WO2024150594A1 - ポリカーボネート樹脂組成物およびそれからなる成形品 - Google Patents
ポリカーボネート樹脂組成物およびそれからなる成形品 Download PDFInfo
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- WO2024150594A1 WO2024150594A1 PCT/JP2023/044873 JP2023044873W WO2024150594A1 WO 2024150594 A1 WO2024150594 A1 WO 2024150594A1 JP 2023044873 W JP2023044873 W JP 2023044873W WO 2024150594 A1 WO2024150594 A1 WO 2024150594A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- the present invention relates to a polycarbonate resin composition that has excellent plating properties when forming circuits, and to a molded article made from the same.
- Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability, and is therefore used as an engineering plastic in a wide range of fields, such as housings for electrical and electronic devices, interior and exterior parts for automobiles, building materials, furniture, musical instruments, and miscellaneous goods.
- various methods for manufacturing antennas and electronic circuits inside electronic devices such as mobile phones, including smartphones, have been considered, and in particular, a method for three-dimensionally designing antennas and electronic circuits inside electronic devices is required.
- laser irradiation three-dimensional circuit molding technology has attracted attention.
- This technology is, for example, a technology that uses a resin material in which a metal complex is dispersed, reduces the complex with laser light to serve as a catalyst nucleus, and can directly form circuits such as antennas by selective plating without an adhesive layer.
- a resin composition consisting of polycarbonate resin and a specific conductive oxide has been proposed as a material using such laser irradiation three-dimensional circuit molding technology (Patent Document 1).
- Patent Document 2 a resin composition capable of appropriately forming a metal thin film under a wide range of laser irradiation conditions has been proposed (Patent Document 2).
- Patent Document 1 a resin composition capable of appropriately forming a metal thin film under a wide range of laser irradiation conditions.
- JP 2012-72338 A International Publication No. 2014/042070
- the object of the present invention is to provide a polycarbonate resin composition that has excellent plating properties during circuit formation, and a molded article made from the same.
- the present invention is as follows. 1. (A) 100 parts by weight of a resin component (A component) consisting of 0 to 99.9% by weight of an aromatic polycarbonate resin (A-1 component) and 0.1 to 100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (A-2 component), and (B) 1 to 50 parts by weight of an additive for forming a three-dimensional circuit by laser irradiation (B component); A polycarbonate resin composition, characterized in that Component A-2 is a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3), and having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, the average size of the polydiorganosiloxane domains being 5 to 100 nm.
- a component a resin component
- R 1 and R 2 each independently represent 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; a and b each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent 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
- 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;
- 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;
- e and f are each integers of 1 to 4;
- p is a natural number;
- q is 0 or a natural number; and
- p+q is a natural number of 4 or more and 150 or less; and
- X is a divalent aliphatic group having 2 to 8 carbon atoms.
- polycarbonate resin composition according to the preceding paragraph 1 which contains 1 to 150 parts by weight of (C) an inorganic filler (component C) per 100 parts by weight of component A.
- the polycarbonate resin composition according to the preceding paragraph 1 or 2 characterized in that the content of the polydiorganosiloxane block represented by the above formula (3) in component A-2 is 0.05 to 50.0% by weight.
- component B is an additive for laser irradiation three-dimensional circuit molding that contains at least two types of metals.
- component C is at least one inorganic filler selected from the group consisting of glass, carbon fiber, and silicate minerals.
- the polycarbonate resin composition of the present invention has excellent plating properties when forming circuits, and can therefore be suitably used as three-dimensional circuit boards or broadband antennas in buildings, construction materials, agricultural materials, marine materials, vehicles, electrical and electronic equipment, machinery, and a variety of other fields. Therefore, the industrial effects of the present invention are extremely significant.
- the present invention relates to a polycarbonate resin composition having the following composition.
- A 100 parts by weight of a resin component (A component) consisting of 0 to 99.9% by weight of an aromatic polycarbonate resin (A-1 component) and 0.1 to 100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (A-2 component), and (B) 1 to 50 parts by weight of an additive for forming a three-dimensional circuit by laser irradiation (B component),
- a polycarbonate resin composition characterized in that Component A-2 is a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3), and having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, the average size of the polydiorganosiloxane domains being 5 to 100 nm.
- R 1 and R 2 each independently represent 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; a and b each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent 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
- 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;
- 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;
- e and f are each integers of 1 to 4;
- p is a natural number;
- q is 0 or a natural number; and
- p+q is a natural number of 4 or more and 150 or less; and
- X is a divalent aliphatic group having 2 to 8 carbon atoms.
- Component A Resin Component
- A-1 component aromatic polycarbonate resin
- Aromatic polycarbonate resins are generally obtained by reacting a dihydroxy compound with a carbonate precursor by interfacial polycondensation or melt transesterification, or by polymerizing a carbonate prepolymer by solid-phase transesterification, or by polymerizing a cyclic carbonate compound by ring-opening polymerization.
- the dihydroxy component used here may be any dihydroxy component that is generally used in aromatic polycarbonates, and may be bisphenols or aliphatic diols. As the bisphenol, the bisphenol represented by the following formula (4) is preferably used.
- R 1 and R 2 each independently represent a hydrogen atom, and when there are a plurality of R 1 and R 2, they may be the same or different, a and b each represent an integer of 1 to 4, and W represents a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2):
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent 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
- bisphenols 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, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, and bis(4-hydroxyphenyl)diphenyl.
- phenylmethane 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 sulfide oxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-
- Aliphatic diols include, for example, 2,2-bis-(4-hydroxycyclohexyl)-propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4'-bis(2-hydroxyethoxy)biphenyl, bis ⁇ (2-hydroxyethoxy)phenyl ⁇ methane, 1,1-bis ⁇ (2-hydroxyethoxy)phenyl ⁇ ethane, 1,1-bis ⁇ (2-hydroxyethoxy)phenyl ⁇ -1-phenylethane, 2,2-bis ⁇ (2-hydroxyethoxy)phenyl ⁇ propane, 2,2-bis ⁇ (2-hydroxyethoxy)-3-methylphenyl ⁇ propane, 1,1-bis ⁇ (2-hydroxyethoxy)phenyl ⁇ -3,3,5-trimethylcyclohexane, 2,2-bis ⁇ 4-(2-hydroxyethoxy)phenyl ⁇ methane, 1,1-bis ⁇ (2-hydroxyethoxy)phenyl
- aromatic bisphenols are preferred, and among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 1,3-bis ⁇ 2-(4-hydroxyphenyl)propyl ⁇ benzene, and 1,4-bis ⁇ 2-(4-hydroxyphenyl)propyl ⁇ benzene are preferred, with 2,2-bis(4-hydroxyphenyl)propane and 4,4'-sulfonyldiphenol being especially preferred.
- 2,2-bis(4-hydroxyphenyl)propane which has excellent strength and good durability, is the most preferred. These may be used alone or in combination of two or more.
- the aromatic polycarbonate resin used as component A-1 of the present invention may be made into a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound.
- Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucide, 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 include trisphenols such as ⁇ 4-hydroxyphenyl)ethyl]benzen
- aromatic polycarbonate resins are produced by known reaction means for producing ordinary aromatic polycarbonate resins, for example, by reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or a carbonic acid diester.
- a carbonate precursor such as phosgene or a carbonic acid diester.
- the reaction is usually carried out in the presence of an acid binder and a solvent.
- an acid binder for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
- the solvent for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used.
- a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction.
- the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.
- an ester exchange reaction using a carbonic acid diester as a carbonate precursor a predetermined ratio of aromatic dihydroxy components is stirred with the carbonic acid diester while heating in an inert gas atmosphere, and the resulting alcohol or phenol is distilled off.
- the reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C.
- the reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol.
- a catalyst usually used in ester exchange reactions can be used to promote the reaction.
- Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
- a terminal terminator is used in the polymerization reaction.
- the terminal terminator is used to adjust the molecular weight, and the resulting aromatic polycarbonate resin has excellent thermal stability compared to those that are not end-blocked because the ends are blocked.
- Examples of such terminal terminators include monofunctional phenols represented by the following general formulas (5) to (7).
- A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion has 1 to 9 carbon atoms), and r is an integer of 1 to 5, preferably 1 to 3.
- Y is -R-O-, -R-CO-O-, or -R-O-CO-, where R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50.
- monofunctional phenols represented by the above general formula (5) include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol, and isooctylphenol.
- the monofunctional phenols represented by the above general formulas (6) and (7) are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and when these are used to block the ends of aromatic polycarbonate resin, they not only function as end terminators or molecular weight regulators, but also improve the melt fluidity of the resin, making molding easier, and have the effect of lowering the water absorption rate of the resin, and are preferably used.
- substituted phenols of the above general formula (6) those in which n is 10 to 30, particularly 10 to 26, are preferred, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol.
- substituted phenols of the above general formula (7) compounds in which Y is -R-CO-O- and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26, are preferred, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and triacontyl hydroxybenzoate.
- the monofunctional phenols represented by the above general formula (5) are preferred, more preferably alkyl- or phenylalkyl-substituted phenols, and particularly preferably p-tert-butylphenol, p-cumylphenol, or 2-phenylphenol. It is desirable that the terminal terminator of these monofunctional phenols is introduced into the terminals in an amount of at least 5 mol%, preferably at least 10 mol%, of the total terminals of the obtained aromatic polycarbonate resin, and the terminal terminator may be used alone or in a mixture of two or more types.
- the aromatic polycarbonate resin used as component A-1 of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof, within the scope of the present invention.
- aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof, within the scope of the present invention.
- the viscosity average molecular weight of the aromatic polycarbonate resin used as the A-1 component of the present invention is preferably in the range of 12,000 to 50,000, more preferably in the range of 12,000 to 30,000, even more preferably in the range of 12,000 to 25,000, and most preferably in the range of 15,000 to 25,000. If the molecular weight exceeds 50,000, the melt viscosity may become too high and moldability may be poor, and if the molecular weight is less than 12,000, problems may occur in mechanical strength.
- the viscosity average molecular weight referred to in the present invention is first calculated by the specific viscosity calculated by the following formula using an Ostwald viscometer from a solution in which 0.7 g of aromatic polycarbonate resin is dissolved in 100 ml of methylene chloride at 20°C, and the calculated specific viscosity is inserted into the following formula to calculate the viscosity average molecular weight M.
- the aromatic polycarbonate resin used as component A-1 in the present invention preferably has a total Cl (chlorine) content of 0 to 200 ppm, more preferably 0 to 150 ppm. If the total Cl content in the aromatic polycarbonate resin exceeds 200 ppm, this is not preferred as it may result in poor color and thermal stability.
- Component A-2 Polycarbonate-polydiorganosiloxane copolymer resin
- Component A-2 of the present invention is a polycarbonate-polydiorganosiloxane copolymer resin which comprises a polycarbonate block represented by formula (1) below and a polydiorganosiloxane block represented by formula (3) below, has an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, and has an average size of the polydiorganosiloxane domains of 5 to 100 nm.
- R 1 and R 2 each independently represent 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; a and b each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent 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
- 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;
- 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;
- e and f are each integers of 1 to 4;
- p is a natural number;
- q is 0 or a natural number; and
- p+q is a natural number of 4 or more and 150 or less; and
- X is a divalent aliphatic group having 2 to 8 carbon atoms.
- Dihydric phenols (I) from which the carbonate structural unit represented by general formula (1) is derived 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, 2,2-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(
- R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently 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, with a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group being particularly preferred.
- R 9 and R 10 are each independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, with a hydrogen atom or an alkyl group having 1 to 4 carbon atoms being particularly preferred.
- a compound as shown in the following general formula [I] is suitably used as shown in the following general formula [I] is suitably used.
- Hydroxyaryl-terminated polydiorganosiloxane (II) is easily produced by subjecting a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, to a polysiloxane chain end having a predetermined degree of polymerization through a hydrosilylation reaction.
- a phenol having an olefinically unsaturated carbon-carbon bond preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol
- (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are particularly preferred.
- the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 4 to 120, more preferably 30 to 120, even more preferably 30 to 100, and most preferably 30 to 95.
- the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably in the range of 5.0 x 10 3 to 5.0 x 10 4.
- Such a viscosity average molecular weight is more preferably 1.0 x 10 4 to 4.0 x 10 4 , further preferably 1.5 x 10 4 to 3.5 x 10 4 , and particularly preferably 1.7 x 10 4 to 2.5 x 10 4.
- the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is less than 5.0 x 10 3 , it is difficult to obtain practical mechanical strength in many fields, and if it exceeds 5.0 x 10 4 , the melt viscosity is high and generally a high molding processing temperature is required, which may cause problems such as thermal degradation of the resin.
- the polydiorganosiloxane domain refers to a domain that is primarily composed of polydiorganosiloxane dispersed in a polycarbonate matrix, and may contain other components. As described above, the polydiorganosiloxane domain does not necessarily consist of a single component, since the structure is formed by phase separation from the polycarbonate matrix.
- hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.
- a method for producing the above-mentioned preferred polycarbonate-polydiorganosiloxane copolymer resin will be described below.
- a mixture solution of chloroformate compounds containing chloroformate of dihydric phenol (I) and/or carbonate oligomer of dihydric phenol (I) having terminal chloroformate groups is prepared by reacting dihydric phenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of dihydric phenol (I) in a mixture of the water-insoluble organic solvent and the aqueous alkali solution.
- phosgene phosgene
- a chloroformate of dihydric phenol (I) in a mixture of the water-insoluble organic solvent and the aqueous alkali solution.
- Phosgene is preferred as the chloroformate-forming compound.
- the entire amount of the dihydric phenol (I) from which the carbonate structural unit represented by the above general formula (1) is derived may be converted into a chloroformate compound at once, or a part of it may be added as a post-added monomer to the subsequent interfacial polycondensation reaction as a reaction raw material.
- the post-added monomer is added to facilitate the subsequent polycondensation reaction, and it is not necessary to add it if it is not necessary.
- the method of this chloroformate compound production 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.
