Polycarbonate resin composition and molded article comprising same

Abstract

The present invention provides: a polycarbonate resin composition that excels in flame retardancy, moldability, low heat build-up, and low smoke emission; and a molded article comprising the same. A polycarbonate resin composition according to the present invention either: contains (A) a resin (component A) having a carbonate structural unit derived from a dihydric phenol compound, (B) a resin (component B) having a siloxane structural unit, and (C) a resin (component C) having 9,9-bis(4-hydroxy-3-alkylphenyl) fluorene or a structural unit derived therefrom, wherein per 100 parts by mass of the resin composition, the content of Si element derived from the siloxane structural unit ranges from 0.3 to 30.0 parts by mass and the content of the C component ranges from 1.0 to 40 parts by mass; or contains the component A and a resin (component E) having a prescribed structural unit E, wherein the content of the structural unit E is 5 to 70 parts by mass.

Description

Polycarbonate resin composition and molded article made thereof

[0001] The present invention relates to a polycarbonate resin composition having excellent flame retardancy and moldability, a polycarbonate resin composition having excellent flame retardancy, low heat generation, and low smoke generation, and a molded article made from the same.

[0002] Polycarbonate resin has excellent transparency, impact resistance, heat resistance, and dimensional stability, and is therefore used as an engineering plastic in a wide range of fields, including housings for electrical and electronic devices, interior and exterior parts for automobiles, building materials, furniture, musical instruments, and miscellaneous goods.

[0003] In recent years, lightweight and easy processability have become major requirements for interior materials for aircraft and railway vehicles. Polycarbonate resin has attracted attention as a material that meets these requirements, but conventional polycarbonate resins have the problem of being unable to meet the strict flame retardancy standards required for aircraft and railway vehicle interior materials. To solve this problem, many studies have been conducted on adding flame retardants, resins with high limiting oxygen index (LOI), or inorganic fillers to polycarbonate resins. Patent Document 1 discloses a method for improving flame retardancy by adding a bisphenol C polycarbonate, a phosphorus-based flame retardant, and a silicone-based flame retardant to polycarbonate resin. However, the flame retardancy achieved by this method is not sufficient. Patent Document 2 also discloses a method for improving flame retardancy by controlling the orientation angle of inorganic fillers in a resin sheet. However, this method also does not provide sufficient flame retardancy, and the processability is not excellent due to the need to control the filler orientation.

[0004] In recent years, there has been a strong demand for flame-retardant resin materials, particularly in applications such as office automation equipment and home appliances. To meet these demands, numerous flame-retardant studies have been conducted. Traditionally, in such polymer alloys, a combination of a halogen-based flame retardant containing a bromine atom or the like and a flame-retardant auxiliary such as antimony trioxide was commonly used. However, due to the problem of the generation of harmful substances during combustion, flame-retardant materials that do not contain halogen-based compounds have been actively studied. For example, a method of blending triphenyl phosphate and fibril-forming polytetrafluoroethylene with a polymer alloy containing polycarbonate resin (Patent Document 3) and a method of blending a phosphate-based oligomer, which is a condensed phosphate ester (Patent Document 4), have been proposed. Meanwhile, in addition to these basic flame-retardant properties, there has also been an increasing demand for low heat generation and low smoke generation during combustion. Interior materials for aircraft and railway vehicles are required to satisfy all of these properties at a high level.

[0005] To solve these problems, for example, a method has been proposed in which a polyarylate resin, a silicone compound, and a phosphate ester are blended with a polycarbonate resin (Patent Document 5). However, the heat generation properties obtained by this method are insufficient, and there is no mention of smoke generation properties. Another method has been proposed in which a polycarbonate having a bisphenol C skeleton, a phosphorus-based flame retardant, and a silicone flame retardant are blended with a polycarbonate resin (Patent Document 6). However, the heat generation properties and smoke generation properties obtained by this method are insufficient, and there is no mention of flame retardancy.

[0006] International Publication No. 2018 / 047693 Patent No. 6568639 JP 2-32154 JP 2-115262 JP 2021-38298 Patent No. 6285085

[0007] The present invention provides a polycarbonate resin composition having excellent flame retardancy and moldability, a polycarbonate resin composition having excellent flame retardancy, low heat generation and low smoke generation, and a molded article made from the same.

[0008] According to the present invention, the above-mentioned object of the present invention is achieved by the following polycarbonate resin composition and molded article thereof.

[0009] (Structure 1) A polycarbonate resin composition comprising: (A) a polycarbonate resin having carbonate structural units derived from a dihydric phenol compound (Component A), (B) a resin having siloxane structural units (Component B), and (C) a resin having 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene or structural units derived therefrom (Component C), wherein, per 100 parts by mass of the polycarbonate resin composition, the amount of Si element derived from the siloxane structural units of Component B is in the range of 0.3 to 30.0 parts by mass, and the content of Component C is in the range of 1.0 to 40 parts by mass. (Structure 2) The polycarbonate resin composition according to Structure 1, further comprising: (D) 5 to 30 parts by mass of at least one inorganic filler (Component D) selected from the group consisting of talc, wollastonite, mica, and kaolin, per 100 parts by mass of the polycarbonate resin composition. (Structure 3) The polycarbonate resin composition according to Structure 1 or 2, wherein Component A comprises a polycarbonate resin having carbonate structural units derived from bisphenol A. (Structure 4) The polycarbonate resin composition according to any one of Structures 1 to 3, wherein Component B comprises a resin having siloxane structural units derived from polydiorganosiloxane. (Structure 5) The polycarbonate resin composition according to any one of Structures 1 to 4, wherein Component B comprises a polycarbonate copolymer obtained from raw materials bisphenol A and polydiorganosiloxane. (Structure 6) The polycarbonate resin composition according to any one of Structures 1 to 5, wherein the resin having structural units derived from 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene of Component C comprises a polycarbonate copolymer obtained from raw materials 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene and another dihydric phenol compound. (Configuration 7) The polycarbonate resin composition according to any one of Configurations 1 to 6, wherein the resin having a 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene structural unit of Component C includes a polycarbonate copolymer obtained from bisphenol A and 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene as raw materials.(Configuration 8) 50kW / m in accordance with ISO 5660-1. ２ The maximum average heat generation rate tested under the condition of heater irradiance of 90 kW / m and ignition is 90 kW / m ２ The polycarbonate resin composition according to any one of Configurations 1 to 7, which is as follows: (Configuration 9) A molded article formed from the polycarbonate resin composition according to any one of Configurations 1 to 8. (Configuration 10) The molded article according to claim 9, which is a railway vehicle interior component. (Configuration 11) A polycarbonate resin composition comprising: (A) a polycarbonate resin (component A) having a carbonate structural unit derived from a dihydric phenol compound, and (E) a resin (component E) having at least one structural unit selected from structural units represented by the following formulas (1) to (3) (structural unit E), wherein the polycarbonate resin composition contains at least one of the structural units E in an amount of 5 to 70 parts by mass per 100 parts by mass of the polycarbonate resin composition: In formulas (1) to (3), R １ ~R １２ represents an alkyl group, W represents the following formula (4), R １３ ~R ２２ represents a hydrogen atom or a methyl group: (Structure 1) The polycarbonate resin composition according to Structure 11, wherein W is a fluorene derivative. (Structure 13) The polycarbonate resin composition according to Structure 11 or 12, further comprising (B) a resin having siloxane structural units (Component B), wherein the amount of elemental Si derived from the siloxane structural units of Component B is 0.3 to 10.0 parts by mass per 100 parts by mass of the polycarbonate resin composition. (Structure 14) The polycarbonate resin composition according to any one of Structures 11 to 13, further comprising (D) 5 to 30 parts by mass of at least one inorganic filler (Component D) selected from the group consisting of talc, wollastonite, mica, and kaolin per 100 parts by mass of the polycarbonate resin composition. (Structure 15) A molded article formed from the polycarbonate resin composition according to any one of Structures 11 to 14. (Structure 16) The molded article according to Structure 15, which is a railway vehicle interior component.

