin is used in many applications, such as mechanical parts, automotive parts, electrical and electronic components, and office equipment parts, due to its excellent properties such as mechanical strength, dimensional stability, and flame retardancy. However, for outdoor electrical and electronic storage boxes such as information communication boxes and solar power junction boxes, which require thin-walled flame retardancy, high impact resistance in low-temperature winter environments, and durability that does not easily deteriorate even when exposed to ultraviolet rays and wind and rain, as exemplified by UL746C f1 certification, previous polycarbonate resins have not been able to fully meet these requirements.

[0003] As a method to improve low-temperature impact resistance and durability, a method has been proposed that uses a polycarbonate-polydiorganosiloxane copolymer, and incorporates polytetrafluoroethylene particles and organometallic salt flame retardants into the polycarbonate-polydiorganosiloxane copolymer (Patent Documents 1 and 2). However, these methods cannot be said to provide sufficient flame retardancy for thin walls, and the flame retardancy after water exposure testing in UL746C f1 rating certification is insufficient. In addition, the polycarbonate-polydiorganosiloxane copolymer obtained by conventional polymerization methods is cloudy and opaque, and the resin composition using this polycarbonate-polydiorganosiloxane copolymer has problems with colorability (Patent Documents 3 and 4). On the other hand, as a method to impart superior flame retardancy, the use of phosphazene compounds as phosphorus-based flame retardants has been proposed (Patent Documents 5 and 6). However, the addition of phosphazene compounds has the disadvantage of reducing impact resistance. Furthermore, these documents do not record the following: by selecting polycarbonate-polydiorganosiloxane copolymers and polycarbonate resins with specific viscosity-average molecular weight ratios as polycarbonate resins, high durability and low-temperature impact resistance can be obtained even with the addition of phosphazene compounds.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 8-81620

[0007] Patent Document 2: International Publication No. 2011 / 1551490

[0008] Patent Document 3: Japanese Patent No. 2662310

[0009] Patent Document 4: Japanese Patent Application Publication No. 3-79626

[0010] Patent Document 5: Japanese Patent Application Publication No. 2013-1801

[0011] Patent Document 6: Japanese Patent Application Publication No. 2012-1580 Summary of the Invention

[0012] The purpose of this invention is to provide polycarbonate resin compositions and molded articles with good low-temperature impact resistance, durability and flame retardancy.

[0013] To address the aforementioned problems, the inventors conducted in-depth research and discovered that by incorporating a phosphazene compound and a fluorinated anti-drip agent into a resin composition consisting of a polycarbonate-polydiorganosiloxane copolymer and a polycarbonate resin with a specific viscosity-average molecular weight ratio, a polycarbonate resin composition exhibiting excellent low-temperature impact resistance, durability, and flame retardancy can be obtained. According to the present invention, the aforementioned problems are achieved through a polycarbonate resin composition characterized in that, relative to 100 parts by weight of a resin composition consisting of 10-90 parts by weight of (A) polycarbonate-polydiorganosiloxane copolymer (component A) and 90-10 parts by weight of polycarbonate resin (component B), it contains 0.5-7 parts by weight of (C) phosphazene compound (component C) and 0.1-0.5 parts by weight of (D) fluorinated anti-drip agent (component D), the viscosity-average molecular weight ratio of component A to component B (Mv(component A) / Mv(component B)) is 1-1.5, and component A satisfies (i) to (ii) below.

[0014] (i) is a polycarbonate-polydiorganosiloxane copolymer composed of polycarbonate blocks represented by the following general formula [1] and polydiorganosiloxane blocks represented by the following general formula [3].

[0015] (ii) The viscosity-average molecular weight is 23,000 to 30,000.

[0016]

[0017] In the above general formula [1], R 1 and R 2Each group independently represents a group selected from hydrogen atom, halogen atom, alkyl group with 1 to 18 carbon atoms, alkoxy group with 1 to 18 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 14 carbon atoms, aryloxy group with 6 to 14 carbon atoms, aralkyl group with 7 to 20 carbon atoms, arylalkoxy group with 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and carboxyl group. When multiple groups exist, they may be the same or different. e and f are integers from 1 to 4, and W is a single bond or at least one group selected from the group represented by the following general formula [2].

[0018]

[0019] (In the above general formula [2], R) 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 Each group independently represents a group selected from hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms, R 19 and R 20 Each group independently represents a group selected from hydrogen atoms, halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, and carboxyl groups. When multiple groups are present, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0020]

[0021] (In the above general formula [3], R) 3 R 4 R 5 R 6 R 7 and R 8 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R 9 and R 10 Each of the following is independently composed of a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms; p is a natural number; q is 0 or a natural number; and the average chain length p+q is a natural number of 30 to 60. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0022] The resin composition of this invention is widely applicable in various fields, including residential equipment, building materials, household materials, infrastructure, automotive, OA / EE, and other applications, particularly in outdoor applications requiring high durability, due to its high levels of low-temperature impact resistance, durability, and flame retardancy. Therefore, this invention has significant industrial benefits. Detailed Implementation

[0023] The present invention will now be described in detail.

[0024] (Component A: Polycarbonate-polydiorganosiloxane copolymer)

[0025] The polycarbonate-polydiorganosiloxane copolymer used as component A is a polycarbonate-polydiorganosiloxane copolymer composed of polycarbonate blocks represented by the following general formula [1] and polydiorganosiloxane blocks represented by the following general formula [3].

[0026]

[0027] In the above general formula [1], R 1 and R 2 Each group independently represents a group selected from hydrogen atom, halogen atom, alkyl group with 1 to 18 carbon atoms, alkoxy group with 1 to 18 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 14 carbon atoms, aryloxy group with 6 to 14 carbon atoms, aralkyl group with 7 to 20 carbon atoms, arylalkoxy group with 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group, and carboxyl group. When multiple groups are present, they may be the same or different. e and f are integers from 1 to 4, and W is a single bond or at least one group selected from the groups represented by the following general formula [2].

[0028]

[0029] (In the above general formula [2], R) 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 Each group independently represents a group selected from hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms, R 19 and R 20Each group independently represents a group selected from hydrogen atoms, halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, and carboxyl groups. When multiple groups are present, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0030]

[0031] (In the above general formula [3], R) 3 R 4 R 5 R 6 R 7 and R 8 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R 9 and R 10 Each of the following is independently composed of a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms; p is a natural number; q is 0 or a natural number; and the average chain length p+q is a natural number of 30 to 60. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0032] Examples of diphenols (I) that derive the carbonate constituent unit represented by the above general formula [1] include, for example, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, and 2,2-bis(4-hydroxy-3-isopropyl) 2,2-Bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-Bis(4-hydroxyphenyl)butane, 2,2-Bis(4-hydroxyphenyl)octane, 2,2-Bis(3-bromo-4-hydroxyphenyl)propane, 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-Bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-Bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-Bis(4-hydroxyphenyl)fluorene, 9,9-Bis(4-hydroxy-3-methylphenyl) Fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, etc.

[0033] Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-sulfonyldiphenol and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane is preferred due to its excellent strength and good durability. Furthermore, two or more of these can be used alone or in combination.

[0034] In the carbonate constituent unit represented by the above general formula [3], R 3 R 4 R 5 R 6 R 7 and R 8 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and particularly preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R 9 and R 10 Each of the constituent elements is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. As a dihydroxyaryl-terminated polydiorganosiloxane (II) that derives from the carbonate constituent unit represented by the above formula [3], a compound represented by the following general formula (I) may be preferred, for example.

[0035]

[0036] The degree of polymerization of the diorganosiloxane is expressed as p, a natural number, q, which is 0 or a natural number, and p+q, which is a natural number from 30 to 60, preferably 30 to 50, and more preferably 35 to 50. When p+q is less than 30, the low-temperature impact resistance and durability are poor; if it exceeds 60, the flame retardancy may sometimes deteriorate.