- a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added, and it is preferable to add it.
- the proportion of the chloroformate-forming compound used may be appropriately adjusted taking into account the stoichiometric ratio (equivalent) of the reaction.
- phosgene which is a suitable chloroformate-forming compound
- a method of blowing gasified phosgene into the reaction system can be preferably adopted.
- the acid binder may be, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or an organic base such as pyridine, or a mixture of these.
- the proportion of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder per mole of dihydric phenol (I) used to form the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents).
- the solvent may be any of the solvents known in the art that are inert to various reactions, such as those used in the production of polycarbonates, and may be used alone or in the form of a mixture of solvents.
- Representative 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 preferably used.
- the pressure in the reaction to produce chloroformate compounds there are no particular restrictions on the pressure in the reaction to produce chloroformate compounds, and it 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 since the reaction often generates heat, it is desirable to cool the reaction with water or ice.
- the reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours.
- the pH range in the reaction to produce chloroformate compounds can use known interfacial reaction conditions, and the pH is usually adjusted to 10 or higher.
- a mixed solution of chloroformate compounds containing a chloroformate of dihydric phenol (I) and a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group is thus prepared, and then, while stirring the mixed solution, dihydroxyaryl-terminated polydiorganosiloxane (II) which derives carbonate structural units represented by general formula (3) is added at a rate of 0.01 mol/min or less per mol of the amount of dihydric phenol (I) charged in preparing the mixed solution, and the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer resin.
- Polycarbonate-polydiorganosiloxane copolymer resins can be made into branched polycarbonate-polydiorganosiloxane copolymer resins by using a branching agent in combination with a dihydric phenol compound.
- Trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucide, 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 include trisphenols such as ⁇ 4-hydroxyphenyl)ethyl]benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4
- the method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin may be a method in which a branching agent is included in the mixed solution during the production reaction of the chloroformate compound, or a method in which a branching agent is added during the interfacial polycondensation reaction after the completion of the production reaction.
- the proportion of carbonate constituent units derived from the branching agent 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%, based on the total amount of carbonate constituent units constituting the copolymer resin.
- the amount of branched structures can be calculated by 1 H-NMR measurement.
- the pressure in the system during the polycondensation reaction may 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, since heat is generated during polymerization, it is desirable to cool the reaction with water or ice.
- the reaction time cannot be generally specified because it varies depending on other conditions such as the reaction temperature, but is usually performed for 0.5 to 10 hours.
- the obtained polycarbonate-polydiorganosiloxane copolymer resin can be appropriately subjected to physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate-polydiorganosiloxane copolymer resin with a desired reduced viscosity [ ⁇ SP /c].
- the obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (purity).
- the content of the polydiorganosiloxane block represented by the above general formula (3) in component A-2 is preferably 0.05 to 50% by weight.
- the content of such polydiorganosiloxane block is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. If the content is less than 0.05% by weight, plating properties at a practical level may not be achieved, and if it exceeds 50% by weight, poor appearance may occur during injection molding.
- the degree of diorganosiloxane polymerization and the content of polydiorganosiloxane block can be calculated by 1 H-NMR measurement.
- the average size of the polydiorganosiloxane domains in the polycarbonate polymer matrix is in the range of 5 to 100 nm. Such an average size is preferably 5 to 80 nm, and more preferably 7 to 30 nm. Outside this range, plating properties at a practical level will not be achieved.
- the average domain size of the polydiorganosiloxane domains is measured using a cross-sectional observation image of the resin composition of 850 nm square (722,500 nm 2 ) using an electron microscope (hereinafter sometimes abbreviated as TEM). Specifically, a molded piece of 10 mm wide, 80 mm long, and 4.0 mm thick produced by injection molding was cut perpendicularly to the flow direction of the resin at a depth of 2 mm from the intersection 15 mm from the gate and 5 mm from the side end using a microtome (EM UC6 manufactured by Leica Microsystems), and an ultra-thin slice was prepared by attaching it to a grid (EM FINE GRID No.
- the content of polycarbonate-polydiorganosiloxane copolymer resin (A-2) in 100% by weight of component A is 0.1 to 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 100% by weight. If the content is less than 0.1% by weight, plating properties at a practical level will not be achieved.
- the use of the polycarbonate-polydiorganosiloxane copolymer resin (A-2) improves plating properties during circuit formation, presumably because the surface becomes more easily roughened during laser irradiation, increasing the surface area.
- the additive for laser irradiation three-dimensional circuit molding used in the present invention is a compound that enables three-dimensional circuit molding by laser irradiation by blending.
- the additive for laser irradiation three-dimensional circuit molding may be a synthetic product or a commercially available product.
- the commercially available product may be a substance sold for other purposes in addition to those commercially available as additives for laser irradiation three-dimensional circuit molding.
- the additive for laser irradiation three-dimensional circuit molding may be a compound containing only one type of metal, but is preferably a mixed metal compound containing at least two types of metal. Examples of the metal include copper, chromium, tin, zinc, and antimony.
- the additive for laser irradiation three-dimensional circuit molding may be used alone or in combination of two or more types.
- the additive for laser irradiation three-dimensional circuit molding used in the present invention a compound containing copper is preferable, and a compound mainly composed of an oxide containing copper and chromium is more preferable.
- the plating property of the resin molded product can be further improved, so that plating can be appropriately formed on the surface of the resin molded product.
- the copper content is preferably 10 to 40% by weight
- the chromium content is preferably 10 to 50% by weight.
- the form in which copper and chromium are contained is preferably a spinel structure.
- the spinel structure is one of the crystal structures of metal double oxides of the general formula AB 2 O 4 type.
- the additive for laser irradiation three-dimensional circuit molding may contain other metal species.
- other metal species include antimony, tin, lead, indium, zinc, cadmium, iron, nickel, bismuth, iron, manganese, magnesium, calcium, arsenic, silver, and iron. These metal species may exist as oxides.
- the additive for laser irradiation three-dimensional circuit molding may be a metal compound whose main component is something other than copper and chromium.
- it is a compound whose main component is tin oxide, and a compound whose main component is an oxide containing antimony and tin is preferable.
- the tin content is greater than the antimony content are preferable, and the tin content relative to the total amount of tin and antimony is more preferably 80% by weight or more, and even more preferably 85% by weight or more.
- examples of such compounds include tin oxide doped with antimony and tin oxide doped with antimony oxide, and tin oxide doped with antimony oxide is preferable.
- the content of antimony relative to the total amount of tin oxide and antimony is preferably 1 to 20% by weight, and more preferably 3 to 15% by weight.
- the content of antimony relative to the total amount of tin oxide and antimony is preferably 0.5 to 10% by weight, and more preferably 1.0 to 8.0% by weight.
- the average particle size of the additive for laser irradiation three-dimensional circuit molding used in the present invention is preferably 0.01 to 50 ⁇ m, and more preferably 0.05 to 30 ⁇ m. This configuration tends to improve the uniformity of the plating surface when plating is applied.
- the additive for laser irradiation three-dimensional circuit molding used in the present invention is preferably an additive that absorbs light with a wavelength of 1064 nm.
- the ability to absorb light with a wavelength of 1064 nm makes it easier to form a plating layer on the surface of a resin molded product.
- the content of component B is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 15 parts by weight, per 100 parts by weight of component A. If the content is less than 1 part by weight, the plating properties will be insufficient, and if it exceeds 50 parts by weight, poor appearance will occur during injection molding.
- the polycarbonate resin composition of the present invention may contain various inorganic fillers known as reinforcing fillers.
- Suitable inorganic fillers include glass (fibrous glass and plate glass), carbon (fibrous carbon), and the like. and non-fibrous carbon), silicate minerals, calcium carbonate, silica and titanium dioxide, among which at least one inorganic filler selected from the group consisting of glass, carbon fiber and silicate minerals is preferred. It is more preferable that
- Fibrous glass filler examples include glass fiber, metal-coated glass fiber, and milled glass fiber.
- the glass fiber that is the base of the fibrous glass filler is made by quenching molten glass while stretching it by various methods to form a predetermined fiber shape. The quenching and stretching in this case are not particularly limited.
- the cross-sectional shape may be a perfect circle, or a shape other than a perfect circle such as an ellipse, cocoon, flat, or trefoil. Furthermore, a mixture of a perfect circle and a shape other than a perfect circle may be used.
- the flat shape is a shape in which the average major axis of the fiber cross section is 10 to 50 ⁇ m, preferably 15 to 40 ⁇ m, and more preferably 20 to 35 ⁇ m, and the average ratio of the major axis to the minor axis (major axis/minor axis) is 1.5 to 8, preferably 2 to 6, and more preferably 2.5 to 5.
- the average fiber diameter of a fibrous glass filler having a high aspect ratio such as glass fiber is preferably 1 to 25 ⁇ m, more preferably 3 to 17 ⁇ m.
- the fiber length of a fibrous glass filler having a high aspect ratio is preferably 60 to 500 ⁇ m, more preferably 100 to 400 ⁇ m, and particularly preferably 120 to 350 ⁇ m, as the number average fiber length in the polycarbonate resin composition.
- the number average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of the fibrous glass filler collected by high-temperature incineration of a molded product, dissolution with a solvent, decomposition with a chemical, etc., using an optical microscope. Furthermore, when calculating this value, the value is calculated by a method in which the fiber diameter is used as a guide and fibers with a length less than this are not counted.
- the aspect ratio of the high aspect ratio fibrous glass filler is preferably 10 to 200, more preferably 15 to 100, and even more preferably 20 to 50.
- the aspect ratio is the average fiber length divided by the average fiber diameter.
- Glass milled fiber is usually produced by breaking glass fiber into short fibers using a grinder such as a ball mill.
- the aspect ratio of a fibrous glass filler having a low aspect ratio such as glass milled fiber is preferably 2 to 10, more preferably 3 to 8.
- the fiber length of a fibrous glass filler having a low aspect ratio is preferably 5 to 150 ⁇ m, more preferably 9 to 80 ⁇ m, as the number average fiber length in the polycarbonate resin composition.
- the average fiber diameter is preferably 1 to 15 ⁇ m, more preferably 3 to 13 ⁇ m.
- the glass composition of the above-mentioned various fibrous glass fillers is not particularly limited, and may be any of various glass compositions represented by A glass, C glass, D glass, E glass, S glass, and NE glass.
- Such fibrous glass fillers may contain components such as TiO 2 , SO 3 , and P 2 O 5 as necessary.
- E glass (alkali-free glass) and NE glass are more preferable.
- fibrous glass fillers that have been surface-treated with a known surface treatment agent, such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent, are preferable from the viewpoint of improving mechanical strength.
- fibrous glass fillers including those coated with the metal or metal oxide described below
- fibrous glass fillers that have been bundled with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, or a urethane resin are preferably used.
- the amount of the bundling agent attached to the bundled fibrous glass filler is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight, based on 100% by weight of the fibrous glass filler.
- the fibrous glass filler includes those having a surface coating of a different material.
- suitable examples of such different materials include metals and metal oxides.
- metals include silver, copper, nickel, and aluminum.
- metal oxides include titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide.
- the method of surface coating such different materials is not particularly limited, and examples include various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering.
- C-2 Plate-shaped glass filler
- the plate-like glass filler examples include glass flakes, metal-coated glass flakes, and metal oxide-coated glass flakes.
- the glass flakes that form the base of the plate-shaped glass filler are plate-shaped glass fillers manufactured by methods such as the cylinder blow method and the sol-gel method.
- the size of the raw material for such glass flakes can be selected from a variety of sizes depending on the degree of crushing and classification.
- the average particle size of the glass flakes used as the raw material is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, and even more preferably 30 to 300 ⁇ m. Glass flakes in the above range are excellent in both handleability and moldability. Normally, plate-shaped glass fillers crack when melted and kneaded with resin, and the average particle size becomes smaller.
- the number average particle size of the plate-shaped glass filler in the polycarbonate resin composition is preferably 10 to 200 ⁇ m, more preferably 15 to 100 ⁇ m, and even more preferably 20 to 80 ⁇ m.
- the number average particle size is a value calculated by an image analyzer from an image obtained by observing under an optical microscope the residue of the plate-shaped glass filler collected after high-temperature incineration of the molded product, dissolution in a solvent, decomposition with chemicals, and other processes. The value is calculated using the flake thickness as a guide and does not count flakes with a length less than that.
- the thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 8 ⁇ m, and even more preferably 1.5 to 6 ⁇ m. Plate-shaped glass fillers having the above number average particle size and thickness may achieve good mechanical strength, appearance, and moldability.
- the glass composition of the plate-shaped glass filler is not particularly limited, and may be any of various glass compositions such as A-glass, C-glass, and E-glass. Such glass filler may contain TiO 2 , SO 3 , and P 2 O 5 , if necessary. Among these, E-glass (alkali-free glass) is more preferable. Furthermore, the plate-shaped glass filler is preferably surface-treated with a known surface treatment agent, such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent, from the viewpoint of improving mechanical strength.
- a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent
- the plate-shaped glass filler is preferably one that has been subjected to bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, or a urethane resin.
- the amount of the bundling agent attached to the plate-shaped glass filler that has been subjected to bundling treatment is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight, based on 100% by weight of the plate-shaped glass filler.
- the plate-shaped glass filler includes those having a surface coating of a different material.
- suitable examples of such different materials include metals and metal oxides.
- metals include silver, copper, nickel, and aluminum.
- metal oxides include titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide.
- the method of surface coating of such different materials is not particularly limited, and examples include various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering.
- fibrous carbon fillers include carbon fiber, metal-coated carbon fiber, carbon milled fiber, vapor-grown carbon fiber, and carbon nanotubes.
- Carbon nanotubes may have a fiber diameter of 0.003 to 0.1 ⁇ m and may be single-walled, double-walled, or multi-walled, with multi-walled (so-called MWCNT) being preferred.
- MWCNT multi-walled
- carbon fiber and metal-coated carbon fiber are preferred because of their excellent mechanical strength and the ability to impart good electrical conductivity. Good electrical conductivity is one of the important properties required of resin materials in recent digital precision instruments (e.g., digital still cameras).