[0010] The polycarbonate resin composition of the first invention is far superior in flame retardancy and moldability to conventional polycarbonate resin compositions, and is therefore widely useful in aviation applications, railway applications, and various other applications, and the industrial effects of the present invention are extremely significant. Also, the polycarbonate resin composition of the second invention is far superior in flame retardancy, low heat generation, and low smoke generation to conventional polycarbonate resin compositions, and is therefore widely useful in housing equipment applications, building materials applications, daily necessities applications, infrastructure equipment applications, automobiles, office automation / electrical equipment applications, aviation applications, railway applications, and various other applications, and the industrial effects of the present invention are extremely significant.

[0011] The present invention will be further described in detail below.

[0012] <First Invention> The polycarbonate resin composition of the first invention contains (A) a polycarbonate resin having carbonate structural units derived from a dihydric phenol compound (component A), (B) a resin having siloxane structural units (component B), and (C) a resin having 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene or structural units derived therefrom (component C), and preferably further contains (D) an inorganic filler (component D). Each component will be described below.

[0013] <(A) Polycarbonate Resin Having Carbonate Structural Units Derived from a Dihydric Phenol Compound (Component A)> The polycarbonate resin (Component A) having carbonate structural units derived from a dihydric phenol compound (A) used in the present invention can be obtained by reacting a dihydric phenol compound with a carbonate precursor. Examples of reaction methods include interfacial polycondensation, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. Note that the dihydric phenol compound does not include 9,9-bis{(4-hydroxy-3-alkyl)phenyl}fluorene, which will be described later.

[0014] Representative examples of the dihydric phenol compound used herein include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5-dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dimethyl)phenyl}propane, 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene benzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl ester, and these can be used alone or in combination of two or more.

[0015] Among these, polycarbonate homopolymers or polycarbonate copolymers having carbonate structural units derived from at least one dihydric phenol compound selected from the group consisting of bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferred, and those containing carbonate structural units derived from bisphenol A are even more preferred. In particular, polycarbonate homopolymers having carbonate structural units derived from bisphenol A, and polycarbonate copolymers having carbonate structural units derived from bisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, or α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferably used.

[0016] Carbonyl halides, carbonate esters, haloformates, etc. are used as carbonate precursors, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0017] When the dihydric phenol and the carbonate precursor are reacted by the interfacial polycondensation method or the melt transesterification method to produce the polycarbonate resin, a catalyst, a terminal terminator, an antioxidant for the dihydric phenol, etc. may be used as necessary. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic bifunctional carboxylic acid, or a mixture of two or more of the obtained polycarbonate resins.

[0018] The reaction modes of the methods for producing the polycarbonate resin of 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 literatures and patent publications.

[0019] If the viscosity average molecular weight of the polycarbonate resin is less than 15,000, cracks may occur during molding, and if it exceeds 25,500, fluidity may deteriorate and moldability may decrease. Therefore, the viscosity average molecular weight is preferably 15,000 to 25,500, more preferably 15,300 to 25,000, and even more preferably 15,500 to 24,500.

[0020] Two or more types of polycarbonate resins may be mixed together, and in this case, it is of course possible to mix a polycarbonate resin having a viscosity average molecular weight outside the above range.

[0021] The viscosity average molecular weight referred to in the present invention is the specific viscosity (η) determined from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. ＳＰ ) into the following equation: η ＳＰ / c = [η] + 0.45 × [η] ２ c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 －４ M ０．８３ c=0.7

[0022] <(B) Resin Having Siloxane Structural Units (Component B)> The resin having siloxane structural units (B) used as Component B of the present invention is not particularly limited as long as it contains an Si component in the structural units, but from the viewpoint of flame retardancy, it preferably contains a siloxane structural unit derived from a polyorganosiloxane represented by the following formula (5). Among these, those having an aromatic ring such as a phenyl group in the molecule are preferred, and from the viewpoint of compatibility with polycarbonate resins in particular, it is preferred to be a polycarbonate copolymer obtained from a bisphenol compound and a polyorganosiloxane as raw materials. In the above formula (5), R ３ , R ４ , R ５ , R ６, R ７ and R ８ are each 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.

[0023] Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0024] Examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0025] R ３ , R ４ , R ５ , R ６ , R ７ and R ８ is preferably a phenyl group, a propyl group, an ethyl group, or a methyl group, and more preferably a methyl group.

[0026] R ９ and R １０ are each 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.

[0027]

[0028] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0029] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0030] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0031] R ９ and R １０ is preferably a hydrogen atom, a methoxy group, or an ethoxy group, more preferably a hydrogen atom or a methoxy group, and even more preferably a hydrogen atom.

[0032] p is a natural number, preferably 20 to 100, more preferably 30 to 90, and even more preferably 35 to 70.

[0033] q is 0 or a natural number, preferably 0 to 80, and more preferably 0 to 50.