[0037] The content of the polydiorganosiloxane block represented by the following general formula [4] contained in the above general formula [3] of the present invention is based on the total weight of the polycarbonate resin composition, preferably 1.0 wt% to 10.0 wt%, more preferably 2.0 wt% to 10.0 wt%, further preferably 2.0 wt% to 8.0 wt%, and particularly preferably 3.0 wt% to 8.0 wt%. When the content of the polydiorganosiloxane component is less than 1.0 wt%, the low-temperature impact resistance and durability are sometimes insufficient; if it exceeds 10.0 wt%, poor appearance during molding and a decrease in heat resistance temperature sometimes occur. It should be noted that the degree of polymerization of the above-mentioned diorganosiloxane and the content of the polydiorganosiloxane component can be determined by... 1 It was calculated by H-NMR measurement.

[0038]

[0039] (In the above general formula [4], R) 3 R 4 R 5 R 6 R 7 and R 8 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number from 30 to 60.

[0040] The polycarbonate-polydiorganosiloxane copolymer used as component A in this invention is preferably a polycarbonate-polydiorganosiloxane copolymer with a condensed structure in which polydiorganosiloxane domains are dispersed in a polycarbonate matrix, and the average size of the polydiorganosiloxane domains is 5 to 15 nm. More preferably, the average size of the polydiorganosiloxane domains is 5 to 12 nm, and even more preferably 8 to 12 nm. When the average size is less than 5 nm, the low-temperature impact resistance is sometimes insufficient; when it exceeds 15 nm, poor appearance during molding sometimes occurs.

[0041] The normalized dispersion of the domain size of the polydiorganosiloxane is preferably 25% or less, more preferably 23% or less, and even more preferably 20% or less. In practical terms, the lower limit of the above-mentioned normalized dispersion is preferably 5% or more, more preferably 10% or more. By having the above-mentioned suitable average domain size and this normalized dispersion, impact resistance and flame retardancy can sometimes be improved.

[0042] The polycarbonate-polydiorganosiloxane copolymer used as component A in this invention preferably has a total light transmittance of 88% or more in a molded article with a thickness of 2.0 mm formed by injection molding. More preferably, the total light transmittance is 88.5% or more, and even more preferably 89% or more. On the other hand, the upper limit is preferably 92%, and more preferably 91.5%. When the total light transmittance is less than 88%, the colorability of the resin composition sometimes deteriorates.

[0043] The average size and normalized dispersion of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer were evaluated using small-angle X-ray scattering (SAXS). SAXS is a method for measuring diffuse scattering and diffraction in small-angle regions with a scattering angle (2θ) less than 10°. In SAXS, if regions of approximately 1–100 nm in size with different electron densities exist in the material, the diffuse scattering of X-rays is measured using this electron density difference. The particle size of the object under test is determined based on the scattering angle and scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin with a condensed structure of polydiorganosiloxane domains dispersed in a polycarbonate-polydiorganosiloxane copolymer matrix, diffuse scattering of X-rays is generated using the electron density difference between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at various scattering angles (2θ) less than 10° was measured, and the small-angle X-ray scattering distribution was determined. Assuming the polydiorganosiloxane domains are spherical and exhibit particle size distribution deviations, commercially available analytical software was used to simulate the distribution using assumed particle sizes and a hypothetical particle size distribution model to determine the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domains. Based on small-angle X-ray scattering, the average size and particle size distribution of polydiorganosiloxane regions dispersed in a polycarbonate polymer matrix, which cannot be accurately measured using transmission electron microscopy, can be determined with good accuracy, simplicity, and reproducibility.

[0044] The average domain size refers to the numerical average of the sizes of each domain. Normalized dispersion refers to the parameter that normalizes the width of the particle size distribution to the average size. Specifically, it is the value of the dispersion of the domain size of polydiorganosiloxane to the average domain size, expressed by the following equation (1).

[0045] Standardized dispersion (%) = δ / D av …(1)

[0046] In equation (1) above, δ is the standard deviation of the domain size of polydiorganosiloxane, and Dav is the average domain size.

[0047] The terms "average domain size" and "normalized dispersion" used in connection with this invention refer to measurements obtained by using a 1.0 mm thick molded article formed by injection molding and measuring it using small-angle X-ray scattering (SAXS). Specifically, the values ​​are obtained by measuring the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domains at the intersection of a 1.0 mm thick section (50 mm wide, 90 mm long, and thicknesses from the gate side of 3.0 mm (20 mm long), 2.0 mm (45 mm long), and 1.0 mm (25 mm long) from the gate side, with an arithmetic mean surface roughness (Ra) of 0.03 μm, using SAXS.

[0048] Next, the method for manufacturing the above-mentioned polycarbonate-polydiorganosiloxane copolymer will be described. A mixed solution of a chloroformate compound containing a chloroformate of diphenol (I) and / or a carbonate oligomer of diphenol (I) having terminal chloroformate groups is prepared by reacting diphenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of diphenol (I) in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution. Phosgene is preferred as the chloroformate-forming compound.

[0049] When generating chloroformate compounds from diphenols (I), the entire amount of diphenols (I) from which the carbonate constituent unit represented by the above general formula [1] is derived into chloroformate compounds in one step, or a portion of it can be added as a reactant in the subsequent interfacial polycondensation reaction as a later-added monomer. The later-added monomer is added to accelerate the subsequent polycondensation reaction and is not necessary. The method for generating chloroformate compounds is not particularly limited, but it is generally preferred to carry out the reaction in a solvent in the presence of an acid-binding agent. Furthermore, small amounts of antioxidants such as sodium sulfite and hydrogen sulfide can be added as needed, and this is preferred. The proportion of chloroformate-forming compounds used can be adjusted appropriately by considering the stoichiometry (equivalents) of the reaction. In addition, when using phosgene, which is a preferred chloroformate-forming compound, it is preferable to blow vaporized phosgene into the reaction system.

[0050] As acid-binding agents, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof can be used.

[0051] Similarly, the proportion of the acid-binding agent used should be appropriately determined by considering the stoichiometric ratio (equivalents) of the reaction. Specifically, for 1 mole of diphenol (I) used in the formation of the chloroformate compound of diphenol (I) (generally 1 mole is equivalent to 2 equivalents), it is preferable to use 2 equivalents or slightly more of the acid-binding agent.

[0052] As the solvents mentioned above, any solvent that is inert to the reaction, such as a solvent known for use in the manufacture of polycarbonate, can be used alone or in a mixture. Examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as dichloromethane and chlorobenzene. Halogenated hydrocarbon solvents such as dichloromethane are particularly preferred.

[0053] There are no particular pressure restrictions for the formation of chloroformate compounds; atmospheric pressure, pressurized pressure, or depressurized pressure are all acceptable, but atmospheric pressure is generally advantageous. The reaction temperature is selected from the range of -20 to 50°C. In many cases, water cooling or ice cooling is preferred due to the heat generated during the reaction. The reaction time is affected by other conditions and cannot be generalized; it is typically carried out over 0.2 to 10 hours.

[0054] The pH range for the formation of chloroformate compounds can be determined using known interfacial reaction conditions, with the pH typically adjusted to above 10.

[0055] In the manufacture of the polycarbonate-polydiorganosiloxane copolymer used as component A of the present invention, a mixed solution of a chloroformate compound containing a chloroformate of a diphenol (I) and a carbonate oligomer of a diphenol (I) having terminal chloroformate groups is prepared. Then, while stirring the mixed solution, a dihydroxyaryl-terminated polydiorganosiloxane of the carbonate constituent unit represented by the derivative general formula [2] is added at a rate of 0.01 mol / min or less relative to 1 mole of the diphenol (I) added when preparing the mixed solution, so that the dihydroxyaryl-terminated polydiorganosiloxane undergoes interfacial polycondensation with the chloroformate compound, thereby obtaining the polycarbonate-polydiorganosiloxane copolymer.

[0056] The polycarbonate-polydiorganosiloxane copolymer used as component A of the present invention can be prepared by combining a branching agent with a diphenolic compound to form a branched polycarbonate-polydiorganosiloxane copolymer. Examples of trifunctional or higher-functionalized aromatic compounds used in the above-mentioned branched polycarbonate resin include phloroglucinol, phloroglucinol, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, and 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methyl Triphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)one, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acyl chlorides, wherein 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0057] The above-mentioned branched polycarbonate-polydiorganosiloxane copolymer can be manufactured by including a branching agent in the mixed solution during the formation reaction of the chloroformate compound, or by adding the branching agent during the interfacial polycondensation reaction after the formation reaction is completed. The proportion of carbonate constituent units from the branching agent in the total amount of carbonate constituent units constituting the copolymer is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, and particularly preferably 0.05 to 1.0 mol%. It should be noted that this amount of branching can be adjusted by... 1 It was calculated by H-NMR measurement.