- any of cellulose-based, polyacrylonitrile-based, and pitch-based carbon fibers can be used.
- Carbon fibers obtained by a method of spinning without a process of infusibility such as a method of preventing or forming a raw material composition consisting of a polymer and a solvent by a methylene bond of aromatic sulfonic acids or their salts, and then carbonizing the raw material composition, can also be used.
- any of general-purpose types, medium elasticity types, and high elasticity types can be used.
- polyacrylonitrile-based high elasticity types are particularly preferred.
- the average fiber diameter of the carbon fibers is not particularly limited, but is usually 3 to 15 ⁇ m, preferably 5 to 13 ⁇ m.
- Carbon fibers having an average fiber diameter in this range may be able to exhibit good mechanical strength and fatigue properties without impairing the appearance of the molded product.
- the preferred fiber length of the carbon fibers is preferably 60 to 500 ⁇ m, more preferably 80 to 400 ⁇ m, and even more preferably 100 to 300 ⁇ m, as the number average fiber length in the polycarbonate resin composition.
- the number average fiber length is a value calculated by an image analyzer from optical microscope observation of carbon fiber residues collected from processes such as high-temperature incineration of molded products, dissolution in solvents, and decomposition with chemicals. In addition, when calculating this value, fibers with lengths less than the fiber diameter are not counted.
- the aspect ratio of carbon fibers is preferably in the range of 10 to 200, more preferably in the range of 15 to 100, and even more preferably in the range of 20 to 50. The aspect ratio is the value obtained by dividing the average fiber length by the average fiber diameter.
- the surface of the carbon fiber is preferably oxidized to enhance adhesion to the matrix resin and improve mechanical strength.
- the oxidation method is not particularly limited, but suitable examples include (1) a method of treating a fibrous carbon filler with an acid or alkali or a salt thereof, or an oxidizing gas, (2) a method of baking a fiber or a fibrous carbon filler that can be made into a fibrous carbon filler at a temperature of 700°C or higher in the presence of an inert gas containing an oxygen-containing compound, and (3) a method of oxidizing the fibrous carbon filler and then heat-treating it in the presence of an inert gas.
- Metal-coated carbon fiber is a carbon fiber with a metal layer coated on its surface.
- metals include silver, copper, nickel, and aluminum, with nickel being preferred in terms of the corrosion resistance of the metal layer.
- As a method for metal coating the various methods described above for surface coating with different materials in plate-shaped glass fillers can be used. Among these, plating is preferably used.
- the carbon fibers listed above can be used as the base carbon fiber.
- the thickness of the metal coating layer is preferably 0.1 to 1 ⁇ m, more preferably 0.15 to 0.5 ⁇ m, and even more preferably 0.2 to 0.35 ⁇ m.
- Such carbon fibers and metal-coated carbon fibers are preferably bundled and treated with olefin-based resins, styrene-based resins, acrylic-based resins, polyester-based resins, epoxy-based resins, urethane-based resins, etc.
- fibrous carbon fillers treated with urethane-based resins and epoxy-based resins are preferred in the present invention because of their excellent mechanical strength.
- non-fibrous carbon fillers examples include carbon black, graphite, and fullerene. Among these, carbon black and graphite are preferred from the viewpoints of mechanical strength, wet heat resistance, and thermal stability.
- carbon black carbon black having a DBP oil absorption of 100 ml/100 g to 500 ml/100 g is preferred from the viewpoint of electrical conductivity.
- Such carbon black is generally acetylene black or ketjen black. Specific examples include Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd., Vulcan XC-72 and BP-2000 manufactured by Cabot Corporation, and Ketjen Black EC and Ketjen Black EC-600JD manufactured by Lion Corporation.
- Graphite can be either natural graphite, known as graphite by its mineral name, or various types of artificial graphite.
- Natural graphite can be any of earthy graphite, vein graphite (also known as lump graphite), and flake graphite.
- Artificial graphite is made by heat treating amorphous carbon to artificially orient irregularly arranged microscopic graphite crystals, and includes the artificial graphite used in general carbon materials, as well as kish graphite, decomposed graphite, and pyrolytic graphite.
- the artificial graphite used in general carbon materials is usually manufactured by graphitizing petroleum coke or coal-based pitch coke as the main raw material.
- the graphite of the present invention may include expanded graphite that has been made thermally expandable by a treatment such as an acid treatment, or graphite that has already been expanded.
- the particle size of the graphite is preferably in the range of 2 to 300 ⁇ m. Such a particle size is more preferably 5 to 200 ⁇ m, even more preferably 7 to 100 ⁇ m, and particularly preferably 7 to 50 ⁇ m. If the average particle size is less than 2 ⁇ m, the effect of improving rigidity may be small, and if the average particle size exceeds 300 ⁇ m, the impact resistance may be significantly reduced, and so-called graphite floating may become noticeable on the surface of the molded product.
- the average particle size refers to the particle size of the graphite itself before it becomes a resin composition, and the particle size is determined by a laser diffraction/scattering method.
- the fixed carbon content of the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 98% by weight or more.
- the volatile content of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and even more preferably 1% by weight or less.
- the surface of the graphite may also be subjected to a surface treatment, such as an epoxy treatment, a urethane treatment, a silane coupling treatment, or an oxidation treatment, in order to increase its affinity with the polycarbonate resin, as long as this does not impair the properties of the composition of the present invention.
- a surface treatment such as an epoxy treatment, a urethane treatment, a silane coupling treatment, or an oxidation treatment
- Suitable silicate minerals include orthosilicate, disilicate, cyclic silicate, and chain silicate.
- the silicate minerals are in a crystalline state, and the crystals may have any form that each silicate mineral can have.
- the crystals may have various shapes, such as fibrous or plate-like.
- the silicate mineral may be any of a compound of a complex oxide, an oxyacid salt (composed of an ion lattice), or a solid solution
- the complex oxide may be any of a combination of two or more single oxides, or a combination of two or more single oxides and oxyacid salts
- the solid solution may be any of a solid solution of two or more metal oxides, or a solid solution of two or more oxyacid salts. It may also be a hydrate.
- the form of the water of crystallization in the hydrate may be any of a form that enters as hydrogen silicate ions as Si-OH, a form that enters ionic form as hydroxide ions (OH-) relative to metal cations, or a form that enters as H 2 O molecules in the gaps in the structure.
- silicate minerals synthetic products corresponding to natural products can also be used.
- synthetic products silicate minerals obtained by various conventionally known methods, such as various synthesis methods using solid-state reactions, hydrothermal reactions, and ultra-high pressure reactions, can be used.
- silicate minerals in each metal oxide component include the following.
- the notation in parentheses here is the name of the mineral, etc. that contains such silicate minerals as the main component, and means that the compound in parentheses can be used as the exemplified metal salt.
- K 2 O examples include K 2 O.SiO 2 , K 2 O.4SiO 2.H 2 O , K 2 O.Al 2 O 3.2SiO 2 (kalsilite), K 2 O.Al 2 O 3.4SiO 2 (leucite), and K 2 O.Al 2 O 3.6SiO 2 (orthoclase).
- Examples of minerals that contain Na2O include Na2O.SiO2 and its hydrates, Na2O.2SiO2 , 2Na2O.SiO2 , Na2O.4SiO2 , Na2O.3SiO2.3H2O , Na2O.Al2O3.2SiO2 , Na2O.Al2O3.4SiO2 ( jadeite ) , 2Na2O.3CaO.5SiO2 , 3Na2O.2CaO.5SiO2 , and Na2O.Al2O3.6SiO2 ( albite ) .
- Examples of materials containing Li2O as a component include Li2O.SiO2 , 2Li2O.SiO2 , Li2O.SiO2.H2O , 3Li2O.2SiO2 , Li2O.Al2O3.4SiO2 ( petalite ) , Li2O.Al2O3.2SiO2 ( eucryptite ) , and Li2O.Al2O3.4SiO2 ( spodumene ) .
- Examples of materials containing BaO as a component include BaO.SiO 2 , 2BaO.SiO 2 , BaO.Al 2 O 3.2SiO 2 (celsian), and BaO.TiO 2.3SiO 2 (bentite).
- Examples of minerals that contain CaO include 3CaO.SiO 2 (alite, a cement clinker mineral), 2CaO.SiO 2 (belite, a cement clinker mineral), 2CaO.MgO.2SiO 2 (akermanite), 2CaO.Al 2 O 3.SiO 2 (gehlenite), a solid solution of akermanite and gehlenite (melilite), CaO.SiO 2 (wollastonite (including both ⁇ -type and ⁇ -type)), CaO.MgO.2SiO 2 (diopside), CaO.MgO.SiO 2 (magnesium olivine), 3CaO.MgO.2SiO 2 (merwinite), CaO.Al 2 O 3.2SiO 2 (anorthite), and 5CaO.6SiO 2.5H 2 .
- 3CaO.SiO 2 alite, a cement clinker mineral
- Tobermorite group hydrates such as 2CaO.SiO 2.H 2 O (tobermorite, 5CaO.6SiO 2.9H 2 O, etc.), wollastonite group hydrates such as 2CaO.SiO 2.H 2 O (hillebrandite), xonotlite group hydrates such as 6CaO.6SiO 2.H 2 O (xonotlite), gyrolite group hydrates such as 2CaO.SiO 2.2H 2 O (gyrolite), CaO.Al 2 O 3.2SiO 2.H 2 O (lawsonite), CaO.FeO.2SiO 2 (hedengite), 3CaO.2SiO 2 (chilcoanite), 3CaO.Al 2 O 3.3SiO 2 (grossula), 3CaO.Fe 2 O 3.3SiO 2 (silicate), 3CaO.Al 2 O 3.3SiO 2
- Portland cement can be mentioned as an example of a silicate mineral that contains CaO as a component.
- a silicate mineral that contains CaO there are no particular limitations on the type of Portland cement, and any type can be used, such as normal, early strength, extra early strength, medium heat, sulfate resistant, and white.
- various types of mixed cements such as blast furnace cement, silica cement, and fly ash cement, can also be used as component B.
- Other examples of silicate minerals that contain CaO as a component include blast furnace slag and ferrite.
- ZnO-containing mineral examples include ZnO.SiO2 , 2ZnO.SiO2 (troostite), and 4ZnO.2SiO2.H2O ( hemimorphite ).
- MnO-containing mineral examples include MnO.SiO2 , 2MnO.SiO2 , CaO.4MnO.5SiO2 (rhodonite), and coesrite .
- FeO-containing mineral examples include FeO.SiO2 (ferrosilite ) , 2FeO.SiO2 (ferroolivine), 3FeO.Al2O3.3SiO2 ( almandine ), and 2CaO.5FeO.8SiO2.H2O ( tetactinocene ).
- Examples of materials containing CoO as a component include CoO.SiO2 and 2CoO.SiO2 .
- Examples of minerals that contain MgO include MgO.SiO2 (steatite, enstatite), 2MgO.SiO2 ( forsterite ) , 3MgO.Al2O3.3SiO2 (byropes), 2MgO.2Al2O3.5SiO2 (cordierite ) , 2MgO.3SiO2.5H2O , 3MgO.4SiO2.H2O ( talc), 5MgO.8SiO2.9H2O (attapulgite ) , 4MgO.6SiO2.7H2O ( sepiolite), 3MgO.2SiO2.2H2O ( chrysolite ) , 5MgO.2CaO.8SiO2.H2O (tremelite), 5MgO.Al2O3.3SiO2 (calcite), 5MgO .
- Examples of materials that contain Fe2O3 as a component include Fe2O3.SiO2 .
- Examples of materials that contain Al 2 O 3 include Al 2 O 3.SiO 2 (sillimanite, andalusite, kyanite), 2Al 2 O 3.SiO 2 , Al 2 O 3.3SiO 2 , 3Al 2 O 3.2SiO 2 (mullite), Al 2 O 3.2SiO 2.2H 2 O (kaolinite), Al 2 O 3.4SiO 2.H 2 O (pyrophyllite ) , Al 2 O 3.4SiO 2.H 2 O (bentonite), K 2 O.3Na 2 O.4Al 2 O 3.8SiO 2 (nepheline), K 2 O.3Al 2 O 3.6SiO 2.2H 2 O ( muscovite , sericite ) , K 2 O.6MgO.Al 2 O 3.6SiO 2.2H 2 O (phlogovite), as well as various zeolites, fluorphlogopite, and biotite.
- talc, mica, and wollastonite are particularly suitable, as they have an excellent balance between rigidity and impact resistance, excellent resistance to moist heat, thermal stability, and appearance, and are also easily available.
- Talc is a hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO2.3MgO.2H2O , and is usually a scaly particle with a layered structure, and is composed of 56-65% by weight of SiO2 , 28-35% by weight of MgO, and approximately 5% by weight of H2O .
- Other minor components include 0.03-1.2 % by weight of Fe2O3 , 0.05-1.5% by weight of Al2O3 , 0.05-1.2% by weight of CaO, 0.2% by weight or less of K2O , and 0.2% by weight or less of Na2O .
- a more preferred composition of talc is SiO 2 : 62-63.5 wt%, MgO: 31-32.5 wt%, Fe 2 O 3 : 0.03-0.15 wt%, Al 2 O 3 : 0.05-0.25 wt%, and CaO: 0.05-0.25 wt%.
- the ignition loss is preferably 2-5.5 wt%.
- the particle size of the talc is preferably in the range of 0.1 to 50 ⁇ m (more preferably 0.1 to 10 ⁇ m, even more preferably 0.2 to 5 ⁇ m, and particularly preferably 0.2 to 3.5 ⁇ m) in terms of the average particle size measured by the sedimentation method. Therefore, a more suitable talc of the present invention is one having the above-mentioned preferred composition and an average particle size of 0.2 to 3.5 ⁇ m. Furthermore, it is particularly suitable to use talc having a bulk density of 0.5 (g/cm 3 ) or more as a raw material. An example of talc that satisfies these conditions is "Upn HS-T0.8" manufactured by Hayashi Kasei Co., Ltd.