[0034] The average chain length p+q is preferably a natural number from 20 to 100, more preferably a natural number from 30 to 90, and even more preferably a natural number from 35 to 70. Within the above range, sufficient impact resistance is obtained, and furthermore, the appearance (color unevenness, peeling failure) is improved.

[0035] X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of the divalent aliphatic group include alkylene groups having 2 to 8 carbon atoms. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group, with a trimethylene group being preferred.

[0036] The polydiorganosiloxane block represented by the above formula (5) is preferably a block derived from an alkenylphenol-terminated polydiorganosiloxane, more preferably a block derived from an allylphenol-terminated polydiorganosiloxane, and even more preferably a block derived from a (2-allylphenol)-terminated polydiorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane. That is, in formula (5), X is a trimethylene group and R ９ and R １０ is a hydrogen atom, or X is a trimethylene group and R ９ and R １０ is preferably a methoxy group.

[0037] The content of Si atoms derived from the siloxane structural units used in the present invention is 0.3 to 30.0 parts by mass, preferably 0.5 to 25.0 parts by mass, and more preferably 2.0 to 20.0 parts by mass, per 100 parts by mass of the polycarbonate resin composition (a total of (A) a polycarbonate resin having carbonate structural units derived from a dihydric phenol compound, (B) a resin having siloxane structural units, (C) 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene or a resin having structural units derived therefrom, and desired additives). Within the above range, sufficient flame retardancy and moldability can be obtained. In the case of a siloxane structural unit derived from a polyorganosiloxane represented by the above formula [1], it is expressed in parts by mass of the Si element of the polyorganosiloxane block.

[0038] <Method for producing polycarbonate-polydiorganosiloxane copolymer> <Raw materials for polycarbonate-polydiorganosiloxane copolymer> (Bisphenol compound component of polycarbonate block) The bisphenol compound used as a raw material for the polycarbonate block is preferably bisphenol (I) represented by the following formula (6). (In the above formula (6), R １ and R ２ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are a plurality of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following formula (4): [In the above formula (4), R １１ , R １２ , R １３ , R １４, R １５ , R １６ , R １７ and R １８ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R １９ and R ２０ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are a plurality of groups, they may be the same or different; g is an integer from 1 to 10, and h is an integer from 4 to 7.]

[0039] Examples of the bisphenol compound (I) include 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 (commonly known as bisphenol A), 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 ... ,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-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,Examples include 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.

[0040] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 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 (bisphenol A), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Of these, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is most preferred because of its excellent strength and good durability. These may be used alone or in combination of two or more.

[0041] (Dihydroxy Compound Component of Polydiorganosiloxane Block) The dihydroxy compound used as a raw material for the polydiorganosiloxane block (A-1) is preferably a polydiorganosiloxane having a specific average chain length, and more preferably a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the following formula (7): (In the above formula (7), R ３ , R ４ , R ５ , R ６ , R ７ , R８ , R ９ , R １０ , p, q and X are the same as those in formula [1] above.)

[0042] In the above formula (7), the average chain length p + q is preferably a natural number between 20 and 100, more preferably between 30 and 90, and even more preferably between 35 and 70. When the average chain length p + q is within the above range, sufficient impact resistance is obtained, and further, the appearance (color unevenness, peeling failure) is improved. Furthermore, to satisfy this specific chain length range, two or more different hydroxyaryl-terminated polydiorganosiloxane (II) raw materials having average chain lengths p + q may be mixed to prepare the polydiorganosiloxane. In this case, it is preferable to use as raw materials a polydiorganosiloxane (B-1) having an average chain length p + q of 1 or more but less than 60 and a polydiorganosiloxane (B-2) having an average chain length p + q of 60 or more but less than 200.

[0043] The polydiorganosiloxane raw material can be prepared by mixing appropriate hydroxyaryl-terminated polydiorganosiloxane raw materials together, or by premixing polydiorganosiloxane precursors having an appropriate average chain length before the end is hydroxyaryl-modified, and then modifying the end with hydroxyaryls. The polycarbonate-polydiorganosiloxane copolymer (PC-POS copolymer) obtained by reacting the polydiorganosiloxane raw material with a bisphenol and a polycarbonate precursor has an average chain length p+q of the polydiorganosiloxane blocks, as described above, of preferably 20 to 100, more preferably 30 to 90, and even more preferably 35 to 70. The average chain length p+q is calculated by nuclear magnetic resonance (NMR) measurement.

[0044] The polycarbonate-polydiorganosiloxane copolymer of the present invention can be produced by the following process: reacting the bisphenol compound (I) represented by the above formula (6) with phosgene in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution to prepare a solution containing a carbonate oligomer having terminal chloroformate groups.

[0045] As described above, the method for producing the PC-POS copolymer used in the present invention uses a polydiorganosiloxane having a specific average chain length as a raw material, and the hydroxyaryl-terminated polydiorganosiloxane (II) may be a single type or two or more types. Specifically, a raw material is used that is represented by the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the above formula (7) and has an average chain length p + q of 20 to 100. Furthermore, in order to satisfy this specific chain length range, two or more different types of hydroxyaryl-terminated polydiorganosiloxane (II) raw materials having average chain lengths p + q may be mixed and used. In this case, the polydiorganosiloxane (B-1) having an average chain length p+q of 1 or more but less than 60 and the polydiorganosiloxane (B-2) having an average chain length p+q of 60 or more but less than 200 may be used as raw materials for preparation, or a raw material obtained by pre-mixing polydiorganosiloxane precursors having an appropriate average chain length before the terminals are hydroxyaryl-modified and then modifying the terminals with hydroxyaryl groups may be used. Furthermore, before reacting with the carbonate precursor and bisphenol, the polydiorganosiloxane (B-1) and the polydiorganosiloxane (B-2) may be pre-blended, or may be added to the reaction solution in parallel without pre-blending, or (B-1) and (B-2) may be added to the reaction solution in portions and sequentially reacted with the carbonate precursor and bisphenol. More preferably, the polydiorganosiloxane (B-1) is added to the reaction solution, and then the polydiorganosiloxane (B-2) is added to the reaction solution to react with the carbonate precursor and dihydric phenol, which is desirable from the viewpoint of efficiency and cost effectiveness due to simplification of the production process equipment. The weight ratio of the polydiorganosiloxanes (B-1) and (B-2) used as raw materials is as described above.