[0058] For the pressure within the polycondensation reaction system, reduced pressure, normal pressure, or increased pressure are all acceptable, but normal pressure or the system's own pressure level is generally preferred. The reaction temperature is selected from the range of -20 to 50°C. In many cases, due to the heat generated during polymerization, water cooling or ice cooling is preferred. The reaction time varies depending on the reaction temperature and other conditions, and therefore cannot be generalized; typically, it is carried out for 0.5 to 10 hours. Depending on the circumstances, the obtained polycarbonate-polydiorganosiloxane copolymer can also be appropriately subjected to physical treatments (mixing, grading, etc.) and / or chemical treatments (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain the desired reduced viscosity [η]. SPThe polycarbonate-polydiorganosiloxane copolymer [c] can be subjected to various post-treatments, such as known separation and purification methods, to recover the polycarbonate-polydiorganosiloxane copolymer with the desired purity.

[0059] The viscosity-average molecular weight (Mv(component A)) of the polycarbonate-polydiorganosiloxane copolymer used as component A in this invention is 23,000 to 30,000, preferably 23,000 to 28,000, more preferably in the range of 23,000 to 27,000, and even more preferably in the range of 23,000 to 25,000. If the molecular weight exceeds 30,000, the melt viscosity becomes too high and the formability is poor; if the molecular weight is less than 23,000, good mechanical properties cannot be obtained.

[0060] It should be noted that the viscosity-average molecular weight of the polycarbonate-polydiorganosiloxane copolymer used as component A of the present invention is calculated according to the following procedure. First, using an Ostwald viscometer, the specific viscosity (η) is calculated from a solution in which 0.7 g of the polycarbonate-polydiorganosiloxane copolymer resin is dissolved in 100 ml of dichloromethane at 20°C, using the following formula. SP ),

[0061] Specific viscosity (η) SP )=(t-t0) / t0

[0062] [t0 is the number of seconds for dichloromethane to drop, and t is the number of seconds for the sample solution to drop.]

[0063] The specific viscosity (η) is obtained from SP Calculate the viscosity-average molecular weight Mv using the following mathematical formula.

[0064] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0065] [η] = 1.23 × 10 －4 Mv 0.83

[0066] c = 0.7

[0067] The content of component A is 10 to 90 parts by weight per 100 parts by weight of resin, preferably 20 to 80 parts by weight, and more preferably 25 to 75 parts by weight. If the content of component A is less than 10 parts by weight, sufficient room temperature and low temperature impact resistance will not be obtained, and if it exceeds 90 parts by weight, the retention rate of physical properties after water exposure will be poor.

[0068] (Component B: Polycarbonate resin)

[0069] The polycarbonate resin used as component B in this invention is obtained by reacting a diphenol with a carbonate precursor. Examples of reaction methods include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0070] Representative examples of diphenols used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2,2-bis(4-hydroxyphenyl) Examples of suitable diphenols include pentane, 4,4'-(p-phenylene diisopropylene)diphenol, 4,4'-(m-phenylene diisopropylene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl) oxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ketone, bis(4-hydroxyphenyl) ester, bis(4-hydroxy-3-methylphenyl) sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred diphenols are bis(4-hydroxyphenyl) alkanes, among which bisphenol A is particularly preferred for its impact resistance and is also widely used.

[0071] In this invention, in addition to bisphenol A polycarbonate, which is a general polycarbonate, special polycarbonates made using other diphenols can also be used as component B.

[0072] For example, polycarbonates (homopolymers or copolymers) using 4,4'-(m-phenylene diisopropylidene)diphenol (hereinafter, sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter, sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter, sometimes abbreviated as "BCF") as part or all of the diphenol components are suitable for applications where the requirements for dimensional changes and morphological stability due to water absorption are particularly stringent. These diphenols other than BPA are preferably used at 5 mol% or more of the total diphenol component constituting the polycarbonate, and particularly preferably at 10 mol% or more.

[0073] Especially when high rigidity and better hydrolysis resistance are required, component B constituting the resin composition is particularly preferably a copolymer polycarbonate of the following (1) to (3).

[0074] (1) A copolymer polycarbonate in which 100 mol% of the diphenol component constituting the polycarbonate has a BPM of 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and a BCF of 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0075] (2) The polycarbonate comprising 100 mol% of the diphenol component, wherein BPA is 10-95 mol% (more preferably 50-90 mol%, even more preferably 60-85 mol%) and BCF is 5-90 mol% (more preferably 10-50 mol%, even more preferably 15-40 mol%).

[0076] (3) The polycarbonate comprising 100 mol% of the diphenol component is a copolymer polycarbonate with BPM of 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and Bis-TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0077] These special polycarbonates can be used alone or in appropriate combinations of two or more. Alternatively, they can be mixed with general-purpose bisphenol A polycarbonates.

[0078] The methods for manufacturing and properties of these special polycarbonates are detailed in publications such as Japanese Patent Application Publication No. 6-172508, Japanese Patent Application Publication No. 8-27370, Japanese Patent Application Publication No. 2001-55435, and Japanese Patent Application Publication No. 2002-117580.

[0079] It should be noted that among the various polycarbonates mentioned above, those with water absorption and Tg (glass transition temperature) within the following ranges due to adjustments in copolymer composition are particularly preferred in fields requiring morphological stability because the polymer itself has good hydrolysis resistance and excellent low warpage after molding.

[0080] (i) a polycarbonate with a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or

[0081] (ii) A polycarbonate with a Tg of 160–250°C, preferably 170–230°C, and a water absorption rate of 0.10–0.30%, preferably 0.13–0.30%, and more preferably 0.14–0.27%.

[0082] Here, the water absorption rate of polycarbonate is determined using a circular test piece with a diameter of 45 mm and a thickness of 3.0 mm, after immersion in water at 23°C for 24 hours according to ISO 62-1980. Additionally, the Tg (glass transition temperature) is determined using a differential scanning calorimeter (DSC) according to JIS K7121.

[0083] As carbonate precursors, acyl halides, diesters of carbonates, or halocarbamates are used. Specifically, examples include dihalocarbamates of phosgene, diphenyl carbonate, or diphenols.

[0084] When manufacturing polycarbonate resin from the aforementioned diphenols and carbonate precursors using interfacial polymerization, catalysts, terminators, and antioxidants to prevent the oxidation of diphenols may be used as needed. Furthermore, the polycarbonate resins of the present invention include branched polycarbonate resins obtained by copolymerizing trifunctional or higher-functional aromatic compounds, polyester polycarbonate resins obtained by copolymerizing aromatic or aliphatic (including alicyclic) difunctional carboxylic acids, copolymerized polycarbonate resins obtained by copolymerizing difunctional alcohols (including alicyclic ones), and polyester polycarbonate resins obtained by copolymerizing the aforementioned difunctional carboxylic acids and difunctional alcohols together. Additionally, mixtures of two or more of the obtained polycarbonate resins may also be used.

[0085] Branched polycarbonate resins can impart anti-drip properties to the resin compositions of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in the aforementioned branched polycarbonate resins include phloroglucinol, phloroglucinol, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, and 2,6-bis(2-hydroxy-5-methylbenzyl)-4- The following are examples of methylphenol, triphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)one, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acyl chlorides, wherein 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0086] In branched polycarbonate, the constituent units derived from polyfunctional aromatic compounds are preferably 0.01 to 1 mol% of the total 100 mol% of the constituent units derived from diphenols and the constituent units derived from the above-mentioned polyfunctional aromatic compounds, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%.

[0087] Furthermore, particularly in the case of melt transesterification, branched structural units are sometimes generated as side reactions. The amount of these branched structural units is preferably 0.001 to 1 mol% of the total 100 mol% of the constituent units derived from the diphenol, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%. It should be noted that the proportion of the above-mentioned branched structure can be determined by… 1 It was calculated by H-NMR measurement.