- the average particle size of talc refers to D50 (median diameter of particle size distribution) measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods.
- D50 medium diameter of particle size distribution
- a specific example of an apparatus for performing such measurements is Sedigraph 5100 manufactured by Micromeritics Co., Ltd.
- talc is preferably classified using various classifiers, and one with a uniform particle size distribution is preferable.
- classifiers include impactor type inertial force classifiers (such as variable impactors), Coanda effect type inertial force classifiers (such as elbow jets), and centrifugal field classifiers (such as multi-stage cyclones, microplexes, dispersion separators, Accucut, turbo classifiers, turboplexes, micron separators, and super separators).
- impactor type inertial force classifiers such as variable impactors
- Coanda effect type inertial force classifiers such as elbow jets
- centrifugal field classifiers such as multi-stage cyclones, microplexes, dispersion separators, Accucut, turbo classifiers, turboplexes, micron separators, and super separators.
- the talc is in an aggregated state from the viewpoint of ease of handling, and methods for producing this include a method using degassing compression, a method using a sizing agent for compression, etc.
- the method using degassing compression is preferable because it is simple and does not mix unnecessary sizing agent resin components into the resin composition of the present invention.
- Mica having an average particle size of 5 to 250 ⁇ m is preferably used. More preferably, mica having an average particle size of 5 to 50 ⁇ m is used. If the average particle size of mica is less than 5 ⁇ m, it is difficult to obtain the effect of improving rigidity. On the other hand, a resin composition containing mica having an average particle size of more than 250 ⁇ m may have poor appearance and flame retardancy while mechanical properties tend to be saturated.
- the average particle size of mica is measured by a laser diffraction/scattering method or a vibrating sieving method. The laser diffraction/scattering method is preferably performed on mica having a 325 mesh pass of 95% by weight or more by the vibrating sieving method.
- the vibrating sieving method For mica having a particle size of more than this, the vibrating sieving method is generally used.
- the vibrating sieving method of the present invention first, 100 g of mica powder to be used is sieved for 10 minutes using a vibrating sieve and JIS standard sieves stacked in the order of mesh size. This method measures the weight of the powder remaining on each sieve to determine the particle size distribution.
- the thickness of the mica is preferably 0.01 to 1 ⁇ m as measured by observation with an electron microscope. More preferably, the thickness is 0.03 to 0.3 ⁇ m.
- the aspect ratio is preferably 5 to 200, more preferably 10 to 100.
- the mica used is preferably muscovite mica, whose Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other micas such as phlogovite, and solves the problem of the present invention at a better level. Therefore, the more suitable mica of the present invention is muscovite with an average particle size of 5 to 250 ⁇ m, more preferably 5 to 50 ⁇ m. An example of such a suitable mica is "A-21" manufactured by Yamaguchi Mica Co., Ltd.
- the mica may be produced by either a dry grinding method or a wet grinding method as a grinding method. Dry grinding is more common and less expensive, but wet grinding is more effective at grinding mica into thinner, finer pieces (which improves the rigidity of the resin composition). In the present invention, mica produced by the wet grinding method is more suitable.
- the fiber diameter of wollastonite is preferably 0.1 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, and even more preferably 0.1 to 3 ⁇ m.
- the aspect ratio (average fiber length/average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less.
- the fiber diameter is measured by observing the reinforcing filler with an electron microscope, determining the individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult to accurately measure the size of the target level with an optical microscope.
- the fiber diameter is measured by randomly extracting the filler to be measured for the image obtained by observation with the electron microscope, measuring the fiber diameter near the center, and calculating the number average fiber diameter from the measured values.
- the magnification of the observation is about 1000 times, and the number of measured fibers is 500 or more (600 or less is suitable for work).
- the average fiber length is measured by observing the filler with an optical microscope, determining the individual lengths, and calculating the number average fiber length from the measured values.
- the observation with an optical microscope starts with preparing a sample in which the fillers are dispersed so that they do not overlap each other too much.
- the observation is performed under the condition of a 20x objective lens, and the observed image is captured as image data by a CCD camera with about 250,000 pixels.
- the obtained image data is used with an image analyzer, and a program for determining the maximum distance between two points of the image data is used to calculate the fiber length.
- the size per pixel corresponds to a length of 1.25 ⁇ m, and the number of measurements is 500 or more (600 or less is preferable for work).
- the iron content in wollastonite is 0.5% by weight or less when converted to Fe 2 O 3 by such magnetic separator treatment.
- more preferred wollastonite of the present invention has a fiber diameter of 0.1 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, and even more preferably 0.1 to 3 ⁇ m, an average particle size of 5 to 250 ⁇ m, more preferably 5 to 50 ⁇ m, and an iron content of 0.5% by weight or less calculated as Fe 2 O 3.
- preferred wollastonite include "SH-1250" and "SH-1800” manufactured by Kinsei Matec Co., Ltd., “KGP-H40” manufactured by Kansai Matec Co., Ltd., and "NYGLOS4" manufactured by NYCO Corporation.
- the silicate mineral is preferably not surface-treated, but may be surface-treated with various surface treatment agents such as silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (e.g., phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydrides), and wax. It may also be granulated into granules using binders such as various resins, higher fatty acid esters, and wax.
- Talc and wollastonite are particularly suitable silicate minerals in the present invention. Such talc and wollastonite are good at achieving both rigidity and impact resistance, and when mixed with polycarbonate resin, there is little deterioration in hue and appearance (e.g., the occurrence of silver streaks).
- Titanium dioxide that is generally used for various purposes can be used, and is itself widely known.
- titanium dioxide that is composed of 100% by weight of TiO 2 (note that in the present invention, the titanium dioxide component of titanium dioxide is expressed as "TiO 2 ", and the whole including the surface treatment agent is expressed as "titanium dioxide”).
- TiO 2 titanium dioxide
- titanium dioxide is usually surface-treated with oxides of various metals such as aluminum, silicon, titanium, zirconium, antimony, tin, and zinc.
- preferred titanium dioxide is one that has been surface-treated with a metal oxide. Note that the metal oxide components for these surface treatments may be in a form in which a part of them is present inside the TiO 2 particles.
- the titanium dioxide is surface-treated with an organic compound.
- a surface treatment agent various treatment agents such as polyol-based, amine-based, and silicone-based treatment agents can be used.
- polyol-based surface treatment agents include pentaerythritol, trimethylolethane, and trimethylolpropane.
- amine-based surface treatment agents include acetate of triethanolamine and acetate of trimethylolamine.
- silicone-based surface treatment agents include halogen-substituted organosilicon compounds and organosilicon compounds containing alkoxy groups and/or Si-H groups, with the latter organosilicon compounds being particularly preferred.
- halogen-substituted organosilicon compounds include alkylchlorosilanes, and examples of organosilicon compounds containing alkoxy groups and/or Si-H groups include alkylalkoxysilanes, alkylalkoxysiloxanes, and alkylhydrogensiloxanes.
- silane and siloxane compounds may have some of their alkyl groups substituted with phenyl groups, but it is more preferable that they are not substituted with phenyl groups.
- the number of carbon atoms in these alkyl groups is preferably 1 to 30, more preferably 1 to 12.
- the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and in particular, a methoxy group is suitable.
- the titanium dioxide in the present invention may have either anatase or rutile crystal form, and these may be mixed and used as necessary.
- the rutile form is more preferable in terms of initial mechanical properties and long-term weather resistance.
- the rutile crystal may contain anatase crystals.
- TiO2 produced by the sulfuric acid method, chlorine method, and other various methods may be used, but the chlorine method is more preferable.
- the shape of the titanium dioxide is not particularly limited, but particulate titanium dioxide is more preferable.
- the average particle size of titanium dioxide is preferably 0.01 to 0.4 ⁇ m, more preferably 0.1 to 0.3 ⁇ m, and even more preferably 0.15 to 0.25 ⁇ m. The average particle size is calculated by measuring the individual single particle sizes from electron microscope observation and averaging the number of particles.
- Coating of the TiO2 surface with various metal oxides can be carried out by various methods that are commonly used. For example, it is produced from the following steps 1) to 8). That is, 1) making untreated TiO2 after dry grinding into an aqueous slurry, 2) wet grinding the slurry to make it fine, 3) collecting the fine-particle slurry, 4) adding a water-soluble compound of a metal salt to the fine-particle slurry, 5) neutralizing and coating the TiO2 surface with a hydrous oxide of the metal, 6) removing by-products, adjusting the slurry pH, filtering, and washing with pure water, 7) drying the washed cake, and 8) pulverizing the dried material with a jet mill or the like.
- a method of reacting an active metal compound with TiO2 particles in the gas phase can be mentioned. Furthermore, in coating the TiO2 surface with a metal oxide surface treatment agent, it is possible to perform calcination after surface treatment, perform surface treatment again after surface treatment, or perform calcination after surface treatment and then perform surface treatment again. Furthermore, the surface treatment with a metal oxide can be either a high-density treatment or a low-density (porous) treatment.
- the titanium dioxide of the present invention is surface-treated with aluminum oxide and silicon oxide. These may be surface-treated in any order or as a mixture, but it is preferable that the titanium dioxide is surface-treated with aluminum oxide followed by silicon oxide. More preferably, the titanium dioxide is surface-treated with an organosilicon compound containing an alkoxy group and/or a Si-H group after the metal oxide treatment as described above.
- the content of component C is preferably 1 to 150 parts by weight, more preferably 3 to 100 parts by weight, and even more preferably 5 to 50 parts by weight, per 100 parts by weight of component A. If the content is less than 1 part by weight, the plating adhesion may be insufficient, and if it exceeds 150 parts by weight, poor appearance may occur during injection molding.
- various stabilizers for preventing a decrease in molecular weight during molding and for stabilizing color, release agents, colorants, impact modifiers, fillers, flame retardants, etc. may be used.
- 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 improves, for example, antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.
- Such flame retardants include (1) organometallic salt-based flame retardants (e.g., organic sulfonic acid alkali (earth) metal salts, boric acid metal salt-based flame retardants, and stannic acid metal salt-based flame retardants, etc.), (2) organophosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, etc.), (3) silicone-based flame retardants made of silicone compounds, and (4) halogen-based flame retardants (e.g., brominated epoxy resins, brominated polystyrene, brominated polycarbonates (including oligomers), brominated polyacrylates, and chlorinated polyethylenes, etc.), etc.
- organometallic salt-based flame retardants e.g., organic sulfonic acid alkali (earth) metal salts, boric acid metal salt-based flame retard
- Organic metal salt flame retardants are advantageous in that they can maintain heat resistance and provide antistatic properties to a certain extent.
- the organic metal salt flame retardant most advantageously used in the present invention is a fluorine-containing organic metal salt compound.
- the fluorine-containing organic metal salt compound of the present invention refers to a metal salt compound consisting of an anion component consisting of an organic acid having a fluorine-substituted hydrocarbon group and a cation component consisting of a metal ion.
- More preferred examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates.
- the fluorine-containing organic metal salt compounds can be used alone or in combination of two or more. Among them, metal salts of fluorine-substituted organic sulfonic acids are preferred, and metal salts of sulfonic acids having a perfluoroalkyl group are particularly preferred.
- the number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8.
- the metals constituting the metal ions of the organic metal salt flame retardant are alkali metals or alkaline earth metals.
- alkali metals include lithium, sodium, potassium, rubidium, and cesium.
- alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Alkaline metals are more preferred. Therefore, the preferred organic metal salt flame retardant is an alkali metal salt of perfluoroalkylsulfonic acid.
- rubidium and cesium are preferred when a higher transparency is required, but they are not versatile and are difficult to refine, which can result in disadvantages in terms of cost.
- the alkali metals in the alkali metal salt of perfluoroalkylsulfonic acid can be used differently, but potassium salt of perfluoroalkylsulfonic acid, which has an excellent balance of properties in all respects, is the most preferred.
- Such potassium salts can also be used in combination with alkali metal salts of perfluoroalkylsulfonic acid made of other alkali metals.
- Such alkali metal salts of perfluoroalkylsulfonic acid include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctane sulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulf
- the above-mentioned fluorine-containing organic metal salt preferably has a fluoride ion content of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less, as measured by ion chromatography.
- the lower the fluoride ion content the better the flame retardancy and light resistance.
- the lower limit of the fluoride ion content can be set to essentially 0, but in terms of the balance between the refining labor hours and the effect, a practical value of about 0.2 ppm is preferable.
- Perfluoroalkylsulfonic acid alkali metal salts with such a fluoride ion content are purified, for example, as follows.
- Perfluoroalkylsulfonic acid alkali metal salt is dissolved in ion-exchanged water in an amount 2 to 10 times the weight of the metal salt at a temperature in the range of 40 to 90°C (more preferably 60 to 85°C).
- the alkali metal salt of perfluoroalkylsulfonic acid is produced by neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or by neutralizing perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide (preferably the latter method).
- the ion-exchanged water is particularly preferably water having an electrical resistance of 18 M ⁇ cm or more.
- the liquid in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably for 0.5 to 2.5 hours.
- the liquid is then cooled to a range of 0 to 40°C, more preferably 10 to 35°C. Crystals are precipitated by cooling. The precipitated crystals are removed by filtration. In this way, a suitable purified alkali metal salt of perfluoroalkylsulfonic acid is produced.
- the content of the fluorine-containing organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, and even more preferably 0.008 to 0.13 parts by weight, per 100 parts by weight of component A.
- the more preferably the content is within this range the more the effects expected from the incorporation of the fluorine-containing organometallic salt (such as flame retardancy and antistatic properties) will be exhibited, and the less adverse effects will be on the light resistance of the polycarbonate resin composition.
- suitable organometallic salt flame retardants are metal salts of organosulfonic acids that do not contain fluorine atoms.
- metal salts include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids (none of which contain fluorine atoms).
- aliphatic sulfonic acid metal salts include alkylsulfonic acid alkali (earth) metal salts, which can be used alone or in combination of two or more kinds (herein, the term "alkali (earth) metal salt” is used to mean both alkali metal salts and alkaline earth metal salts).