[0046] In the interfacial polycondensation method for obtaining the PC-POS copolymer used in the present invention, the amount of the water-insoluble organic solvent per mole of the total amount of the dihydroxy compounds represented by the above formulas (6) and (7) is preferably 8 moles or more and less than 16 moles.

[0047] Here, the total amount of dihydroxy compounds means the total amount of bisphenol and polydiorganosiloxane monomer, which are raw materials for polycarbonate.

[0048] The amount of the insoluble organic solvent is the total amount used up to the point at which the catalyst is added and the polycondensation reaction is initiated, and is the total amount of the amount used in producing the polycarbonate oligomer, the amount used to dissolve the polydiorganosiloxane monomer and the terminal terminator, and the amount added to adjust the emulsified state during the interfacial polycondensation reaction.

[0049] In the interfacial polycondensation method for obtaining the PC-POS copolymer used in the present invention, if the amount of water-insoluble organic solvent per mole of the total amount of dihydroxy compounds represented by the above formulas (6) and (7) is less than the lower limit, the emulsion state during polymerization deteriorates, resulting in reduced polymer quality and a decrease in productivity due to excessively high solution viscosity. If the amount exceeds the upper limit, the poor emulsion state makes it difficult to incorporate polydiorganosiloxane blocks into the copolymer, resulting in poor appearance. Furthermore, the water-insoluble organic solvent may be added immediately after the reaction between the carbonate precursor, the bisphenol compound, and the polydiorganosiloxane proceeds. Specifically, it is desirable to add 2 moles or more of the water-insoluble organic solvent per mole of the total amount of dihydroxy compounds represented by the above formulas (6) and (7). This ensures sufficient reaction progress while also reducing the risk of precipitation of polymer components due to high concentration.

[0050] Furthermore, other comonomers than the bisphenol compound (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that the comonomer does not interfere with the production method of the present invention.

[0051] In the production method of the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by reacting bisphenol (I) with a carbonate ester-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution.

[0052] In producing an oligomer of bisphenol compound (I), the entire amount of bisphenol compound (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0053] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0054] The proportion of the carbonate ester-forming compound used may be appropriately adjusted taking into consideration the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to employ a method in which the gaseous compound is blown into the reaction system.

[0055] Examples of the acid binder include 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, and mixtures of these.

[0056] The proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of bisphenol compound (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0057] The solvent may be any of various solvents inert to reactions, such as those used in the production of known polycarbonates, and may be used alone or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0058] The reaction pressure for producing the oligomer is not particularly limited, and may be normal pressure, elevated pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time depends on other conditions and cannot be specified in general, but is usually 0.2 to 10 hours.

[0059] The pH range of the oligomer formation reaction is the same as that of known interfacial reactions, and the pH is always adjusted to 10 or higher.

[0060] In the present invention, after obtaining a mixed solution containing an oligomer of bisphenol compound (I) having terminal chloroformate groups in this manner, the hydroxyaryl-terminated polydiorganosiloxane (II) is added to the bisphenol compound (I) while stirring the mixed solution, and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0061] When carrying out the interfacial polycondensation reaction, an acid binder may be added appropriately taking into account the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders include 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, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used or a portion of the bisphenol compound (I) as described above is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added bisphenol compound (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0062] The polycondensation by interfacial polycondensation reaction between the oligomer of the bisphenol compound (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0063] In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used. Naturally, two or more compounds can be used in combination.

[0064] To promote the polycondensation reaction, a catalyst such as a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt may be added. The reaction time for this polymerization reaction must be relatively long to reduce unreacted polydiorganosiloxane blocks. It is preferably 30 minutes or longer, more preferably 50 minutes or longer. On the other hand, since prolonged stirring of the reaction solution can cause polymer precipitation, the reaction time is preferably 180 minutes or shorter, more preferably 90 minutes or shorter. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0065] The PC-POS copolymer used in the present invention can be converted into a branched polycarbonate by using a branching agent in combination with the above-mentioned dihydroxy compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)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, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 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.

[0066] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the natural pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally specified because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0067] If necessary, the obtained polycarbonate copolymer may be subjected to a suitable physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η ＳＰ It can also be obtained as a polycarbonate copolymer of the formula [1 / c].

[0068] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer of the desired purity (degree of purification).

[0069] <(C) Resin Having 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene or a Structural Unit Derived Therefrom (Component C)> The 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene used in the present invention or a structural unit derived therefrom includes a structural unit represented by the following formula (8) or a structural unit derived therefrom. (R １１ and R １２ indicates an alkyl group)

[0070] R １１ and R １２ represents an alkyl group, and is preferably an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group), more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0071] From the viewpoint of compatibility with polycarbonate resins, the polycarbonate copolymer is preferably a polycarbonate copolymer derived from a dihydric phenol compound and 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene.

[0072] Examples of the dihydric phenol compound include the same dihydric phenol compounds as those explained in the section <(A) Carbonate structural units derived from dihydric phenol compounds>, ​​with bisphenol A being particularly preferred.

[0073] (C) The resin having a structural unit derived from 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene is preferably in a polycarbonate copolymer obtained from 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene and another dihydric phenol compound as raw materials, and particularly preferably in a polycarbonate copolymer obtained from bisphenol A and 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene as raw materials.

[0074] In a polycarbonate copolymer obtained from a dihydric phenol compound and 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene as raw materials, the proportion of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene structural units is not particularly limited, but is preferably 25 to 90 mol %, more preferably 30 to 85 mol %, and even more preferably 35 to 80 mol %. Using a polycarbonate copolymer in this range results in excellent flame retardancy and moldability.

[0075] The content of 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene or a structural unit derived therefrom used in the present invention is 1.0 to 40 parts by mass, preferably 1.2 to 35 parts by mass, and more preferably 1.3 to 30 parts by mass, per 100 parts by mass of the polycarbonate resin composition. Within the above range, sufficient flame retardancy and moldability can be obtained.

[0076] <(D) Inorganic Filler (Component D)> In the present invention, the inorganic filler preferably used as Component D is at least one inorganic filler selected from the group consisting of talc, wollastonite, mica, and kaolin. Inorganic fillers other than these may have poor flame retardancy.

[0077] The content of component D is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and even more preferably 15 to 20 parts by mass, relative to 100 parts by mass of the polycarbonate resin composition. When the content is 5 parts by mass or more, excellent flame retardancy is achieved, and when it is 30 parts by mass or less, excellent moldability is achieved.