[0088] Aliphatic difunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of aliphatic difunctional carboxylic acids include, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decanoic acid), dodecanoic acid, tetradecanoic acid, octadecanoic acid, and eicosanoic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Alicyclic diols are more preferably difunctional alcohols, such as cyclohexanediethanol, cyclohexanediol, and tricyclodecanediethanol.

[0089] The reaction methods used in the manufacturing of polycarbonate resins according to the present invention, such as interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well known in various documents and Japanese Patent Publications.

[0090] The viscosity-average molecular weight (Mv(B component)) of the polycarbonate resin used as component B in this invention is preferably in the range of 15,000 to 30,000, more preferably 16,000 to 28,000, and particularly preferably 18,000 to 25,000. If the molecular weight exceeds 30,000, the melt viscosity may become too high, resulting in poor moldability; if the molecular weight is less than 15,000, good mechanical properties may not be obtained. The viscosity-average molecular weight ratio (Mv(A component) / Mv(B component)) of the resin component in this invention is 1 to 1.5, preferably 1 to 1.3, and more preferably 1 to 1.25. If the viscosity-average molecular weight ratio of component A to component B is less than 1, the flame retardancy and flame retardancy after water exposure deteriorate. If it exceeds 1.5, the low-temperature impact resistance and the retention rate of physical properties after water exposure are poor.

[0091] (Component C: Phosphazene compound)

[0092] The resin composition of the present invention contains a phosphazene compound as component C. Phosphazenes, by containing phosphorus and nitrogen atoms in their molecules, can impart the resin composition with the effect of inhibiting the reduction of durability and flame retardancy. When using compounds other than phosphazenes, such as phosphate esters, condensed phosphate esters, etc., as flame retardants, the durability and flame retardancy are reduced due to the plasticization of the polycarbonate resin. There is no particular limitation as long as the phosphazene is a compound that does not contain halogen atoms and has a phosphazene structure in its molecule. The phosphazene structure referred to here is the structure represented by the formula: -P(R)=N- [where R is an organic group]. Phosphazene compounds are represented by general formulas [5] and [6].

[0093]

[0094]

[0095] (where R is in the formula) 21 R 22 R 23 and R 24 This indicates a hydrogen, hydroxyl, amino, or organic group that does not contain a halogen atom. Additionally, n represents an integer from 3 to 10.

[0096] In the above equations [5] and [6], R is used as 21 R 22 R 23 and R 24 The organic group that does not contain halogen atoms can be represented by, for example, alkoxy, phenyl, amino, allyl, etc.

[0097] Among them, the cyclic phenoxyphosphazene represented by the following general formula [7] is preferred.

[0098]

[0099] [In the formula, n represents an integer from 3 to 25. Ph represents phenyl.]

[0100] The phosphazene used as component C preferably contains 98.5 mol% or more of phosphazene cyclic trimers (n = 3). This content is preferably 99 mol% to 100 mol%, more preferably in the range of 99.5 mol% to 100 mol%. If the content of phosphazene cyclic trimers is less than 98.5 mol%, the durability and flame retardancy may be poor.

[0101] Methods for manufacturing phosphazenes are described in European Patent Application Publication No. 728811 and International Publication No. 97 / 40092, etc.

[0102] In addition to cyclic trimers, phosphazenes also generate higher oligomers, such as cyclic tetramers or higher, as byproducts during the manufacturing process. The content of cyclic trimers of phosphazenes can be increased by purification using column chromatography or other methods.

[0103] It should be noted that the content of phosphazene cyclic trimers in phosphazenes can be determined by... 31 Quantification was performed using PNMR (chemical shift, δ trimer 6.5–10.0 ppm, δ tetramer -10 to -13.5 ppm, δ higher oligomers -16.5 to -25.0 ppm).

[0104] The content of component C is 0.5 to 7 parts by weight relative to 100 parts by weight of resin, preferably 0.7 to 5 parts by weight, and more preferably 1 to 3.5 parts by weight. If the content of component C is less than 0.5 parts by weight, no flame retardant effect can be obtained, and if it exceeds 7 parts by weight, the retention rate of physical properties after water exposure and the low-temperature impact resistance are poor.

[0105] (Component D: Fluorine-containing anti-drip agent)

[0106] The resin composition of the present invention contains a fluorinated anti-drip agent as component D. By including this fluorinated anti-drip agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.

[0107] As a fluorinated anti-drip agent, fluorinated polymers with fibrillation ability can be cited as examples. Examples of such polymers include polytetrafluoroethylene (PTFE), tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers), partially fluorinated polymers as disclosed in U.S. Patent No. 4,379,910, and polycarbonate resins made from fluorinated diphenols. Among these, polytetrafluoroethylene (hereinafter, sometimes referred to as PTFE) is preferred.

[0108] PTFE with fibrillation ability has an extremely high molecular weight and exhibits a tendency to bond together to form fibers through external forces such as shear force. Its molecular weight, calculated from standard specific gravity, is between 1 million and 10 million, more preferably between 2 million and 9 million. In addition to solid form, the aforementioned PTFE can also be used in aqueous dispersion form. Furthermore, to improve dispersibility in resins and obtain good flame retardancy and mechanical properties, the aforementioned PTFE with fibrillation ability can also be used in PTFE mixtures with other resins.

[0109] Commercially available PTFE products with fibrillation capabilities include, for example, Teflon 6J (registered trademark) from Mitsui-DuPont Fluoropolymers, Ltd., and Polyflon MPA FA500 and F-201L from Daikin Industries, Ltd. Commercially available aqueous dispersions of PTFE include Fluon AD-1 and AD-936 from Asahi ICI Fluoropolymers, Ltd., Fluon D-1 and D-2 from Daikin Industries, Ltd., and Teflon 31J (registered trademark) from Mitsui-DuPont Fluoropolymers, Ltd.

[0110] As a mixed form of PTFE, PTFE obtained by the following methods can be used: (1) a method of co-precipitating a co-aggregated mixture by mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer (the method described in Japanese Patent Application Publication No. 60-258263, Japanese Patent Application Publication No. 63-154744, etc.); (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (the method described in Japanese Patent Application Publication No. 4-272957); (3) uniformly mixing an aqueous dispersion of PTFE with a solution of organic polymer particles. Methods for simultaneously removing each medium from the above mixture (methods described in Japanese Patent Application Publication No. 06-220210, Japanese Patent Application Publication No. 08-188653, etc.), (4) methods for polymerizing monomers that form organic polymers in an aqueous dispersion of PTFE (methods described in Japanese Patent Application Publication No. 9-95583), and (5) methods for uniformly mixing an aqueous dispersion of PTFE with an organic polymer dispersion, and then further polymerizing vinyl monomers in the mixed dispersion to obtain a mixture (methods described in Japanese Patent Application Publication No. 11-29679, etc.). Commercially available products of these mixed forms of PTFE include Mitsubishi Rayon Co., Ltd.'s "Metablen A3800" (trade name) and GE Specialty Chemicals' "BLENDEX B449" (trade name).

[0111] As for the proportion of PTFE in the mixed form, in 100% by weight of the PTFE mixture, PTFE is preferably 1 to 60% by weight, more preferably 5 to 55% by weight. When the proportion of PTFE is within the above range, good dispersibility of PTFE can be achieved. It should be noted that the content of component D represents the amount of anti-drip agent by net weight, and in the case of PTFE in the mixed form, it represents the amount of PTFE by net weight.

[0112] The content of component D is 0.1 to 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight, and more preferably 0.1 to 0.2 parts by weight, relative to 100 parts by weight of the resin component. If the amount of anti-drip agent exceeds the above range and is too small, the flame retardancy is insufficient. On the other hand, if the amount of anti-drip agent exceeds the above range and is excessive, the low-temperature impact resistance and the retention rate of physical properties after water exposure are poor.

[0113] (Other additives)

[0114] Furthermore, the resin composition of the present invention can also be combined with ultraviolet absorbers, heat stabilizers, mold release agents, etc.