- alkanesulfonic acids used in such alkylsulfonic acid alkali (earth) metal salts include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, etc., which can be used alone or in combination of two or more kinds.
- the aromatic sulfonic acid used in the alkali (earth) metal salt of aromatic sulfonate may be at least one acid selected from the group consisting of monomeric or polymeric aromatic sulfide sulfonic acids, aromatic carboxylic acid and ester sulfonic acids, monomeric or polymeric aromatic ether sulfonic acids, aromatic sulfonate sulfonic acids, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfone sulfonic acids, aromatic ketone sulfonic acids, heterocyclic sulfonic acids, aromatic sulfoxide sulfonic acids, and aromatic sulfonic acid condensates with methylene bonds, and these may be used alone or in combination of two or more.
- aromatic sulfonic acid alkali (earth) metal salts include, for example, disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butyl
- examples of the alkali (earth) metal salts of sulfates include, in particular, the alkali (earth) metal salts of sulfates of monohydric and/or polyhydric alcohols.
- examples of such sulfates of monohydric and/or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, sulfates of polyoxyethylene alkyl phenyl ethers, mono-, di-, tri-, and tetrasulfates of pentaerythritol, sulfates of lauric acid monoglyceride, sulfates of palmitic acid monoglyceride, and sulfates of stearic acid monoglyceride.
- the alkali (earth) metal salts of these sulfates the alkali (earth) metal salt of these sulf
- alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides, such as saccharin, N-(p-tolylsulfonyl)-p-toluenesulfonimide, N-(N'-benzylaminocarbonyl)sulfanilimide, and alkali (earth) metal salts of N-(phenylcarboxyl)sulfanilimide.
- the preferred metal salts of organic sulfonic acids that do not contain fluorine atoms are the alkali (earth) metal salts of aromatic sulfonates, with the potassium salt being particularly preferred.
- the content is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, and even more preferably 0.01 to 0.1 parts by weight, per 100 parts by weight of component A.
- Organic phosphorus flame retardant As the organic phosphorus flame retardant of the present invention, a condensed phosphoric acid ester compound and a phosphazene compound are preferable.
- Condensed phosphate ester compound As the condensed phosphate ester compound, an aryl phosphate compound is preferably used. Condensed phosphate ester compounds have a plasticizing effect, and are therefore advantageous in that they can improve molding processability.
- the aryl phosphate compound various phosphate compounds known as flame retardants can be used, but more preferably, one or more phosphate compounds represented by the following general formula (8) can be used.
- M represents a divalent organic group derived from a dihydric phenol
- Ar 1 , Ar 2 , Ar 3 , and Ar 4 each represent a monovalent organic group derived from a monohydric phenol.
- a, b, c, and d each independently represent 0 or 1
- m represents an integer from 0 to 5.
- m represents the average value thereof and is a value from 0 to 5.
- the phosphate compound of the above formula may be a mixture of compounds having different m numbers, and in such a mixture, the average m number is preferably in the range of 0.5 to 1.5, more preferably 0.8 to 1.2, even more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.
- suitable dihydric phenols from which M is derived include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, of which resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.
- Preferred specific examples of the monohydric phenol from which Ar 1 , Ar 2 , Ar 3 and Ar 4 are derived include phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol, and among these, phenol and 2,6-dimethylphenol are preferred.
- Such monohydric phenols may be substituted with halogen atoms
- specific examples of phosphate compounds having groups derived from such monohydric phenols include tris(2,4,6-tribromophenyl)phosphate, tris(2,4-dibromophenyl)phosphate, and tris(4-bromophenyl)phosphate.
- phosphate compounds not substituted with halogen atoms include monophosphate compounds such as tri(2,6-xylyl)phosphate, as well as phosphate oligomers based on resorcinol bis(di(2,6-xylyl)phosphate), phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphoric ester oligomers based on bisphenol A bis(diphenyl phosphate).
- Phosphazene compounds have a plasticizing effect, and therefore are advantageous in that they can improve molding processability.
- various phosphazene compounds conventionally known as flame retardants can be used, but phosphazene compounds represented by the following general formulas (9) and (10) are preferred.
- X 1 , X 2 , X 3 , and X 4 represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom, and r represents an integer of 3 to 10.
- examples of the organic groups not containing halogen atoms represented by X1 , X2 , X3 , and X4 include an alkoxy group, a phenyl group, an amino group, an allyl group, etc.
- the cyclic phosphazene compound represented by the above formula (9) is preferred, and further, a cyclic phenoxyphosphazene in which X1 and X2 in the above formula (9) are phenoxy groups is particularly preferred.
- the content of the organophosphorus flame retardant is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and even more preferably 2 to 12 parts by weight, per 100 parts by weight of component A.
- the silicone compound used as the silicone-based flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion.
- various compounds proposed as flame retardants for aromatic polycarbonate resins can be used. It is believed that the silicone compound imparts flame retardant effect to the polycarbonate resin by forming a structure by itself or by combining with a component derived from the resin during combustion, or by a reduction reaction during the formation of the structure. Therefore, it is preferable that the silicone compound contains a group that is highly active in such a reaction, and more specifically, it is preferable that the silicone compound contains a predetermined amount of at least one group selected from alkoxy groups and hydrogens (i.e., Si-H groups).
- the content ratio of such groups is preferably in the range of 0.1 to 1.2 mol/100g, more preferably in the range of 0.12 to 1 mol/100g, and even more preferably in the range of 0.15 to 0.6 mol/100g.
- the ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by an alkali decomposition method.
- the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.
- silicone compounds used in silicone-based flame retardants include the rational formulas Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq.
- preferred silicone compound structures are MmDn, MmTp, MmDnTp, and MmDnQq
- more preferred structures are MmDn and MmDnTp.
- the coefficients m, n, p, and q in the above rational formula are integers of 1 or more that represent the degree of polymerization of each siloxane unit, and the sum of the coefficients in each rational formula is the average degree of polymerization of the silicone compound.
- This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, even more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more preferable the range, the better the flame retardancy.
- silicone compounds that contain a specified amount of aromatic groups also have excellent transparency and hue.
- the siloxane unit with that coefficient can be two or more types of siloxane units with different bonded hydrogen atoms or organic residues.
- the silicone compound may be linear or branched.
- the organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
- Specific examples of such organic residues include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and decyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, and aralkyl groups such as tolyl groups. More preferred are alkyl groups, alkenyl groups, or aryl groups having 1 to 8 carbon atoms. As the alkyl group, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, are particularly preferred.
- the silicone compound used as the silicone flame retardant contains an aryl group. More preferably, the proportion of aromatic groups represented by the following general formula (11) (aromatic group amount) is 10 to 70% by weight (more preferably 15 to 60% by weight).
- X's each independently represent an OH group or a monovalent organic residue having 1 to 20 carbon atoms.
- n represents an integer of 0 to 5. Furthermore, when n is 2 or more in formula (11), X's can each be different from one another.
- the silicone compounds used as silicone flame retardants may contain reactive groups other than the Si-H and alkoxy groups described above.
- reactive groups include amino groups, carboxyl groups, epoxy groups, vinyl groups, mercapto groups, and methacryloxy groups.
- Silicon compounds having Si-H groups are preferably exemplified by silicone compounds containing at least one of the structural units represented by the following general formulas (12) and (13).
- Z 1 to Z 3 each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (14).
- ⁇ 1 to ⁇ 3 each independently represent 0 or 1.
- m1 represents an integer of 0 or 1 or more.
- the repeating unit can be a plurality of repeating units different from each other.
- Z4 to Z8 each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms.
- ⁇ 4 to ⁇ 8 each independently represent 0 or 1.
- m2 represents an integer of 0 or 1 or more.
- the repeating units can each be a plurality of mutually different repeating units.
- examples of the silicone compounds having an alkoxy group include at least one compound selected from the compounds represented by the general formula (15) and the general formula (16).
- ⁇ 1 represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms.
- ⁇ 1 , ⁇ 2 , ⁇ 3 , ⁇ 4 , ⁇ 5 , and ⁇ 6 represent an alkyl group and a cycloalkyl group having 1 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, at least one group being an aryl group or an aralkyl group.
- ⁇ 1 , ⁇ 2 , and ⁇ 3 represent an alkoxy group having 1 to 4 carbon atoms.
- ⁇ 2 and ⁇ 3 represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms.
- ⁇ 7 , ⁇ 8 , ⁇ 9 , ⁇ 10 , ⁇ 11 , ⁇ 12 , ⁇ 13 and ⁇ 14 represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, at least one group being an aryl group or an aralkyl.
- ⁇ 4 , ⁇ 5 , ⁇ 6 and ⁇ 7 represent an alkoxy group having 1 to 4 carbon atoms.
- the content of the above components is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 5 parts by weight, per 100 parts by weight of component A.
- Brominated polycarbonate (including oligomer) is particularly suitable as the halogen-based flame retardant of the present invention.
- Brominated polycarbonate has excellent heat resistance and can significantly improve flame retardancy.
- the brominated polycarbonate used in the present invention is a brominated polycarbonate compound in which the structural unit represented by the following general formula (17) accounts for at least 60 mol %, preferably at least 80 mol %, of all structural units, and particularly preferably substantially consists of the structural unit represented by the following general formula (17).
- R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO 2 -.
- R preferably represents a methylene group, an ethylene group, an isopropylidene group, or --SO 2 --, and particularly preferably an isopropylidene group.
- the brominated polycarbonate preferably has a small amount of residual chloroformate terminals, with the amount of terminal chlorine being 0.3 ppm or less, and more preferably 0.2 ppm or less.
- the amount of terminal chlorine can be determined by dissolving a sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine to react with the terminal chlorine (terminal chloroformate), and measuring the result with an ultraviolet-visible spectrophotometer (U-3200, manufactured by Hitachi, Ltd.). If the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition is improved, enabling molding at even higher temperatures, resulting in a polycarbonate resin composition with superior molding processability.
- the brominated polycarbonate preferably has few residual terminal hydroxyl groups. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less, per mol of the constituent units of the brominated polycarbonate.
- the amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring by 1 H-NMR. Such an amount of terminal hydroxyl groups is preferable because it further improves the thermal stability of the polycarbonate resin composition.
- the specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, and more preferably in the range of 0.015 to 0.08.
- the specific viscosity of the brominated polycarbonate is calculated according to the above-mentioned formula for calculating the specific viscosity used when calculating the viscosity average molecular weight of the polycarbonate resin, which is the component A of the present invention.
- the content of the above components is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, and even more preferably 0.05 to 7 parts by weight, per 100 parts by weight of component A.
- the polycarbonate resin composition of the present invention can contain a fluorine-containing drip-preventing agent.
- a fluorine-containing drip-preventing agent can be exemplified by a fluorine-containing polymer having fibril forming ability, and such a polymer can be exemplified by polytetrafluoroethylene, tetrafluoroethylene-based copolymers (e.g., tetrafluoroethylene/hexafluoropropylene copolymers, etc.), partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc., and preferably polytetrafluoroethylene (hereinafter sometimes referred to as PTFE).
- PTFE polytetrafluoroethylene
- Polytetrafluoroethylene having fibril forming ability has an extremely high molecular weight, and shows a tendency to bond PTFE to each other and become fibrous by external action such as shear force. Its number average molecular weight is in the range of 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380°C as disclosed in JP-A-6-145520. That is, the melt viscosity of fibrillated PTFE at 380°C measured by the method described in the publication is in the range of 10 7 to 10 13 poise, preferably 10 8 to 10 12 poise.
- Such PTFE can be used in the form of a solid or an aqueous dispersion.
- PTFE with such fibril-forming ability can also be used in a mixed form with other resins to improve dispersibility in resins and obtain even better flame retardancy and mechanical properties.
- a structure with such fibrillated PTFE as a core and low molecular weight polytetrafluoroethylene as a shell is also preferably used.
- fibrillated PTFE Commercially available products of fibrillated PTFE include, for example, Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L from Daikin Chemical Industries, Ltd.
- Representative examples of commercially available aqueous dispersions of fibrillated PTFE include Fluon AD-1 and AD-936 from Asahi ICI Fluoropolymers Co., Ltd., Fluon D-1 and D-2 from Daikin Industries, Ltd., and Teflon (registered trademark) 30J from Mitsui DuPont Fluorochemicals Co., Ltd.
- the mixed form of fibrillated PTFE (1) a method of mixing an aqueous dispersion of fibrillated PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coagulated mixture (methods described in JP-A-60-258263, JP-A-63-154744, etc.), (2) a method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (method described in JP-A-4-272957), (3) a method of uniformly mixing an aqueous dispersion of fibrillated PTFE with an organic polymer particle solution and extracting coagulated particles from the mixture (method described in JP-A-4-272957), and (4) a method of uniformly mixing an aqueous dispersion of fibrillated PTFE with an organic polymer particle solution and extracting coagulated particles from the mixture (method described in JP-A-4-272957).
- Examples of commercially available products of these mixed forms of fibrillated PTFE include “Metablen A3800” (product name) from Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (product name) from GE Specialty Chemicals, and “POLY TS AD001” (product name) from Pacific Interchem Corporation.
- the fibrillated PTFE is preferably as finely dispersed as possible so as not to reduce the mechanical strength.
- the fibrillated PTFE in the above mixed form is advantageous as a means of achieving such fine dispersion.
- a method of directly supplying the aqueous dispersion form to a melt kneader is also advantageous for fine dispersion.
- the proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, of 100% by weight of the mixture. When the proportion of fibrillated PTFE is within this range, good dispersibility of the fibrillated PTFE can be achieved.
- the content of the above components is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and even more preferably 0.05 to 1.5 parts by weight, per 100 parts by weight of component A.
- 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.
- Phosphorus-based stabilizers examples include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, as well as tertiary phosphines. Among these, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferred.
- the organic group in the acid phosphate compound includes both mono-substituted and di-substituted groups, and mixtures thereof. The following exemplary compounds corresponding to the compounds also include both of these groups.
- triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate.
- trialkyl phosphates are preferred.
- the number of carbon atoms in such trialkyl phosphates is preferably 1 to 22, more preferably 1 to 4.
- a particularly preferred trialkyl phosphate is trimethyl phosphate.
- acid phosphate compounds include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, and bisphenol A acid phosphate.
- long-chain dialkyl acid phosphates having 10 or more carbon atoms are preferred because they are effective in improving thermal stability and the acid phosphate itself is highly stable.
- phosphite compounds include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris(diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)pho
- phosphite compounds that react with dihydric phenols to form a cyclic structure
- 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, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.
- Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-pheny
- Such phosphonite compounds can be used in combination with the phosphite compounds having an aryl group substituted with two or more alkyl groups, and are therefore preferred.
- Phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
- tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine.
- a particularly preferred tertiary phosphine is triphenylphosphine.
- Suitable phosphorus-based stabilizers are triorganophosphate compounds, acid phosphate compounds, and phosphite compounds represented by the following general formula (18). It is particularly preferable to use a triorganophosphate compound.
- R and R' represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different.
- the phosphonite compound is preferably tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite, and stabilizers containing this phosphonite as the main component are commercially available as Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), either of which can be used.
- More preferred phosphite compounds of the above formula (18) are distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis ⁇ 2,4-bis(1-methyl-1-phenylethyl)phenyl ⁇ pentaerythritol diphosphite.
- Hindered phenol-based antioxidants As the hindered phenol compound, various compounds that are usually blended into resins can be used. Examples of such hindered phenol compounds include ⁇ -tocopherol, butyl hydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)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, 3,5-di-tert-butyl-4-hydroxybenzylphosphone, and the like.
- tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2- ⁇ 3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy ⁇ -1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention.
- a phosphorus-based stabilizer or a hindered phenol-based antioxidant It is preferable to use either a phosphorus-based stabilizer or a hindered phenol-based antioxidant. It is particularly preferable to use a phosphorus-based stabilizer, and it is even more preferable to use a triorganophosphate compound.
- the content of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is preferably 0.005 to 1 part by weight, and more preferably 0.01 to 0.3 parts by weight, per 100 parts by weight of component A.
- the polycarbonate resin composition of the present invention may contain an ultraviolet absorbent. Since the polycarbonate resin composition of the present invention has a good hue, the incorporation of an ultraviolet absorbent can maintain such a hue for a long period of time even when used outdoors.
- benzophenones examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.
- hydroxyphenyltriazines 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-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol.
- phenyl group of the above example compounds is a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol.
- cyclic iminoesters examples include 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one).
- cyanoacrylate-based ultraviolet absorbers 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.
- the above-mentioned UV absorber may be a polymer-type UV absorber obtained by copolymerizing such a UV absorbing monomer and/or a light stable monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate by adopting a structure of a monomer compound capable of radical polymerization.
- Suitable examples of the above-mentioned UV absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester.
- UV absorbents may be used alone or in a mixture of two or more types.
- the content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, even more preferably 0.03 to 1 part by weight, and most preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of component A.
- the polycarbonate resin composition of the present invention may also contain heat stabilizers other than the phosphorus-based stabilizer and the hindered phenol-based antioxidant.
- heat stabilizers are preferably used in combination with either one of these stabilizers and antioxidants, and particularly preferably used in combination with both.
- Suitable examples of such other heat stabilizers include lactone-based stabilizers such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160).
- Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers in which this compound is mixed with various phosphite compounds and hindered phenol compounds are commercially available. Suitable examples include Irganox HP-2921 manufactured by the above company. In the present invention, such premixed stabilizers can also be used.
- the content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of component A.
- stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate.
- sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate.
- Such stabilizers are particularly effective when the polycarbonate resin composition is applied to rotational molding.
- the amount of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A.
- the polycarbonate resin composition of the present invention may further contain known mold release agents such as fatty acid esters, polyolefin waxes, silicone compounds, fluorine compounds (fluorine oils such as polyfluoroalkyl ethers), paraffin wax, and beeswax, in order to improve the productivity during molding and the dimensional accuracy of the molded product.
- the polycarbonate resin composition of the present invention has good fluidity, so that a molded product with good pressure transmission and uniform distortion can be obtained.
- a molded product with a complex shape that has a large mold release resistance there is a risk of deformation of the molded product during mold release.
- the blending of the above specific components solves this problem without impairing the properties of the polycarbonate resin composition.
- the fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid.
- the aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having dihydric or higher valence.
- the carbon number of the alcohol is preferably 3 to 32, more preferably 5 to 30.
- the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred.
- the fatty acid ester of the present invention is preferred in that the full ester has excellent thermal stability at high temperatures.
- the acid value of the fatty acid ester of the present invention is preferably 20 or less (can be substantially 0).
- the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30.
- the iodine value of the fatty acid ester is preferably 10 or less (can be substantially 0).
- polyolefin waxes examples include ethylene homopolymers, homopolymers or copolymers of ⁇ -olefins having 3 to 60 carbon atoms, or copolymers of ethylene and ⁇ -olefins having 3 to 60 carbon atoms, each having a molecular weight of 1,000 to 10,000.
- Such molecular weights are number average molecular weights measured in standard polystyrene equivalent by GPC (gel permeation chromatography). The upper limit of such number average molecular weight is more preferably 6,000, and even more preferably 3,000.
- the number of carbon atoms of the ⁇ -olefin component in the polyolefin wax is preferably 60 or less, more preferably 40 or less.
- More preferred examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
- Preferred polyolefin waxes are ethylene homopolymers or copolymers of ethylene and ⁇ -olefins having 3 to 60 carbon atoms. The proportion of ⁇ -olefins having 3 to 60 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less. It is preferable to use commercially available polyethylene wax.
- the content of the release agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and even more preferably 0.02 to 3 parts by weight, per 100 parts by weight of component A.
- the polycarbonate resin composition of the present invention further contains various dyes and pigments, and can provide molded products that exhibit a variety of designs.
- dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes.
- the polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color.
- Aluminum powder is suitable as the metallic pigment.
- a fluorescent brightener or other fluorescent dye that emits light a better design effect that makes use of the luminous color can be imparted.
- Fluorescent dyes (including fluorescent brighteners) used in the present invention include, for example, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes.
- coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and are less susceptible to deterioration during the molding process of polycarbonate resin.
- the content of the dye or pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of component A.
- the polycarbonate resin composition of the present invention may contain a compound with heat absorption ability.
- Suitable examples of such compounds include phthalocyanine-based near infrared absorbing agents, metal oxide-based near infrared absorbing agents such as ATO, ITO, iridium oxide, ruthenium oxide, and immonium oxide, various metal compounds with excellent near infrared absorbing ability such as metal boride-based and tungsten oxide-based near infrared absorbing agents such as lanthanum boride, cerium boride, and tungsten boride, and carbon fillers.
- phthalocyanine-based near infrared absorbing agents for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available.
- carbon fillers include carbon black, graphite (both natural and artificial), and fullerene, and preferably carbon black and graphite. These can be used alone or in combination of two or more.
- the content of the phthalocyanine-based near infrared absorber 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, relative to 100 parts by weight of Component A.
- the contents of the metal oxide-based near infrared absorber, metal boride-based near infrared absorber, and carbon filler in the resin composition of the present invention are preferably in the range of 0.1 to 200 ppm (weight ratio), and more preferably in the range of 0.5 to 100 ppm.
- the polycarbonate resin composition of the present invention can be blended with a light diffuser to impart a light diffusion effect.
- light diffusers include polymer fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof.
- Such polymer fine particles are fine particles already known as light diffusers for polycarbonate resins. More preferred examples include acrylic crosslinked particles with a particle size of several ⁇ m and silicone crosslinked particles represented by polyorganosilsesquioxane.
- the shape of the light diffuser include spherical, discoid, columnar, and indefinite shapes.
- Such a sphere does not need to be a perfect sphere and includes deformed ones, and such a columnar shape includes a cube.
- a preferred light diffuser is spherical, and the more uniform the particle size, the more preferred it is.
- the content of the light diffuser is 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, relative to 100 parts by weight of component A. Two or more types of light diffusers can be used in combination.
- Highly light-reflective white pigment A highly light-reflective white pigment can be blended into the polycarbonate resin composition of the present invention to impart a light-reflecting effect. Titanium dioxide pigment (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment.
- the content of such highly light-reflective white pigment is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, per 100 parts by weight of component A. Two or more types of highly light-reflective white pigments can be used in combination.
- the polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent.
- antistatic agents include (1) arylsulfonic acid phosphonium salts, such as dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts, such as alkylsulfonic acid phosphonium salts, and boric acid phosphonium salts, such as tetrafluoroborate phosphonium salts.
- the content of the phosphonium salt is appropriately 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 1.5 to 3 parts by weight, per 100 parts by weight of component A.
- antistatic agents include (2) organic sulfonate alkali (earth) metal salts such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate.
- organic sulfonate alkali (earth) metal salts such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate.
- organic sulfonate alkali (earth) metal salts such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulf
- the content of the organic sulfonate alkali (earth) metal salt is appropriately 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, per 100 parts by weight of component A.
- alkali metal salts such as potassium, cesium, and rubidium are suitable.
- Antistatic agents include, for example, (3) ammonium salts of organic sulfonates, such as ammonium salts of alkylsulfonates and ammonium salts of arylsulfonates. The amount of the ammonium salts is appropriately 0.05 parts by weight or less based on 100 parts by weight of the total of components A, B, and C.
- Antistatic agents include, for example, (4) polymers that contain a poly(oxyalkylene) glycol component as a constituent component, such as polyether ester amide. The amount of the polymer is appropriately 5 parts by weight or less based on 100 parts by weight of component A.
- organic fibrous filler in addition to the inorganic filler, a known organic fibrous filler can be blended as a reinforcing filler in the polycarbonate resin composition of the present invention.
- the organic fibrous filler is an organic filler having a fibrous shape (including any of rod-like, needle-like, flattened, and shapes whose axes extend in multiple directions).
- the fiber diameter of the organic fibrous filler is preferably in the range of 0.1 to 20 ⁇ m.
- the upper limit of the fiber diameter is more preferably 13 ⁇ m, and even more preferably 10 ⁇ m. Meanwhile, the lower limit of the fiber diameter is more preferably 1 ⁇ m.
- the fiber diameter here refers to the number average fiber diameter.
- the number average fiber diameter is a value calculated from images obtained by observing with a scanning electron microscope the residue collected after dissolving the molded product in a solvent or decomposing the resin with a basic compound, and the ashing residue collected after ashing in a crucible.
- organic fibrous fillers examples include fibrous heat-resistant organic fillers such as aramid fiber, polyimide fiber, and polybenzthiazole fiber, as well as vegetable fibrous fillers such as hemp and bamboo.
- the aspect ratio of the organic fibrous filler is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more.
- the upper limit of the aspect ratio is about 10,000, and preferably 200.
- the aspect ratio of such a filler is the value in the resin composition.
- the organic fibrous filler may be surface-treated with various coupling agents, similar to the inorganic fibrous filler, and may be bundled with various resins or granulated by compression.
- the content of the organic fibrous filler is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, even more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less, per 100 parts by weight of component A.
- the polycarbonate resin composition of the present invention may contain thermoplastic resins other than Component A and Component B, elastomers, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents and photochromic agents, ionic liquids, and the like.
- Such other resins include, for example, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resins such as polyethylene and polypropylene, polystyrene resin, acrylonitrile/styrene copolymer (AS resin), acrylonitrile/butadiene/styrene copolymer (ABS resin), polymethacrylate resin, phenolic resin, epoxy resin, cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, and thermoplastic fluororesin (e.g., polyvinylidene fluoride resin).
- polyamide resin polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resins such as polyethylene and polyprop
- elastomers examples include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and core-shell elastomers such as MBS (methyl methacrylate/styrene/butadiene) rubber and MAS (methyl methacrylate/acrylonitrile/styrene) rubber.
- MBS methyl methacrylate/styrene/butadiene
- MAS methyl methacrylate/acrylonitrile/styrene
- the content of other thermoplastic resins is preferably 100 parts by weight or less, and more preferably 50 parts by weight or less, per 100 parts by weight of component A.
- the method for producing the polycarbonate resin composition of the present invention is not particularly limited, and any known method can be used.
- the A component, the B component, and any 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 melt-kneaded in a melt kneader typified by a vented twin-screw extruder, and then pelletized with a pelletizer.
- 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 melt-kneaded in a melt kneader typified by a vente
- Other methods include feeding each component independently to a melt mixer such as a vented twin-screw extruder, feeding the components to a melt mixer using a supercritical fluid, and premixing a portion of each component and feeding the remaining components to the melt mixer independently.
- a method of premixing a portion of each component is a method of premixing components other than component A in advance and then mixing them with component A or feeding them directly to the extruder.
- component A contains a powder
- a method of premixing is to blend a portion of the powder with the additive to be mixed to produce a master batch of the additive diluted with the powder, and use the master batch.
- Another example is a method of feeding one component independently from the middle of the melt extruder. If the components to be mixed are liquid, a so-called liquid injection device or liquid addition device can be used to feed the components to the melt extruder.
- the extruder preferably has a vent that can remove moisture in the raw materials and volatile gases generated from the melt-kneaded resin.
- a vacuum pump is preferably installed from the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. It is also possible to remove foreign matter from the resin composition by installing a screen in the zone before the extruder die to remove foreign matter mixed into the extrusion raw materials. Examples of such screens include wire mesh, screen changers, and sintered metal plates (disc filters, etc.).
- melt-kneaders include Banbury mixers, kneading rolls, single-screw extruders, and multi-screw extruders with three or more screws, in addition to twin-screw extruders.