[0078] <Second Invention> The polycarbonate resin composition of the second invention comprises (A) a polycarbonate resin (component A) having carbonate structural units derived from a dihydric phenol compound, and (E) a resin (component E) having at least one structural unit selected from the structural units represented by the above formulas (1) to (3) (structural unit E), and more preferably comprises (B) a resin (component B) having a siloxane structural unit, and / or (D) an inorganic filler (component D). Each component will be described below.

[0079] In the polycarbonate resin composition of the second invention, component A (a polycarbonate resin having carbonate structural units derived from a dihydric phenol compound), component B (a resin having siloxane structural units), and component D (an inorganic filler) are the same as component A, component B, and component D in the first invention, and the contents thereof are also the same.

[0080] <Resin Having at Least One Structural Unit E (Component E)> Component E in the polycarbonate resin composition of the second present invention is a resin having at least one structural unit (structural unit E) represented by any of the following formulas (1) to (3): (In formulas (1) to (3), R １ ~R １２ represents an alkyl group, W represents the following formula (4), and R １３ ~R ２２ represents a hydrogen atom or a methyl group.)

[0081] In the above formulas (1) to (3), R １ ~R １２ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0082] Preferred specific examples of the structural units represented by the above formulas (1) to (3) include 2,2-bis(4-hydroxy-3,5-dialkylphenyl)propane, 1,1-bis(4-hydroxy-3,5-dialkylphenyl)cyclohexane, and 9,9-bis(4-hydroxy-3,5-dialkylphenyl)fluorene, with 9,9-bis(4-hydroxy-3,5-dialkylphenyl)fluorene being preferred.

[0083] From the viewpoint of compatibility with polycarbonate resins, the copolymer is preferably a polycarbonate copolymer derived from a dihydric phenol compound and a compound that constitutes the structural unit represented by the above formula (2).

[0084] Examples of the dihydric phenol compound include the same dihydric phenol compounds as those explained in the section <(A) Carbonate structural unit (A) derived from a dihydric phenol compound>, and bisphenol A is particularly preferred.

[0085] In a polycarbonate copolymer obtained from a dihydric phenol compound and a compound constituting the structural unit represented by formula (2) as raw materials, the proportion of the structural unit represented by formula (2) is not particularly limited, but is preferably 25 to 90 mol %, more preferably 30 to 85 mol %, and even more preferably 35 to 80 mol %. When a polycarbonate copolymer in this range is used, the copolymer has excellent flame retardancy, heat buildup, and smoke generation properties.

[0086] The content of the structural units represented by formulas (1) to (3) used in the present invention is 5 to 70 parts by mass, preferably 6 to 60 parts by mass, and more preferably 7 to 50 parts by mass, per 100 parts by mass of the polycarbonate resin composition. Within the above ranges, sufficient flame retardancy, heat generation properties, and smoke generation properties can be obtained.

[0087] <Other Additives> In addition to the above components, the polycarbonate resin compositions of the first and second inventions may contain flame retardants, various stabilizers, and mold release agents for preventing a decrease in molecular weight during molding and stabilizing color tone.

[0088] (i) Flame Retardant Various compounds known as flame retardants can be blended into the polycarbonate resin composition of the present invention. The blending of compounds used as flame retardants not only improves flame retardancy, but also brings about improvements in, for example, antistatic properties, fluidity, rigidity, and thermal stability depending on the properties of each compound.

[0089] Examples of such flame retardants include organic metal salt-based flame retardants (e.g., organic alkali (earth) metal sulfonates, metal borate-based flame retardants, and metal stannate-based flame retardants), organic phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), silicone-based flame retardants made of silicone compounds, and halogen-based flame retardants (e.g., brominated epoxy resins, brominated polystyrene, brominated polycarbonates (including oligomers), brominated polyacrylates, and chlorinated polyethylene).

[0090] (ii) Stabilizers The polycarbonate resin composition of the present invention may contain various known stabilizers, such as phosphorus-based stabilizers, hindered phenol-based antioxidants, ultraviolet absorbers, and light stabilizers.

[0091] (iii) Mold Release Agents The polycarbonate resin composition of the present invention can further contain known mold release agents such as fatty acid esters, polyolefin waxes, silicone compounds, fluorine compounds (such as fluorine oils typified by polyfluoroalkyl ethers), paraffin wax, and beeswax, in order to improve productivity during molding and the dimensional accuracy of molded articles. The polycarbonate resin composition of the present invention has good fluidity, resulting in good pressure transmission and molded articles with uniform strain. On the other hand, in the case of molded articles with complex shapes that have high mold release resistance, there is a risk of deformation of the molded article during mold release. The incorporation of the above specific components solves this problem without impairing the properties of the polycarbonate resin composition.

[0092] [Method for Producing Polycarbonate Resin Composition] The method for producing the polycarbonate resin composition of the present invention is not particularly limited, and well-known methods can be used. For example, there can be mentioned a method in which the above-mentioned components A, B, and C (first invention) or the above-mentioned components A and E (second invention) and, optionally, other additives are thoroughly mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, and then the premix is ​​granulated as necessary using an extrusion granulator or a briquetting machine, and then the mixture is melt-kneaded in a melt kneader typified by a vented twin-screw extruder, and then pelletized using a pelletizer.

[0093] Other examples include a method of independently feeding each component into a melt kneader, such as a vented twin-screw extruder; a method of feeding into a melt kneader using a supercritical fluid; and a method of premixing a portion of each component and then feeding the remaining components into a melt kneader independently. Examples of a method of premixing a portion of each component include a method of premixing components other than component A in advance and then mixing them with component A or feeding them directly into an extruder. Examples of premixing methods include, when component A is in powder form, blending a portion of the powder with the additives to be added to produce a masterbatch of the additives diluted with the powder, and using this masterbatch. Another example is a method of independently feeding one component into the middle of a melt extruder. When the components to be added are liquid, a so-called liquid injection device or liquid addition device can be used to feed the components into the melt extruder.

[0094] The extruder preferably has a vent that can remove moisture from the raw materials and volatile gases generated from the melt-kneaded resin. A vacuum pump is preferably installed in the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. A screen for removing foreign matter mixed into the extrusion raw materials can also be installed in a zone before the extruder die to remove foreign matter from the resin composition. Examples of such a screen include wire mesh, a screen changer, and a sintered metal plate (such as a disc filter). Examples of melt-kneaders include a twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder with three or more screws.