[0115] (i) Ultraviolet absorbers

[0116] As ultraviolet absorbers, specifically for benzophenone-based compounds, examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonate sodium salt, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxylbenzophenone, etc. As ultraviolet absorbers, specifically for benzotriazole series, examples include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol], 2-(2 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolebenzene), 2,2'-p-phenylenebis(1,3-benzotriazole) Polymers having a 2-hydroxyphenyl-2H-benzotriazole backbone include 2-(2'-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole, copolymers of 2-(2'-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole with vinyl monomers capable of copolymerizing with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloyloxyethylphenyl)-2H-benzotriazole with vinyl monomers capable of copolymerizing with the monomer. As ultraviolet absorbers, specifically for hydroxyphenyl triazine compounds, examples include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methoxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethoxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propoxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butoxyphenol. Further examples include 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, where the phenyl group of the above-mentioned compounds is 2,4-dimethylphenyl. As a UV absorber, specifically for cyclic imine esters, 2,2'-p-phenylenebis(3,1-benzo[a]) can be exemplified, for example. Azine-4-one), 2,2'-m-phenylenebis(3,1-benzo[] (azinone-4-one) and 2,2'-p,p'-diphenylenebis(3,1-benzoxane) Examples of UV absorbers include aziridine-4-one, etc. Specifically, for cyanoacrylate-based UV absorbers, examples include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, etc. Furthermore, the aforementioned UV absorbers can also be polymer-type UV absorbers obtained by copolymerizing the aforementioned UV-absorbing monomers and / or photostable monomers with monomers such as (meth)acrylate alkyl esters using a free radical polymerizable monomer compound structure. As the aforementioned UV-absorbing monomers, compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imine ester skeleton, and a cyanoacrylate skeleton in the ester substituents of the (meth)acrylate are preferred examples. Of the above, benzotriazole and hydroxyphenyltriazine derivatives are preferred in terms of UV absorption capacity, while cyclic imide and cyanoacrylate derivatives are preferred in terms of heat resistance and colorfastness. Specifically, examples include CHEMIPRO Chemical Co., Ltd.'s "KEMISORB 79" and BASF Japan Co., Ltd.'s "Tinuvin 234". These UV absorbers can be used alone or in mixtures of two or more.

[0117] The content of the ultraviolet absorber relative to 100 parts by weight of the resin component is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.05 to 1 part by weight, and particularly preferably 0.05 to 0.5 parts by weight. When the content is less than 0.01 parts by weight, the durability is insufficient; if it exceeds 3 parts by weight, the flame retardancy and durability may sometimes be insufficient.

[0118] (ii) Heat stabilizers

[0119] Various known stabilizers can be incorporated into the resin composition of the present invention. Examples of stabilizers include phosphorus-based stabilizers and hindered phenolic stabilizers.

[0120] (ii-i) Phosphorus stabilizers

[0121] The resin composition of the present invention preferably incorporates a phosphorus-based stabilizer to improve thermal stability, mechanical properties, color, and molding stability during manufacturing or molding, without promoting hydrolysis. Examples of phosphorus-based stabilizers include phosphoric acid, phosphorous acid, phosphonic acid, phosphonic acid and their esters, and tert-phosphine.

[0122] Specifically, examples of phosphate ester stabilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyltoluene phosphate, diphenylmono-o-biphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate.

[0123] Examples of phosphite stabilizers include triphenyl phosphite, tri(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri(octadecyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylene bis(4,6-di-tert-butylphenyl)octyl phosphite, tri(diethylphenyl) phosphite, tri(diisopropylphenyl) phosphite, and tri(di-n-butylphenyl) phosphite. Phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, distearate pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, etc.

[0124] Furthermore, as other phosphite stabilizers, phosphite stabilizers that have a cyclic structure due to reaction with diphenols can also be used. Examples include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite, and 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite.

[0125] Examples of phosphonite stabilizers include tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphonite, tetra(2,4-di-tert-butylphenyl)-4,3'-biphenyl diphosphonite, tetra(2,4-di-tert-butylphenyl)-3,3'-biphenyl diphosphonite, tetra(2,6-di-tert-butylphenyl)-4,4'-biphenyl diphosphonite, tetra(2,6-di-tert-butylphenyl)-4,3'-biphenyl diphosphonite, tetra(2,6-di-tert-butylphenyl)-3,3'-biphenyl diphosphonite, and bis(2,4-di-tert-butylphenyl)-4-phenyl Phosphite esters, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphite esters, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphite esters, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphite esters, bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphite esters, etc., are preferred, with tetra(di-tert-butylphenyl)-biphenyl-phosphite esters and bis(di-tert-butylphenyl)-phenyl-phenylphosphite esters being more preferred. The above-mentioned phosphite ester compounds can preferably be used in combination with the above-mentioned phosphite ester compounds having aryl groups substituted with two or more alkyl groups. Examples of phosphite ester compounds include dimethyl phenylphosphonate, diethyl phenylphosphonate, and dipropyl phenylphosphonate.

[0126] Examples of tertiary phosphine stabilizers include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. Triphenylphosphine is a particularly preferred tertiary phosphine stabilizer. Not only can one of the above phosphorus stabilizers be used, but two or more can also be used in combination.

[0127] (ii-ii) Hindered phenolic stabilizers

[0128] The resin composition of the present invention can be further formulated with hindered phenolic stabilizers. This formulation can, for example, suppress color fading during molding and processing, and color fading over long-term use. Examples of hindered phenolic stabilizers include α-tocopherol, butylated hydroxytoluene, mustard alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2 2'-Methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylenebis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-butylidenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl] terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl) [Propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylaniline)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris(2-[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetra[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane, etc. These are all readily available. The above-mentioned hindered phenolic stabilizers can be used alone or in combination of two or more. The combined amount of the phosphorus-based stabilizer and the hindered phenolic stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight, and even more preferably 0.005 to 0.3 parts by weight, respectively, relative to 100 parts by weight of the resin component. If the amount of stabilizer is too small compared to the above ranges, it is difficult to obtain a good stabilizing effect; if it exceeds the above ranges and is excessive, the physical properties of the composition may sometimes decrease.

[0129] (ii-iii) Heat stabilizers other than those mentioned above

[0130] Other heat stabilizers besides the phosphorus-based stabilizers and hindered phenolic stabilizers described above can also be incorporated into the resin composition of the present invention. Examples of these other heat stabilizers include, for instance, lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Details of these stabilizers are described in Japanese Patent Application Publication No. 7-233160. The above-mentioned compound is commercially available in the form of Irganox HP-136 (trademark, manufactured by CIBA SPECIALTYCHEMICALS). Furthermore, stabilizers prepared by mixing this compound with various phosphite compounds and hindered phenolic compounds are also commercially available. For example, Irganox HP-2921 manufactured by the aforementioned company is a preferred example. The amount of lactone-based stabilizer incorporated relative to 100 parts by weight of the resin component is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight. In addition, other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate. The amount of the above-mentioned sulfur-containing stabilizer relative to 100 parts by weight of the resin component is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight. An epoxy compound may be incorporated into the resin composition of the present invention as needed. The epoxy compound is incorporated for the purpose of inhibiting mold corrosion, and essentially all epoxy compounds having epoxy functional groups can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, copolymers of methyl methacrylate and glycidyl methacrylate, and copolymers of styrene and glycidyl methacrylate. The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and even more preferably 0.005 to 0.1 parts by weight, relative to 100 parts by weight of the resin component.