- the resin extruded as described above is either directly cut and pelletized, or formed into strands, which are then cut by a pelletizer and pelletized. 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 manufacture of such pellets, various methods already proposed for polycarbonate resins for optical disks can be used to narrow the shape distribution of the pellets, reduce miscuts, reduce fine powder generated during transportation or shipping, and reduce bubbles (vacuum bubbles) generated inside the strands or pellets. These prescriptions can be used to increase the cycle time of molding and reduce the rate of defects such as silver.
- the shape of the pellets can be any of the general shapes such as cylinders, prisms, and spheres, but is more preferably a cylinder.
- the diameter of such a 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.
- the polycarbonate resin composition of the present invention can be used to manufacture various products by injection molding the pellets produced as described above to obtain molded articles.
- injection molding can include 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, insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding.
- foam molding including the method of injecting a supercritical fluid
- insert molding in-mold coating molding
- insulating mold molding rapid heating and cooling mold molding
- two-color molding sandwich molding
- ultra-high speed injection molding two-color molding
- either the cold runner method or the hot runner method can be selected for molding.
- 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 using inflation, calendaring, casting, etc. Furthermore, it can be molded into heat shrinkable tubes by subjecting it to a specific stretching operation.
- the polycarbonate resin composition of the present invention can also be molded into molded products by rotational molding, blow molding, etc.
- the viscosity average molecular weight Mv was calculated from the determined specific viscosity ( ⁇ SP ) according to the following formula.
- Plating property (ii) Plating depositability Plating was carried out under the following conditions using plate-shaped test pieces of 50 mm ⁇ 100 mm ⁇ 1 mm thickness obtained by the method described below. Plating depositability was evaluated as follows by visually judging the thickness of the thin metal film plated within a specified time. The evaluation results are shown in Tables 1 and 2. Comparative Examples 1-3 and 2-3 could not be evaluated due to poor surface appearance. ⁇ : The metal thin film is uniformly thick and applied over the entire surface. ⁇ : The metal thin film is thick, but somewhat uneven. ⁇ : Metal thin film is applied but uneven (practical level). ⁇ : A small amount of metal thin film is present (not at practical level). XX: Almost no metal thin film is present.
- Examples 1-1 to 1-14, Comparative Examples 1-1 to 1-5, Examples 2-1 to 2-23, Comparative Examples 2-1 to 2-5] (Preparation of plate-shaped test pieces)
- Aromatic polycarbonate resin, polycarbonate-polydiorganosiloxane copolymer resin, additive for laser irradiation three-dimensional circuit molding, inorganic filler and other various additives were mixed in a blender in the amounts shown in Tables 1 to 4, and then melt-kneaded using a vented twin-screw extruder to obtain pellets.
- the various additives used were pre-mixed with aromatic polycarbonate resin in advance at a concentration of 10 to 100 times the amount of each additive, and then the entire mixture was mixed using a blender.
- the mixture of aromatic polycarbonate resin, polycarbonate-polydiorganosiloxane copolymer resin, additive for laser irradiation three-dimensional circuit molding, inorganic filler, and other various additives was fed into the extruder from the first feed port.
- the first feed port here is the feed port farthest from the die.
- the obtained pellets were extruded into the extruder for 12 hours. After drying at 0°C for 5 hours in a hot air circulation dryer, a test piece for evaluation was molded using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) under molding conditions of a cylinder temperature of 280°C and a mold temperature of 80°C.
- the plating property of the molded product was evaluated after plating according to the following conditions:
- the obtained test piece was printed with a width of 5 mm using a 1064 nm YAG laser with a Keyence MDX-2000 under the conditions of a pulse frequency of 80 kHz, a scanning speed of 2 m/s, an output of 1.45 W, a laser spot diameter of 60 ⁇ m, and an overlap of 30 ⁇ m, and then the following operations were carried out.
- A-1-1 Aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 22,400, manufactured by Teijin Limited, Panlite L-1225WP (product name)]
- A-2-1 Polycarbonate-polydiorganosiloxane copolymer resin [Polydiorganosiloxane block content: 8% by weight, average siloxane polymerization degree (p+q): 37, average size of polydiorganosiloxane domain: 10 nm]
- A-2-2 Polycarbonate-polydiorganosiloxane copolymer resin [Polydiorganosiloxane block content: 4% by weight, average siloxane polymerization degree (p+q): 50, average size of polydiorganosiloxane domain: 30 nm]
- A-2-3 Polycarbonate-polydiorganosiloxane copo
- B-1 Copper/chromium oxide [Black 1G (product name), manufactured by Shepherd Color Japan, Inc.]
- B-2 Antimony tin oxide [Stanostat CP5C (trade name), manufactured by Keeling & Walker]
- B-3 Antimony trioxide [STOX-M (product name), manufactured by Nihon Seiko Co., Ltd.]
- B-4 Titanium oxide/tin-antimony oxide [Mitsubishi Materials Corporation, W-1 (product name)]
- B-5 Aluminum-doped zinc oxide [23K (product name), manufactured by Hakusui Tech Co., Ltd.]
- Component C Glass fiber [manufactured by Nitto Boseki Co., Ltd., CS-3PE-455 (product name)]
- C-2 Glass flakes [MEG160FYX (product name), manufactured by Nippon Sheet Glass Co., Ltd.]
- C-3 Talc [Victorilite TK-RC (product name), manufactured by Shokoyama Kogyo Co., Ltd.]
- C-4 Mica [A-41 (product name), manufactured by Yamaguchi Mica Co., Ltd.]
- C-5 Wollastonite [SH-1250 (product name), manufactured by Kinseimatic Co., Ltd.]
- C-6 Carbon fiber [Teijin Limited, HT C493 (product name)]
- C-7 Carbon black [manufactured by Koshigaya Chemical Industry Co., Ltd., RB-90003S (product name)]
- C-8 Titanium oxide [manufactured by Resinocolor Co., Ltd., DCF-T-17007 (product name)
- STB-1 Hindered phenol-based antioxidant [Irganox 1076 (trade name), manufactured by BASF Ltd.]
- STB-2 phosphite stabilizer [Irgafos 168 (trade name), manufactured by BASF Ltd.]
- L Pentaerythritol fatty acid ester-based release agent [Rikestar EW-400 (product name), manufactured by Riken Vitamin Co., Ltd.]
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Abstract
Description
1.(A)芳香族ポリカーボネート樹脂(A-1成分)0~99.9重量%およびポリカーボネート-ポリジオルガノシロキサン共重合樹脂(A-2成分)0.1~100重量%からなる樹脂成分(A成分)100重量、及び
(B)レーザー照射立体回路形成用添加剤(B成分)1~50重量部
を含有し、
A-2成分が、下記式(1)で表されるポリカーボネートブロックおよび下記式(3)で表されるポリジオルガノシロキサンブロックからなり、かつポリカーボネートポリマーのマトリックス中にポリジオルガノシロキサンドメインが分散した凝集構造であり、該ポリジオルガノシロキサンドメインの平均サイズが5~100nmであるポリカーボネート-ポリジオルガノシロキサン共重合樹脂であることを特徴とするポリカーボネート樹脂組成物。
本発明は、以下の構成のポリカーボネート樹脂組成物である。
(B)レーザー照射立体回路形成用添加剤(B成分)1~50重量部
を含有し、
A-2成分が、下記式(1)で表されるポリカーボネートブロックおよび下記式(3)で表されるポリジオルガノシロキサンブロックからなり、かつポリカーボネートポリマーのマトリックス中にポリジオルガノシロキサンドメインが分散した凝集構造であり、該ポリジオルガノシロキサンドメインの平均サイズが5~100nmであるポリカーボネート-ポリジオルガノシロキサン共重合樹脂であることを特徴とするポリカーボネート樹脂組成物。
(A成分:樹脂成分)
(A-1成分:芳香族ポリカーボネート樹脂)
芳香族ポリカーボネート樹脂は、通常ジヒドロキシ化合物とカーボネート前駆体とを界面重縮合法、溶融エステル交換法で反応させて得られたものの他、カーボネートプレポリマーを固相エステル交換法により重合させたもの、または環状カーボネート化合物の開環重合法により重合させて得られるものである。ここで使用されるジヒドロキシ成分としては、通常芳香族ポリカーボネートのジヒドロキシ成分として使用されているものであればよく、ビスフェノール類でも脂肪族ジオール類でも良い。ビスフェノール類としては、下記式(4)で表されるビスフェノール類が好ましく用いられる。
比粘度(ηSP)=(t-t0)/t0
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数]
ηSP/c=[η]+0.45×[η]2c(但し[η]は極限粘度)
[η]=1.23×10-4M0.83
c=0.7
本発明のA-2成分は、下記式(1)で表されるポリカーボネートブロックおよび下記式(3)で表されるポリジオルガノシロキサンブロックからなり、かつポリカーボネートポリマーのマトリックス中にポリジオルガノシロキサンドメインが分散した凝集構造であり、該ポリジオルガノシロキサンドメインの平均サイズが5~100nmであるポリカーボネート-ポリジオルガノシロキサン共重合樹脂である。
本発明に使用されるレーザー照射立体回路成形用添加剤とは、配合することによって、レーザー照射による立体回路成形を可能とする化合物である。レーザー照射立体回路成形用添加剤は、合成品であってもよいし、市販品を用いてもよい。また、市販品はレーザー照射立体回路成形用添加剤として市販されているものの他、他の用途として販売されている物質であってもよい。レーザー照射立体回路成形用添加剤は、1種のみの金属を含む化合物でも構わないが、少なくとも2種の金属を含む混合金属化合物であることが好ましい。該金属としては、銅、クロム、スズ、亜鉛およびアンチモンが例示される。レーザー照射立体回路成形用添加剤は、1種類のみを用いてもよいし、2種類以上を併用してもよい。
本発明のポリカーボネート樹脂組成物は、強化フィラーとして公知の各種無機充填材を含有することができる。好適に使用される無機充填材として、ガラス(繊維状ガラスおよび板状ガラス)炭素(繊維状炭素および非繊維状炭素)、ケイ酸塩鉱物、炭酸カルシウム、シリカおよび二酸化チタン等が挙げられ、その中でもガラス、炭素繊維およびケイ酸塩鉱物からなる群より選ばれる少なくとも1種の無機充填材であることがより好ましい。