[0095] The extruded resin as described above is either directly cut and pelletized, or formed into strands, which are then cut and pelletized using a pelletizer. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical disks can be used to narrow the pellet shape distribution, reduce miscuts, reduce fine powder generated during shipping and handling, and reduce bubbles (vacuum bubbles) generated inside the strands or pellets. These methods can achieve high molding cycle times and reduce the incidence of defects such as silver spots. The pellets can be shaped in any of the common shapes, including cylindrical, prismatic, and spherical, with cylindrical shapes being 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. 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.

[0096] The polycarbonate resin composition of the present invention can be used to produce various products by injection molding the pellets prepared as described above to obtain molded articles. Such injection molding can be carried out not only by conventional molding methods, but also by injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding. Molding can be carried out using either a cold runner system or a hot runner system.

[0097] The polycarbonate resin composition of the present invention can also be used in the form of various profile extrusion molded products, sheets, films, etc. by extrusion molding. Sheets and films can also be molded by inflation, calendaring, casting, etc. Furthermore, by subjecting the composition to a specific stretching operation, it can also be molded into heat-shrinkable tubing. The polycarbonate resin composition of the present invention can also be molded into molded articles by rotational molding, blow molding, etc.

[0098] <Characteristic Values ​​of Resin Molded Article> (Flame Retardancy) A combustion test was carried out using a 1.5 mm thick UL test piece obtained by the following method in accordance with the UL94 vertical combustion test established by Underwriters Laboratories, Inc., USA. The results were evaluated and classified as V-0, V-1, V-2, or not V. For the polycarbonate resin composition of the present invention, the UL94 vertical combustion test result is preferably V-1 or higher, and more preferably V-0 or higher.

[0099] (Heat generation) The polycarbonate resin composition of the present invention was subjected to a heat generation test of 50 kW / m using a cone calorimeter in accordance with ISO 5660-1. ２ When tested under conditions of heater irradiance of 1000 W / m and ignition on, the maximum average heat emission rate (MARHE) is preferably 90 kW / m ２ The smaller the MARHE value, the more preferable it is, but 85 kW / m is more preferable. ２ It is more preferably 80 kW / m or less.２ The following is particularly preferred: ２ The most preferred is 70 kW / m ２ The following is shown: MARHE is 90 kW / m ２ In the following cases, for example, in the European Railway Standard EN45545-2, it can be applied to components that require a higher level of flame retardancy at the hazard level (HL) set based on escape time and vehicle structure.

[0100] (Molding Processability) The resin composition of the present invention is excellent in preventing mold contamination during molding.

[0101] (Smoke Generation) In accordance with ISO 5659-2, the above-mentioned test piece was cut into a length of 75 mm, a width of 75 mm, and a thickness of 3 mm. The test piece was then subjected to a 50 kW / m ２ The specific optical density Ds(4), which serves as an index of smoke generation, was determined 4 minutes after the start of the test. A smaller Ds(4) value is preferable, and in the polycarbonate resin composition of the present invention, it is preferably 200 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, or 130 or less.

[0102] <Uses of Resin Molded Article> The resin molded article of the present invention can be used as parts such as automobile-related parts, railway-related parts, aircraft-related parts, household electrical appliance parts, electric / electronic appliance parts, housing equipment parts, office automation equipment parts, play equipment parts, and eyeglass parts.

[0103] Examples of railway-related parts include interior walls, heat insulating materials, interior equipment housings, luggage areas, operating surfaces, windows, curtains, tables, seating components, air ducts, and interior displays. Of these, interior walls, tables, and seating are preferred.

[0104] Examples of aircraft-related parts include ceiling interior walls, partitions, galley components, luggage racks, windows, soundproofing materials, air ducts, in-flight displays, and switches, with partitions, luggage racks, windows, and switches being preferred.

[0105] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. Unless otherwise specified, parts in the examples are parts by weight and % is % by weight. Evaluations were made according to the following methods.

[0106] (Component A: Polycarbonate resin) A: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity-average molecular weight of 23,900, produced by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name Panlite L-1250WP)

[0107] (Component B: Resin Having Siloxane Structural Units) B-1 to B-3: Polycarbonate-Polydiorganosiloxane Copolymers (Production Method of B-1) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 17,890 parts of ion-exchanged water and 7,003 parts of a 25% aqueous sodium hydroxide solution, and 3,812 parts of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) as the dihydric phenol (I) represented by the general formula [4] and 7.5 parts of hydrosulfite were dissolved therein. Then, 14,310 parts of methylene chloride was added, and 1,900 parts of phosgene was blown in over 70 minutes at 22 to 30°C with stirring. 7,150 parts of methylene chloride was added, and a solution of 1,347 parts of a 25% aqueous sodium hydroxide solution and 149 parts of p-tert-butylphenol dissolved in 850 parts of methylene chloride was added. With stirring, a solution of 428 parts of the above KF-2201 as dihydric phenol (II) represented by general formula [5] dissolved in 800 parts of methylene chloride (0.55 molar equivalents relative to the total amount of dihydric phenol) was added at a rate such that the dihydric phenol (II) was 0.0008 molar equivalents / min relative to the dihydric phenol (I) to form an emulsion, and the mixture was again vigorously stirred. With such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, washed with water, and then acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase reached almost the same level as that of ion-exchanged water, the mixture was placed in a kneader filled with warm water and the methylene chloride was evaporated with stirring to obtain a polycarbonate-polydiorganosiloxane copolymer powder. After dehydration, the mixture was dried at 100°C for 12 hours in a hot air circulating dryer. The viscosity-average molecular weight of the resulting polycarbonate-polydiorganosiloxane copolymer was 16,000, and the Si content of the polydiorganosiloxane blocks was 8.4 parts by mass.

[0108] (Production Method of B-2) A polycarbonate-polydiorganosiloxane copolymer was prepared in the same manner as Production Method B-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3,996 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 648 parts. The viscosity average molecular weight of the resulting polycarbonate-polydiorganosiloxane copolymer was 20,500, and the Si element content of the polydiorganosiloxane block was 14.5 parts by mass.

[0109] (Production Method of B-3) A polycarbonate-polydiorganosiloxane copolymer was prepared in the same manner as Production Method B-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 4,320 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 2,023 parts. The viscosity average molecular weight of the resulting polycarbonate-polydiorganosiloxane copolymer was 22,500, and the Si element content of the polydiorganosiloxane block was 50.0 parts by mass.