[0131] (iii) Release agent

[0132] In the resin composition of the present invention, a release agent may be further incorporated to improve the productivity during molding and reduce the strain of the molded article. Known release agents can be used as such release agents. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-olefin polymers, etc., and polyolefin waxes modified with compounds containing acid-modified functional groups may also be used), organosilicon compounds, fluorinated compounds (fluorinated oils, such as polyfluoroalkyl ethers), paraffin wax, beeswax, etc. Among these, fatty acid esters are preferred release agents. These fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohols may be monohydric alcohols or polyhydric alcohols with two or more carbon atoms. Furthermore, the number of carbon atoms in the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of monohydric alcohols include dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, eicosyl alcohol, tetradecyl alcohol, cetyl alcohol, and triacontanol. Examples of the aforementioned polyols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerides to hexaglycerides), bis(trimethylol)propane, xylitol, sorbitol, and mannitol. Polyols are more preferably found in the fatty acid esters of the present invention. On the other hand, the aliphatic carboxylic acid is preferably aliphatic carboxylic acid with 3 to 32 carbon atoms, and particularly preferably aliphatic carboxylic acids with 10 to 22 carbon atoms. Examples of such aliphatic carboxylic acids include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, benzanoic acid, eicosanoic acid, and docosanoic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetyl oleate. Of the above, aliphatic carboxylic acids with 14 to 20 carbon atoms are preferred. Saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred. The aforementioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are typically manufactured from natural oils such as animal fats (e.g., tallow and lard) and vegetable oils (e.g., palm oil and sunflower oil). Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the manufacture of the fatty acid esters of the present invention, it is also preferable to use aliphatic carboxylic acids, especially stearic acid and palmitic acid, which are manufactured from the aforementioned natural oils and are composed of mixtures containing other carboxylic acid components. The fatty acid ester can be either a partial ester or a full ester. However, partial esters generally have a higher hydroxyl value, which easily induces resin decomposition at high temperatures; therefore, a full ester is more preferred. From the perspective of thermal stability, the acid value of the fatty acid esters of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12. It should be noted that the acid value can essentially be 0. Furthermore, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Furthermore, the iodine value is preferably 10 or less. It should be noted that the iodine value can actually be taken as 0.These properties can be determined using the methods specified in JIS K 0070.

[0133] The content of the release agent relative to 100 parts by weight of the resin component is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 2.5 parts by weight.

[0134] (iv) Dyes and Pigments

[0135] The polycarbonate resin composition of the present invention can be further contained with various dyes and pigments to provide molded articles exhibiting diverse design possibilities. Examples of dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as iron blue, violet ketone dyes, quinoline dyes, quinacridone dyes, and dioxinone dyes. Zine dyes, isoindolinone dyes, and phthalocyanine dyes, etc. Furthermore, the polycarbonate resin composition of the present invention can also be combined with metallic pigments to obtain better metallic colors. Aluminum powder is preferred as a metallic pigment. In addition, by combining it with a fluorescent brightener or other luminescent fluorescent dye, a further improved design effect of producing luminescent color can be achieved. The content of the aforementioned dye pigments relative to 100 parts by weight of the resin component is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 parts by weight.

[0136] (v) Fluorescent whitening agents

[0137] The fluorescent whitening agent in the resin composition of the present invention is not particularly limited as long as it is a fluorescent whitening agent used to improve the hue of the resin, etc., to white or bluish-white. Examples include stilbene-based, benzimidazole-based, and benzo[…]. Zazole series, naphthalenedicarboximide series, rhodamine series, coumarin series, Zine compounds, etc. Specifically, examples include CIFluorescent Brightener 219:1, Eastman Chemical's EASTOBRITE OB-1, and Showa Chemical Co., Ltd.'s "Hakkol PSR," etc. Here, the fluorescent whitening agent has the function of absorbing the ultraviolet energy of light and radiating that energy into the visible portion. The content of the fluorescent whitening agent relative to 100 parts by weight of the resin component is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight. Even if it exceeds 0.1 parts by weight, the color-improving effect of the composition is small.

[0138] (vi) Compounds with the ability to absorb thermal rays

[0139] The polycarbonate resin composition of the present invention may contain compounds with thermal radiation absorption capabilities. Suitable examples of such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, ammonium oxide, and titanium oxide, metal boride-based absorbers such as lanthanum boride, cerium boride and tungsten boride, and tungsten oxide-based near-infrared absorbers, as well as carbon fillers. For example, MIR-362 manufactured by Mitsui Chemicals Co., Ltd. is commercially available and readily accessible as a phthalocyanine-based near-infrared absorber. Examples of carbon fillers include carbon black, graphite (including both natural and artificial graphite), and fullerenes, with carbon black and graphite being preferred. These can be used individually or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber, based on 100 parts by weight of the resin component, is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and even more preferably 0.001 to 0.07 parts by weight. The content of the metal oxide-based near-infrared absorber, the metal boride-based near-infrared absorber, and the carbon filler in the polycarbonate resin composition of the present invention is preferably in the range of 0.1 to 200 ppm (by weight), more preferably in the range of 0.5 to 100 ppm.

[0140] (vii) Light diffusing agents

[0141] The polycarbonate resin composition of the present invention can be combined with a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymeric microparticles, low-refractive-index inorganic microparticles such as calcium carbonate, and their complexes. The aforementioned polymeric microparticles are known microparticles as light diffusing agents for polycarbonate resins. More preferably, examples include acrylic cross-linked particles with a particle size of a few μm and organosilicon cross-linked particles represented by polyorganosilsesquioxanes. Examples of the shape of the light diffusing agent include spherical, disc-shaped, cylindrical, and amorphous shapes. The aforementioned spherical shapes do not need to be perfectly spherical and include deformed spheres, while the aforementioned cylindrical shapes include cubes. Spherical light diffusing agents are preferred, and the more uniform their particle size, the more preferred. The content of the light diffusing agent is based on 100 parts by weight of the resin component, preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 3 parts by weight. It should be noted that two or more light diffusing agents can be used together.

[0142] (viii) White pigment for high light reflection

[0143] The polycarbonate resin composition of the present invention can be combined with a white pigment for high light reflectance to impart a light-reflecting effect. As the aforementioned white pigment, titanium dioxide (especially titanium dioxide treated with organic surface treatment agents such as organosilicon) pigment is particularly preferred. The content of the aforementioned white pigment for high light reflectance is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of the resin component. It should be noted that two or more types of white pigment for high light reflectance can be used together.

[0144] (ix) Antistatic agent

[0145] Sometimes, antistatic properties are required for the polycarbonate resin composition of the present invention. In such cases, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) dodecylbenzenesulfonic acid. Arylsulfonic acids, represented by salts Salts and alkyl sulfonic acids Salts and other organic sulfonic acids Salt, and tetrafluoroboric acid Boric acid salts Salt. The salt content relative to 100 parts by weight of the resin component is preferably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably in the range of 1.5 to 3 parts by weight. Examples of antistatic agents include (2) alkali (earth) metal salts of organic sulfonates such as lithium organic sulfonates, sodium organic sulfonates, potassium organic sulfonates, cesium organic sulfonates, rubidium organic sulfonates, calcium organic sulfonates, magnesium organic sulfonates, and barium organic sulfonates. These metal salts can also be used as flame retardants. More specifically, examples of these metal salts include metal salts of dodecylbenzene sulfonic acid and perfluoroalkane sulfonic acids. The content of the alkali (earth) metal salt of the organic sulfonate is preferably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight, based on 100 parts by weight of the resin component. Alkali metal salts such as potassium, cesium, and rubidium are particularly preferred.

[0146] Examples of antistatic agents include, for example, organic sulfonate ammonium salts such as (3) alkyl sulfonate ammonium salts and aryl sulfonate ammonium salts. The ammonium salt is preferably 0.05 parts by weight or less, based on 100 parts by weight of the resin component. Examples of antistatic agents include, for example, polymers containing poly(oxyethylene) glycol components, such as polyether ester amides. The polymer is preferably 5 parts by weight or less, based on 100 parts by weight of the resin component.

[0147] (x) Other additives

[0148] The polycarbonate resin composition of the present invention can be combined with other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalyst-based antifouling agents, and photochromic agents.

[0149] (Preparation of the resin composition)

[0150] In manufacturing the resin composition of the present invention, any method may be used. For example, the following method may be used: after fully mixing components A to D and any other additives using a premixing device such as a V-type mixer, Henschel mixer, mechanochemical apparatus, or extrusion mixer, the premix is ​​granulated as needed using an extruder, briquetting machine, etc., then melt-blended using a melt-blending machine such as a vented twin-shaft extruder, and finally granulated using a granulator.

[0151] In addition, methods such as supplying each component independently to a melt-mixing mill, such as a vented twin-screw extruder, and methods such as premixing a portion of each component and then independently supplying it to the melt-mixing mill along with the remaining components can be cited. As a method of premixing a portion of each component, examples include premixing components other than A and B and then mixing them into the resin of components A and B, or directly supplying them to the extruder.

[0152] As a premixing method, one can exemplify the following: for example, when a component in powder form is included as component B, a portion of the powder is blended with a formulated additive to produce a masterbatch of the additive diluted with powder, and the masterbatch is then used. Another example is a method of independently supplying a component from the melt extruder midway through the process. It should be noted that when a liquid component is present in the formulated components, a so-called liquid injection device or liquid addition device can be used in the supply to the melt extruder.

[0153] As an extruder, an extruder having an exhaust port capable of degassing moisture from the raw material and volatile gases generated from the molten resin is preferred. A vacuum pump for efficiently discharging the generated moisture and volatile gases from the exhaust port to the outside of the extruder is also preferred. Alternatively, a wire mesh for removing foreign matter mixed into the extruded raw material can be provided in the area in front of the extruder die to remove foreign matter from the resin composition. Examples of such wire mesh include metal wire mesh, a screen changer, and sintered metal plates (disc filters, etc.).

[0154] In addition to twin-screw extruders, other examples of melt mixing machines include Banbury internal mixers, mixing drums, single-screw extruders, and multi-screw extruders with three or more shafts.

[0155] As described above, the extruded resin is directly cut into granules, or the filament is formed and then cut into granules using a granulator. When it is necessary to reduce the influence of external dust during granulation, it is preferable to purify the atmosphere around the extruder. Furthermore, in the manufacture of the granules, various methods already proposed for optical disc polycarbonate resins can be used to appropriately reduce the particle shape distribution, reduce miscutting, reduce the amount of fine powder generated during transport or conveying, and reduce the amount of air bubbles (vacuum bubbles) generated inside the filament and granules. These formulations can achieve high recyclability of molding and reduce the occurrence of defects such as silver streaks. In addition, the shape of the granules can be a general shape such as cylindrical, prismatic, and spherical, but cylindrical is more preferred. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 3.5 mm.

[0156] (Molded articles made of the resin composition of the present invention)

[0157] The resin composition of this invention can typically be used to injection mold the particles obtained by the above methods to manufacture various products. In the injection molding process described above, not only conventional molding methods can be used, but also, depending on the purpose, injection compression molding, injection pressurization molding, gas-assisted injection molding, foam molding (including molding via supercritical fluid injection), insert molding, in-mold coating molding, heat-insulated mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding can be appropriately employed to obtain molded articles. The advantages of these various molding methods are well known. Furthermore, molding can be performed using either a cold runner or a hot runner system.

[0158] (Impact resistance)

[0159] For the polycarbonate resin composition of the present invention, the value obtained by measuring the notched Charpy impact strength according to ISO 179 is preferably 40 kJ / m. 2 The above, more preferably 50 kJ / m 2 The above is further optimized to 60 kJ / m 2 That's all. If the value obtained by measuring the Charpy impact strength with a notch is less than the appropriate range, it will be difficult to apply it in various uses.

[0160] (Ultra-low temperature impact strength)

[0161] For the polycarbonate resin composition of the present invention, the value obtained by measuring the notched Charpy impact strength of a test piece cooled to -30°C according to ISO 179 is preferably 25 kJ / m. 2 The above, more preferably 30 kJ / m 2The above is further optimized to 35 kJ / m 2 The above applies. If the measured Charpy impact strength with a notch is less than the appropriate range, it is difficult to apply it to outdoor structural components, various housing components, and automotive-related components intended for extremely cold regions.

[0162] (Durability)

[0163] For the polycarbonate resin composition of the present invention, the retention rate expressed by the following formula, obtained from the value of the notched Charpy impact strength of the test piece before and after the water exposure test according to UL746C, is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. If the retention rate is less than the appropriate range, it is difficult to use in structural components, various housing components, and automotive-related components for outdoor applications.

[0164] Retention rate (%) = (Charpy impact strength after water exposure test / Charpy impact strength before water exposure test) × 100

[0165] Furthermore, it is preferable to maintain the UL94 flame retardant rating of the test piece before and after the water exposure test according to UL746C. If the flame retardant rating cannot be maintained, it is difficult to use it in structural components, various housing components, and automotive-related components intended for outdoor applications.

[0166] The present invention is carried out by means of preferred embodiments that incorporate the above-described elements, for example, as described in the following embodiments. Of course, the present invention is not limited to these embodiments.

[0167] Example

[0168] The present invention will now be described in more detail with reference to embodiments. Unless otherwise specified, parts in the embodiments refer to parts by weight, and % refers to weight percentages. It should be noted that the evaluation is performed according to the method described below.

[0169] (1) Evaluation of polycarbonate-polydiorganosiloxane copolymer

[0170] (i) Viscosity-average molecular weight

[0171] The specific viscosity (η) was calculated using the following formula from a solution of 0.7 g of polycarbonate-polydiorganosiloxane copolymer dissolved in 100 ml of dichloromethane at 20 °C using an Ostwald viscometer. SP ),

[0172] Specific viscosity (η) SP )=(t-t0) / t0

[0173] [t0 is the number of seconds for dichloromethane to drop, and t is the number of seconds for the sample solution to drop.]

[0174] The specific viscosity (η) is obtained from SP The viscosity-average molecular weight Mv can be calculated using the following mathematical formula.

[0175] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0176] [η] = 1.23 × 10 －4 Mv 0.83

[0177] c = 0.7

[0178] (ii) Total transmittance

[0179] Using a vented twin-screw extruder (Kobe Steel KTX-30, diameter...) The polycarbonate-polydiorganosiloxane copolymer was mixed at 280°C and granulated. The resulting granules were then hot-air dried at 120°C for 5 hours. Using an injection molding machine (JSW J-75EIII, manufactured by Nippon Steel Works Co., Ltd.), three sections of the molded sheet were formed at a molding temperature of 280°C, a mold temperature of 80°C, and a molding cycle of 50 seconds. The sections had a width of 50 mm, a length of 90 mm, and thicknesses from the gate side of 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm), with an arithmetic mean roughness (Ra) of 0.03 μm. The total light transmittance of the 2.0 mm thick section of the three sections was measured using a Haze Meter NDH 2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) according to ASTM D1003.

[0180] (iii) Average size and normalized dispersion of polydiorganosiloxane domains

[0181] Using the three-segment template prepared in (ii), the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane structural domains at the intersection of 5 mm from the end and 5 mm from the side of the 1.0 mm thick section were measured using an X-ray diffraction apparatus (RINT-TTRII, Rigaku Corporation). CuKα characteristic X-rays (wavelength 0.1541841 nm) were used as the X-ray source at a tube voltage of 50 kV and a tube current of 300 mA. The small-angle scattering optical system was: Slit: 1st 0.03 mm, HS 10 mm, SS 0.2 mm, RS 0.1 mm. Measurements were performed using an asymmetric scanning method (2θ scan) with an FT of 0.01° step, 4 sec / step, and a scan range of 0.06–3°. Curve fitting analysis was performed using the small-angle scattering analysis software NANO-Solver (Ver. 3.3), manufactured by Rigaku Corporation. The analysis is as follows: It is assumed that the polycarbonate matrix contains aggregated spherical domains of polydiorganosiloxane with variations in particle size distribution, resulting in a polycarbonate matrix density of 1.2 g / cm³. 3 This resulted in a polydiorganosiloxane domain density of 1.1 g / cm³. 3 It is implemented using an independent particle model that does not consider inter-particle interactions (inter-particle interference).

[0182] (2) Evaluation of resin composition

[0183] (i) Durability

[0184] Using a 3 mm thick ISO bending test piece obtained by the following method, the notched Charpy impact strength was determined according to ISO 179 at 23°C. Next, the bending test piece was immersed in warm water at 70°C for 7 days according to the UL 746C water exposure test established by Underwriters Laboratories, and then the notched Charpy impact strength was determined according to ISO 179 at 23°C. Based on the results, the retention rate of the notched Charpy impact strength was calculated using the following formula.

[0185] Retention rate (%) = (Charpy impact strength after water exposure test / Charpy impact strength before water exposure test) × 100

[0186] (ii) Charpy impact strength at -30℃

[0187] Using ISO bending test specimens with a thickness of 3 mm obtained by the following method, the Charpy impact strength with notches was determined in accordance with ISO 179 at an atmosphere of -30°C.