[0110] B-4: KR-2710 (silicone flame retardant manufactured by Shin-Etsu Chemical Co., Ltd., Si element content 15% by weight)

[0111] (Component C) C-1: BCF (Osaka Gas Chemicals Co., Ltd., 9,9-bis(4-hydroxy-3-methylphenyl)fluorene) C-2, C-3: Polycarbonate copolymers obtained from bisphenol A and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene as raw materials

[0112] (Production method C-2) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 4,554 parts of 48% aqueous sodium hydroxide solution and 22,730 parts of ion-exchanged water, to which 4,345 parts of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Chemical Industry Co., Ltd.), 1,125 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.), and 7.94 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved, and 13,415 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in over about 70 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, 650 parts of 48% aqueous sodium hydroxide solution and 92.3 parts of p-tert-butylphenol were added, stirring was resumed, and 5.6 parts of triethylamine were added after emulsification, and the reaction was terminated by further stirring at 28 to 35 ° C. for 1 hour.

[0113] After the reaction was completed, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to acidify the mixture and washed with water. Further washing with water was repeated until the conductivity of the aqueous phase was approximately the same as that of ion-exchanged water, yielding a methylene chloride solution of polycarbonate resin. This solution was then passed through a filter with a mesh size of 0.3 μm and added dropwise to warm water in a kneader with an isolation chamber and a foreign matter outlet in the bearing section. The polycarbonate resin was flaked while the methylene chloride was distilled off, and the liquid-impregnated flakes were subsequently pulverized and dried to obtain powder (C-2). The evaluation results of this powder are shown in Table 1.

[0114] (Production method of C-3) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 4,555 parts of 48% aqueous sodium hydroxide solution and 22,730 parts of ion-exchanged water, to which 2,386 parts of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Chemical Industry Co., Ltd.), 2,162 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.), and 7.94 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved, and 13,415 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in over about 70 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, 650 parts of 48% aqueous sodium hydroxide solution and 92.3 parts of p-tert-butylphenol were added, stirring was resumed, and 5.6 parts of triethylamine were added after emulsification, and the reaction was terminated by further stirring at 28 to 35 ° C. for 1 hour.

[0115] After the reaction was completed, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to acidify the mixture and washed with water. Further washing with water was repeated until the conductivity of the aqueous phase was approximately the same as that of ion-exchanged water, yielding a methylene chloride solution of polycarbonate resin. This solution was then passed through a filter with a mesh size of 0.3 μm and added dropwise to warm water in a kneader with an isolation chamber and a foreign matter outlet in the bearing section. The polycarbonate resin was flaked while the methylene chloride was distilled off, and the liquid-impregnated flakes were subsequently pulverized and dried to obtain powder (C-2). The evaluation results of this powder are shown in Table 1.

[0116] C-4: BPF (Osaka Cas Chemical Co., Ltd., 9,9-bis(4-hydroxyphenyl)fluorene) C-5: Polycarbonate copolymer obtained from bisphenol A and 9,9-bis(4-hydroxyphenyl)fluorene

[0117] (Production method of C-5) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 4,555 parts of 48% aqueous sodium hydroxide solution and 22,730 parts of ion-exchanged water, to which 2,386 parts of 9,9-bis(4-hydroxyphenyl)fluorene (manufactured by Honshu Chemical Industry Co., Ltd.), 1,439 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.), and 7.94 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved, and 13,415 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in over about 70 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, 650 parts of 48% aqueous sodium hydroxide solution and 92.3 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 5.6 parts of triethylamine was added, and the mixture was further stirred at 28 to 35 ° C. for 1 hour to complete the reaction.

[0118] (Component D) D-1: Victorilite TK-RC, talc (manufactured by Shokoyama Mining Co., Ltd.) D-2: SH-1250, wollastonite (manufactured by Kinseimatec Co., Ltd.) D-3: MT200B, mica (manufactured by Kinseimatec Co., Ltd.) D-4: TRANSLINK TL-77, kaolin (manufactured by BASF Japan) D-5: MEG160FYX, glass flakes (Nippon Sheet Glass Co., Ltd.)

[0119] (Component E) E-1: Polycarbonate copolymer obtained using bisphenol A and 9,9-bis(4-hydroxy-3,5-methylphenyl)fluorene (referred to as BXF) as raw materials (bisphenol A:BXF=30:70 (molar ratio)) (Method for producing E-1) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 4,554 parts of a 48% aqueous sodium hydroxide solution and 22,730 parts of ion-exchanged water, and 4,345 parts of 9,9-bis(4-hydroxy-3,5-methylphenyl)fluorene (manufactured by Osaka Gas Chemicals), 1,125 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.), and 7.94 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved therein, followed by the addition of 13,415 parts of methylene chloride, and then 2,000 parts of phosgene was blown in over approximately 70 minutes at 15 to 25° C. with stirring. After the phosgene injection was completed, 650 parts of a 48% aqueous sodium hydroxide solution and 92.3 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 5.6 parts of triethylamine was added. The mixture was further stirred at 28 to 35°C for 1 hour to complete the reaction.

[0120] After the reaction was completed, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to make it acidic and washed with water, and washing with water was repeated until the conductivity of the aqueous phase was approximately the same as that of ion-exchanged water, yielding a methylene chloride solution of polycarbonate resin. Next, this solution was passed through a filter with a mesh size of 0.3 μm and further dropped into warm water in a kneader with an isolation chamber and a foreign matter outlet in the bearing section, and the polycarbonate resin was flaked while distilling off the methylene chloride. The liquid-containing flakes were then pulverized and dried to obtain powder (B-1). B-2: A polycarbonate copolymer obtained from bisphenol A and 9,9-bis(4-hydroxy-3,5-ethylphenyl)fluorene (referred to as BZF) as raw materials (bisphenol A:BZF=50:50 (molar ratio)).

[0121] (Production method of E-2) Powder E-2 was obtained in the same manner as in the production example of E-1, except that 2,386 parts of 9,9-bis(4-hydroxy-3,5-methylphenyl)fluorene was used instead of 2,386 parts of 9,9-bis(4-hydroxy-3,5-ethylphenyl)fluorene and 1,439 parts of bisphenol A.

[0122] E-3: BXF (Osaka Gas Chemicals, 9,9-bis(4-hydroxy-3,5-methylphenyl)fluorene) E-4 (Comparative Example): BCF (Osaka Gas Chemicals, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene) E-5 (Comparative Example): BPF (Osaka Gas Chemicals, 9,9-bis(4-hydroxyphenyl)fluorene)

[0123] (Other components) F-1: Diakaruna 30M, modifier (Mitsubishi Chemical Corporation) F-2: KBM3130, modifier (Shin-Etsu Chemical Co., Ltd.)