[0188] (iii) Flame retardancy

[0189] According to the UL94 vertical burning test established by Underwriters Laboratories, a 1.5 mm thick molded article obtained by the following method was subjected to a burning test. Next, the bending test piece was immersed in warm water at 70°C for 7 days according to the UL746C water exposure test established by Underwriters Laboratories, and then evaluated in the same manner. The results were evaluated as V-0, V-1, V-2, and not V.

[0190] [Examples 1-12, Comparative Examples 1-11]

[0191] Components A through D and various additives, as shown in Tables 1 and 2, were uniformly mixed using a mixer and then melt-blended using a vented twin-screw extruder to obtain granules. Each additive was pre-mixed with the polycarbonate resin at a concentration of 10 to 100 times the formulation amount before being fully mixed using the mixer. The vented twin-screw extruder used was a Kobe Steel KTX-30 (diameter...) The wire rod was extruded under the following conditions: barrel and die temperatures of 280°C, screw speed of 150 rpm, discharge rate of 20 kg / h, and exhaust suction of 3 kPa. After cooling in a water bath, the wire rod was cut into granules using a pelletizer. The resulting granules were dried in a hot air circulating dryer at 100°C for 6 hours, and then molded into ISO bending test pieces (ISO179) and UL test pieces using an injection molding machine (manufactured by Nippon Steel Works Co., Ltd., JSW J-75EIII) at a barrel temperature of 280°C and a die temperature of 80°C. The various evaluation results are shown in Tables 1 and 2.

[0192] [Table 1]

[0193]

[0194] [Table 2]

[0195]

[0196] It should be noted that the following substances are used as raw materials.

[0197] (A ingredient)

[0198] A-1: Polycarbonate-polydiorganosiloxane copolymer (viscosity-average molecular weight 23900, PDMS content 8.4%, PDMS degree of polymerization 37, average domain size of polydiorganosiloxane domains 10.8 nm, normalized dispersion 18.9, total transmittance 89.6%)

[0199] A-2: Polycarbonate-polydiorganosiloxane copolymer (viscosity-average molecular weight 19700, PDMS content 8.4%, PDMS degree of polymerization 37, average domain size of polydiorganosiloxane domains 10.1 nm, normalized dispersion 18.5, total transmittance 89.7%)

[0200] A-3: A polycarbonate-polydiorganosiloxane copolymer (bisphenol A) made using 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), a bisphenol (I) represented as a carbonate constituent unit of derivatization formula [1], and a polydiorganosiloxane (II) represented as a carbonate constituent unit of derivatization formula [3], represented by the following formula [8] (Shin-Etsu Chemical Industry Co., Ltd. X-22-1821). The copolymer has a viscosity-average molecular weight of 35,000, PDMS content of 8.4%, PDMS degree of polymerization of 37, average domain size of polydiorganosiloxane domain of 12.1 nm, normalized dispersion of 18.0, and total transmittance of 89.3%.

[0201]

[0202] (Component B)

[0203] B-1: Polycarbonate resin (a polycarbonate resin powder with a viscosity-average molecular weight of 30,000, produced from bisphenol A and phosgene using conventional methods).

[0204] B-2: Polycarbonate resin (a polycarbonate resin powder with a viscosity-average molecular weight of 23,900, produced from bisphenol A and phosgene using conventional methods).

[0205] B-3: Polycarbonate resin (a polycarbonate resin powder with a viscosity-average molecular weight of 22,400, produced from bisphenol A and phosgene using conventional methods).

[0206] B-4: Polycarbonate resin (a polycarbonate resin powder with a viscosity-average molecular weight of 19,700, produced by conventional methods from bisphenol A and phosgene).

[0207] B-5: Polycarbonate resin (a polycarbonate resin powder with a viscosity-average molecular weight of 16,000, produced from bisphenol A and phosgene using conventional methods).

[0208] B-6: Polycarbonate resin (a polycarbonate resin powder with a viscosity-average molecular weight of 14,000, produced by conventional methods from bisphenol A and phosgene).

[0209] (Component C)

[0210] C-1: Cyclophenoxyphosphazene with a content of 68 mol% for the trimer of n=3, 18 mol% for the tetramer of n=4, and 14 mol% for the polymer of n=5 or more in the following formula (7).

[0211] C-2: Cyclophenoxyphosphazene with n=3 trimer content of 100 mol% in formula (7) below.

[0212]

[0213] [In the formula, Ph represents phenyl]

[0214] C-3: A phosphate ester with bisphenol A bis(diphenyl phosphate) as the main component (CR-741 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)

[0215] (Component D)

[0216] D-1: PTFE (Polyflon MPA FA500H manufactured by Daikin Industries, Ltd. (trade name))

[0217] D-2: Coated PTFE (polytetrafluoroethylene coated with styrene-acrylonitrile copolymer (polytetrafluoroethylene content 50% by weight), manufactured by Shine Polymer SN3307PF (trade name))

[0218] (Other ingredients)

[0219] Release agent: Pentaerythritol fatty acid ester-based release agent (Rikester EW-400, manufactured by Riken Vitamin Co., Ltd., trade name)

[0220] UV absorber: (BASF's TINUVIN 234 (trade name))

[0221] Heat stabilizer-1: Phenolic heat stabilizer (BASF IRGANOX 1076 (trade name))

[0222] Heat stabilizer - 2: Phosphorus-based heat stabilizer (BASF IRGAFOS168 (trade name))

Claims

1. A polycarbonate resin composition, characterized in that, Relative to 100 parts by weight of a resin component consisting of 10-90 parts by weight of (A) polycarbonate-polydiorganosiloxane copolymer (component A) and 90-10 parts by weight of (B) polycarbonate resin (component B), the resin component contains 0.5-7 parts by weight of (C) phosphazene compound (component C) and 0.1-0.5 parts by weight of (D) fluorinated anti-drip agent (component D), wherein component C is a cyclic phenoxyphosphazene, the viscosity-average molecular weight ratio of component A to component B (Mv of component A / Mv of component B) is 1-1.5, and component A satisfies (i)-(ii) below. (i) is a polycarbonate-polydiorganosiloxane copolymer composed of polycarbonate blocks represented by the following general formula [1] and polydiorganosiloxane blocks represented by the following general formula [3]. (ii) The viscosity-average molecular weight is 23,000 to 30,000. In the general formula [1], R 1 and R 2 Each group independently represents a group selected from hydrogen atom, halogen atom, alkyl group with 1 to 18 carbon atoms, alkoxy group with 1 to 18 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 14 carbon atoms, aryloxy group with 6 to 14 carbon atoms, aralkyl group with 7 to 20 carbon atoms, arylalkoxy group with 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and carboxyl group. When multiple groups are present, they may be the same or different. e and f are integers from 1 to 4. W is a single bond or at least one group selected from the groups represented by the following general formula [2]. In the general formula [2], R 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 Each of these groups independently represents a group selected from hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms, R 19 and R 20 Each group independently represents a group selected from hydrogen atoms, halogen atoms, alkyl groups with 1 to 18 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, cycloalkoxy groups with 6 to 20 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 14 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, arylalkoxy groups with 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, and carboxyl groups. When multiple groups are present, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7. In the general formula [3], R 3 R 4 R 5 R 6 R 7 and R 8 Each is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R 9 and R 10 Each of the following is independently composed of a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, p being a natural number, q being 0 or a natural number, an average chain length of p+q being a natural number of 30 to 60, and X being a divalent aliphatic group with 2 to 8 carbon atoms.

2. The polycarbonate resin composition according to claim 1, wherein, Component A is a polycarbonate-polydiorganosiloxane copolymer, wherein the polycarbonate-polydiorganosiloxane copolymer is a condensed structure formed by dispersing polydiorganosiloxane domains in a polycarbonate matrix, the average size of the polydiorganosiloxane domains is 5-15 nm, the normalized dispersion is less than 25%, and the total light transmittance of the polycarbonate-polydiorganosiloxane copolymer is more than 88%.

3. The polycarbonate resin composition according to claim 1 or 2, wherein, Component C is a cyclic phenoxyphosphazene containing more than 98.5 mol% of cyclic trimers of phosphazene.

4. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 3.

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