[0124] [Production of Resin Compositions] (Examples 1 to 27, Comparative Examples 1 to 15) The components shown in Tables 1 to 3 were mixed in the proportions shown in Tables 1 to 3, and each was melt-kneaded at 280°C using a twin-screw extruder [TEX30α-3, manufactured by The Japan Steel Works, Ltd.] and degassed through a vacuum vent to produce pellets. A portion of the resulting pellets was dried in a hot air circulation dryer at 120°C for 6 hours, and then molded into flat plates and UL test pieces using an injection molding machine at a cylinder temperature of 280°C and a mold temperature of 80°C.

[0125] [Evaluation of Resin Composition] (i) Heat Release [Maximum Average Heat Release Rate: MARHE] The pellets obtained by the above method were dried at 120°C for 5 hours or more, and then molded into flat plates (150 mm x 150 mm x 3 mmt) using a molding machine ("α-S10iSA" manufactured by Mitsubishi-FANUC Corporation) at a resin temperature of 280°C and a mold temperature of 80°C. The obtained test pieces were cut into 100 mm x 100 mm x 3 mmt.

[0126] In accordance with ISO 5660-1, the obtained test piece was subjected to a calorie test at 50 kW / m using a cone calorimeter C3 manufactured by Toyo Seiki Seisakusho. ２ The test was carried out under the condition of heater irradiance of 1000 W, ignition on, and the heat release rate was measured. The integrated value of the heat release rate obtained was divided by the number of seconds up to that point to determine the maximum average heat release rate: MARHE (unit: kW / m ２ A smaller MARHE value is preferred.

[0127] (ii) Molding processability The pellets obtained by the above method were dried at 120°C for 5 hours or more, and then molded using a molding machine ("α-S10iSA" manufactured by Mitsubishi-FANUC Corporation) at a resin temperature of 280°C and a mold temperature of 80°C. Mold contamination due to gas generated by the resin composition was evaluated visually and rated according to the following criteria: P: No or very little mold contamination due to generated gas. F: Mold contamination due to generated gas was observed.

[0128] (iii) Flame Retardancy A flame test was carried out using the 1.5 mm thick UL test piece obtained by the above method in accordance with the UL94 vertical flame test established by Underwriters Laboratories, Inc. The results were evaluated and classified as V-0, V-1, V-2, or not V.

[0129] (iv) Smoke Generation According to ISO 5659-2, the above test pieces were cut into a length of 75 mm, a width of 75 mm, and a thickness of 3 mm. The test pieces were then subjected to a 50 kW / m Smoke Density Chamber manufactured by Fire Testing Technology. ２ The test was carried out using a flameless method with a heater irradiance of 1000 kJ / cm2, and the specific optical density Ds(4) was determined 4 minutes after the start of the test, which is an index of smoke generation.

[0130]

[0131]

[0132]

[0133] It is clear from Tables 1 to 3 that the formulation of the present invention makes it possible to provide polycarbonate resin compositions having excellent flame retardancy and moldability, and molded articles made from the same.

[0134] The polycarbonate resin composition and molded article of the present invention can be widely used in aviation applications, railway applications, and various other applications.

Claims

1. A polycarbonate resin composition comprising: (A) a polycarbonate resin (component A) having a carbonate structural unit derived from a dihydric phenol compound; (B) a resin having a siloxane structural unit (component B); and (C) 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene or a resin having a structural unit derived therefrom (component C), wherein the amount of Si element derived from the siloxane structural unit of the component B is in the range of 0.3 to 30.0 parts by mass, and the content of the component C is in the range of 1.0 to 40 parts by mass, based on 100 parts by mass of the polycarbonate resin composition.

2. The polycarbonate resin composition according to claim 1, further comprising 5 to 30 parts by mass of at least one inorganic filler (component D) selected from the group consisting of talc, wollastonite, mica, and kaolin, based on 100 parts by mass of the polycarbonate resin composition.

3. The polycarbonate resin composition according to claim 1 or 2, wherein the component A comprises a polycarbonate resin having a carbonate structural unit derived from bisphenol A.

4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the component B comprises a resin having a siloxane structural unit derived from a polydiorganosiloxane.

5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the component B comprises a polycarbonate copolymer obtained from bisphenol A and a polydiorganosiloxane as raw materials.

6. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the resin having a structural unit derived from 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene of the component C comprises a polycarbonate copolymer obtained from 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene and another dihydric phenol compound as raw materials.

7. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the resin having a 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene structural unit of the component C comprises a polycarbonate copolymer obtained from bisphenol A and 9,9-bis(4-hydroxy-3-alkylphenyl)fluorene as raw materials.

8. In accordance with ISO 5660-1, a heater irradiance of 50 kW / m ２ and a maximum average heat release rate tested under conditions with ignition are 90 kW / m ２ or less. The polycarbonate resin composition according to any one of claims 1 to 7.

9. A molded article formed from the polycarbonate resin composition according to any one of claims 1 to 8.

10. The molded article according to claim 9, which is an interior member of a railway vehicle.

11. A polycarbonate resin composition comprising (A) a polycarbonate resin (component A) having a carbonate structural unit derived from a dihydric phenol compound and (E) a resin (component E) having at least one structural unit of the structural units represented by the following formulas (1) to (3) (structural unit E), wherein, based on 100 parts by mass of the polycarbonate resin composition, at least one of the structural units E is contained in the range of 5 to 70 parts by mass: In formulas (1) to (3), １ R １２ to R １３ represent an alkyl group, W represents the following formula (4), and R ２２ to R represent a hydrogen atom or a methyl group:

12. The polycarbonate resin composition according to claim 11, wherein W is a fluorene derivative.

13. Further comprising a resin (component B) having a siloxane structural unit, and the amount of Si element derived from the siloxane structural unit of the component B is 0.3 to 10.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin composition. The polycarbonate resin composition according to claim 11 or 12.

14. Further, with respect to 100 parts by mass of the polycarbonate resin composition, containing 5 to 30 parts by mass of at least one inorganic filler (component D) selected from the group consisting of talc, wollastonite, mica, and kaolin. The polycarbonate resin composition according to any one of claims 11 to 13.

15. A molded article formed from the polycarbonate resin composition according to any one of claims 11 to 14.

16. The molded article according to claim 15, which is an interior member of a railway vehicle.

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