繊維状ガラス充填材としては、ガラスファイバー、金属コートガラスファイバーおよびガラスミルドファイバー等が挙げられる。かかる繊維状ガラス充填材の基体となるガラスファイバーは溶融ガラスを種々の方法にて延伸しながら急冷し、所定の繊維状にしたものである。かかる場合の急冷および延伸についても特に限定されるものではない。また、断面の形状は真円状の他に、楕円状、マユ状、扁平状および三つ葉状などの真円以外の形状であってもよい。更に真円状と真円以外の形状が混合したものでもよい。扁平状とは、繊維断面の長径の平均値が10~50μm、好ましくは15~40μm、より好ましくは20~35μmで、長径と短径の比(長径/短径)の平均値が1.5~8、好ましくは2~6、更に好ましくは2.5~5である形状である。
板状ガラス充填材としては、ガラスフレーク、金属コートガラスフレークおよび金属酸化物コートガラスフレーク等が挙げられる。
繊維状炭素充填材としては、例えばカーボンファイバー、金属コートカーボンファイバー、カーボンミルドファイバー、気相成長カーボンファイバー、およびカーボンナノチューブ等が挙げられる。カーボンナノチューブは繊維径0.003~0.1μm、単層、2層、および多層のいずれであってもよく、多層(いわゆるMWCNT)が好ましい。これらの中でも機械的強度に優れる点、並びに良好な導電性を付与できる点において、カーボンファイバー、および金属コートカーボンファイバーが好ましい。尚、良好な導電性は近年のデジタル精密機器(例えばデジタルスチルカメラに代表される)において、樹脂材料に求められる重要な特性の1つになっている。
非繊維状炭素充填材としては、例えば、カーボンブラック、黒鉛、フラーレン等が挙げられる。これらの中でも機械的強度、耐湿熱性、熱安定性の点から、カーボンブラック、黒鉛が好ましい。カーボンブラックとしては、DBP吸油量が100ml/100g~500ml/100gであるカーボンブラックが導電性の点で好ましい。かかるカーボンブラックは、一般的にはアセチレンブラック、ケッチェンブラックである。具体的には、例えば電気化学工業(株)製のデンカブラック、キャボット社製バルカンXC-72およびBP-2000、ライオン(株)製ケッチェンブラックECおよびケッチェンブラックEC-600JD等が挙げられる。
ケイ酸塩鉱物としては、オルトシリケート、ジシリケート、環状シリケート、および鎖状シリケートなどが好適である。珪酸塩鉱物は結晶状態を取るものであり、更に該結晶は各珪酸塩鉱物が取り得るいずれの形態であってもよく、また結晶の形状も繊維状や板状などの各種の形状を取ることができる。
タルクとは、化学組成的には含水珪酸マグネシウムであり、一般的には化学式4SiO2・3MgO・2H2Oで表され、通常層状構造を持った鱗片状の粒子であり、また組成的にはSiO2を56~65重量%、MgOを28~35重量%、H2O約5重量%程度から構成されている。その他の少量成分としてFe2O3が0.03~1.2重量%、Al2O3が0.05~1.5重量%、CaOが0.05~1.2重量%、K2Oが0.2重量%以下、Na2Oが0.2重量%以下などを含有している。より好適なタルクの組成としては、SiO2:62~63.5重量%、MgO:31~32.5重量%、Fe2O3:0.03~0.15重量%、Al2O3:0.05~0.25重量%、およびCaO:0.05~0.25重量%が好ましい。更に強熱減量が2~5.5重量%であることが好ましい。かかる好適な組成においては、良好な熱安定性および色相を有する樹脂組成物が得られ、更なる成形加工温度の上昇によっても良好な成形品が製造される。これにより本発明の組成物は更に高流動化が可能となり、より大型または複雑形状の薄肉成形品に対応可能となる。
マイカは、その平均粒径が5~250μmのものが好ましく使用できる。より好ましくは平均粒径が5~50μmのマイカである。マイカの平均粒径が5μm未満では剛性向上の効果が得られにくくなる。一方250μmを超える平均粒径のマイカを含有する樹脂組成物は、機械的物性が飽和傾向にある一方で外観や難燃性が劣るようになる場合がある。尚、マイカの平均粒径は、レーザー回折・散乱法または振動式篩分け法により測定される。レーザー回折・散乱法は、振動式篩分け法により325メッシュパスが、95重量%以上のマイカに対して行うのが好適である。それ以上の粒径のマイカに対しては、振動式篩分け法を使用するのが一般的である。本発明の振動式篩分け法は、まず振動篩器を用い使用するマイカ粉体100gを目開きの順番に重ねたJIS規格の標準篩により10分間篩分けを行う。各篩の上に残った粉体の重量を測定して粒度分布を求める方法である。
ワラストナイトの繊維径は0.1~10μmが好ましく、0.1~5μmがより好ましく、0.1~3μmが更に好ましい。またそのアスペクト比(平均繊維長/平均繊維径)は3以上が好ましい。アスペクト比の上限としては30以下が挙げられる。ここで繊維径は電子顕微鏡で強化フィラーを観察し、個々の繊維径を求め、その測定値から数平均繊維径を算出する。電子顕微鏡を使用するのは、対象とするレベルの大きさを正確に測定することが光学顕微鏡では困難なためである。繊維径は、電子顕微鏡の観察で得られる画像に対して、繊維径を測定する対象のフィラーをランダムに抽出し、中央部の近いところで繊維径を測定し、得られた測定値より数平均繊維径を算出する。観察の倍率は約1000倍とし、測定本数は500本以上(600本以下が作業上好適である)で行う。一方平均繊維長の測定は、フィラーを光学顕微鏡で観察し、個々の長さを求め、その測定値から数平均繊維長を算出する。光学顕微鏡の観察は、フィラー同士があまり重なり合わないように分散されたサンプルを準備することから始まる。観察は対物レンズ20倍の条件で行い、その観察像を画素数が約25万であるCCDカメラに画像データとして取り込む。得られた画像データを画像解析装置を使用して、画像データの2点間の最大距離を求めるプログラムを使用して、繊維長を算出する。かかる条件の下では1画素当りの大きさが1.25μmの長さに相当し、測定本数は500本以上(600本以下が作業上好適である)で行う。ワラストナイトは、その元来有する白色度を十分に樹脂組成物に反映させるため、原料鉱石中に混入する鉄分並びに原料鉱石を粉砕する際に機器の摩耗により混入する鉄分を磁選機によって極力取り除くことが好ましい。かかる磁選機処理によりワラストナイト中の鉄の含有量はFe2O3に換算して、0.5重量%以下であることが好ましい。したがって、本発明のより好適なワラストナイトは、その繊維径が0.1~10μm、より好ましくは0.1~5μm、更に好ましくは0.1~3μmであり、平均粒径が5~250μm、より好ましくは5~50μmであり、鉄の含有量はFe2O3に換算して0.5重量%以下のワラストナイトである。かかる好適なワラストナイトとしては例えばキンセイマテック社製「SH-1250」、「SH-1800」、関西マテック社製「KGP-H40」、NYCO社製「NYGLOS4」等が例示される。
二酸化チタンは、通常各種用途に使用されるものが使用でき、それ自体広く知られたものである。TiO2100重量%からなる二酸化チタンも存在する(尚、本発明においては二酸化チタンの二酸化チタン成分を”TiO2”と表記し、表面処理剤を含む全体を”二酸化チタン”と表記する)。しかしながら、通常、アルミニウム、ケイ素、チタン、ジルコニウム、アンチモン、スズ、亜鉛などの各種金属の酸化物による表面処理がなされる。本発明においても、好ましい二酸化チタンは、金属酸化物の表面処理がなされたものである。尚、これらの表面処理のための金属酸化物成分は、一部がTiO2粒子の内部に存在する態様であってもよい。
本発明のポリカーボネート樹脂組成物には、成形加工時の分子量低下や色相を安定化させるための各種安定剤、離型剤、色剤、衝撃改質剤、充填剤及び難燃剤等を使用することができる。
本発明のポリカーボネート樹脂組成物には、難燃剤として知られる各種の化合物が配合することができる。尚、難燃剤として使用される化合物の配合は難燃性の向上のみならず、各化合物の性質に基づき、例えば帯電防止性、流動性、剛性、および熱安定性の向上などがもたらされる。
有機金属塩系難燃剤は、耐熱性がほぼ維持されると共に少なからず帯電防止性を付与できる点で有利である。本発明において最も有利に使用される有機金属塩系難燃剤は、含フッ素有機金属塩化合物である。本発明の含フッ素有機金属塩化合物とは、フッ素置換された炭化水素基を有する有機酸からなるアニオン成分と金属イオンからなるカチオン成分からなる金属塩化合物をいう。より好適な具体例としては、フッ素置換有機スルホン酸の金属塩、フッ素置換有機硫酸エステルの金属塩、およびフッ素置換有機リン酸エステルの金属塩が例示される。含フッ素有機金属塩化合物は1種もしくは2種以上を混合して使用することができる。その中でも好ましいのはフッ素置換有機スルホン酸の金属塩であり、とくに好ましいのはパーフルオロアルキル基を有するスルホン酸の金属塩である。ここでパーフルオロアルキル基の炭素数は、1~18の範囲が好ましく、1~10の範囲がより好ましく、更に好ましくは1~8の範囲である。
本発明の有機リン系難燃剤としては、縮合リン酸エステル化合物およびホスファゼン化合物が好適である。
1)縮合リン酸エステル化合物
縮合リン酸エステル化合物としては、アリールホスフェート化合物が好適に用いられる。縮合リン酸エステル化合物は可塑化効果があるため、成形加工性を高められる点で有利である。アリールホスフェート化合物は、従来難燃剤として公知の各種ホスフェート化合物が使用できるが、より好適には特に下記一般式(8)で表される1種または2種以上のホスフェート化合物を挙げることができる。
ホスファゼン化合物は可塑化効果があるため、成形加工性を高められる点で有利である。ホスファゼン化合物は、従来難燃剤として公知の各種ホスファゼン化合物が使用できるが、下記一般式(9)、(10)で表されるホスファゼン化合物が好ましい。
本発明のシリコーン系難燃剤として使用されるシリコーン化合物は、燃焼時の化学反応によって難燃性を向上させるものである。該化合物としては従来芳香族ポリカーボネート樹脂の難燃剤として提案された各種の化合物を使用することができる。シリコーン化合物はその燃焼時にそれ自体が結合してまたは樹脂に由来する成分と結合してストラクチャーを形成することにより、または該ストラクチャー形成時の還元反応により、ポリカーボネート樹脂に難燃効果を付与するものと考えられている。したがってかかる反応における活性の高い基を含んでいることが好ましく、より具体的にはアルコキシ基およびハイドロジェン(即ちSi-H基)から選択された少なくとも1種の基を所定量含んでいることが好ましい。かかる基(アルコキシ基、Si-H基)の含有割合としては、0.1~1.2mol/100gの範囲が好ましく、0.12~1mol/100gの範囲がより好ましく、0.15~0.6mol/100gの範囲が更に好ましい。かかる割合はアルカリ分解法より、シリコーン化合物の単位重量当たりに発生した水素またはアルコールの量を測定することにより求められる。尚、アルコキシ基は炭素数1~4のアルコキシ基が好ましく、特にメトキシ基が好適である。
M単位:(CH3)3SiO1/2、H(CH3)2SiO1/2、H2(CH3)SiO1/2、(CH3)2(CH2=CH)SiO1/2、(CH3)2(C6H5)SiO1/2、(CH3)(C6H5)(CH2=CH)SiO1/2等の1官能性シロキサン単位、D単位:(CH3)2SiO、H(CH3)SiO、H2SiO、H(C6H5)SiO、(CH3)(CH2=CH)SiO、(C6H5)2SiO等の2官能性シロキサン単位、T単位:(CH3)SiO3/2、(C3H7)SiO3/2、HSiO3/2、(CH2=CH)SiO3/2、(C6H5)SiO3/2等の3官能性シロキサン単位、Q単位:SiO2で示される4官能性シロキサン単位である。
本発明のハロゲン系難燃剤としては、臭素化ポリカーボネート(オリゴマーを含む)が特に好適である。臭素化ポリカーボネートは耐熱性に優れ、かつ大幅に難燃性を向上できる。本発明で使用する臭素化ポリカーボネートは、下記一般式(17)で表される構成単位が全構成単位の少なくとも60モル%、好ましくは少なくとも80モル%であり、特に好ましくは実質的に下記一般式(17)で表される構成単位からなる臭素化ポリカーボネート化合物である。
また、かかる式(17)において、好適にはRはメチレン基、エチレン基、イソプロピリデン基、-SO2-、特に好ましくはイソプロピリデン基を示す。
本発明のポリカーボネート樹脂組成物には、含フッ素滴下防止剤を含むことができる。かかる含フッ素滴下防止剤を上記難燃剤と併用することにより、より良好な難燃性を得ることができる。かかる含フッ素滴下防止剤としては、フィブリル形成能を有する含フッ素ポリマーを挙げることができ、かかるポリマーとしてはポリテトラフルオロエチレン、テトラフルオロエチレン系共重合体(例えば、テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体、など)、米国特許第4379910号公報に示されるような部分フッ素化ポリマー、フッ素化ジフェノールから製造されるポリカーボネート樹脂などを挙げることかできるが、好ましくはポリテトラフルオロエチレン(以下PTFEと称することがある)である。
本発明のポリカーボネート樹脂組成物には公知の各種安定剤を配合することができる。安定剤としては、リン系安定剤、ヒンダードフェノール系酸化防止剤、紫外線吸収剤および光安定剤などが挙げられる。
リン系安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル、並びに第3級ホスフィンなどが例示される。これらの中でも特に、亜リン酸、リン酸、亜ホスホン酸、およびホスホン酸、トリオルガノホスフェート化合物、およびアシッドホスフェート化合物が好ましい。尚、アシッドホスフェート化合物における有機基は、一置換、二置換、およびこれらの混合物のいずれも含む。該化合物に対応する下記の例示化合物においても同様にいずれをも含むものとする。
ヒンダードフェノール化合物としては、通常樹脂に配合される各種の化合物が使用できる。かかるヒンダードフェノール化合物としては、例えば、α-トコフェロール、ブチルヒドロキシトルエン、シナピルアルコール、ビタミンE、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、2-tert-ブチル-6-(3’-tert-ブチル-5’-メチル-2’-ヒドロキシベンジル)-4-メチルフェニルアクリレート、2,6-ジ-tert-ブチル-4-(N,N-ジメチルアミノメチル)フェノール、3,5-ジ-tert-ブチル-4-ヒドロキシベンジルホスホネートジエチルエステル、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-エチル-6-tert-ブチルフェノール)、4,4’-メチレンビス(2,6-ジ-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-シクロヘキシルフェノール)、2,2’-ジメチレン-ビス(6-α-メチル-ベンジル-p-クレゾール)、2,2’-エチリデン-ビス(4,6-ジ-tert-ブチルフェノール)、2,2’-ブチリデン-ビス(4-メチル-6-tert-ブチルフェノール)、4,4’-ブチリデンビス(3-メチル-6-tert-ブチルフェノール)、トリエチレングリコール-N-ビス-3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート、1,6-へキサンジオールビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、ビス[2-tert-ブチル-4-メチル6-(3-tert-ブチル-5-メチル-2-ヒドロキシベンジル)フェニル]テレフタレート、3,9-ビス{2-[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]-1,1,-ジメチルエチル}-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、4,4’-チオビス(6-tert-ブチル-m-クレゾール)、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-チオビス(4-メチル-6-tert-ブチルフェノール)、ビス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)スルフィド、4,4’-ジ-チオビス(2,6-ジ-tert-ブチルフェノール)、4,4’-トリ-チオビス(2,6-ジ-tert-ブチルフェノール)、2,2-チオジエチレンビス-[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、2,4-ビス(n-オクチルチオ)-6-(4-ヒドロキシ-3,5-ジ-tert-ブチルアニリノ)-1,3,5-トリアジン、N,N’-ヘキサメチレンビス-(3,5-ジ-tert-ブチル-4-ヒドロキシヒドロシンナミド)、N,N’-ビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオニル]ヒドラジン、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-tert-ブチルフェニル)ブタン、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)ベンゼン、トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)イソシアヌレート、トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)イソシアヌレート、1,3,5-トリス(4-tert-ブチル-3-ヒドロキシ-2,6-ジメチルベンジル)イソシアヌレート、1,3,5-トリス2[3(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]エチルイソシアヌレート、テトラキス[メチレン-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン、トリエチレングリコール-N-ビス-3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート、トリエチレングリコール-N-ビス-3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)アセテート、3,9-ビス[2-{3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)アセチルオキシ}-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、テトラキス[メチレン-3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート]メタン、1,3,5-トリメチル-2,4,6-トリス(3-tert-ブチル-4-ヒドロキシ-5-メチルベンジル)ベンゼン、およびトリス(3-tert-ブチル-4-ヒドロキシ-5-メチルベンジル)イソシアヌレートなどが例示される。
本発明のポリカーボネート樹脂組成物は紫外線吸収剤を含有することができる。本発明のポリカーボネート樹脂組成物は良好な色相をも有することから、紫外線吸収剤の配合により屋外の使用においてもかかる色相を長期間維持することができる。
本発明のポリカーボネート樹脂組成物には、上記のリン系安定剤およびヒンダードフェノール系酸化防止剤以外の他の熱安定剤を配合することもできる。かかるその他の熱安定剤は、これらの安定剤および酸化防止剤のいずれかと併用されることが好ましく、特に両者と併用されることが好ましい。かかる他の熱安定剤としては、例えば3-ヒドロキシ-5,7-ジ-tert-ブチル-フラン-2-オンとo-キシレンとの反応生成物に代表されるラクトン系安定剤(かかる安定剤の詳細は特開平7-233160号公報に記載されている)が好適に例示される。かかる化合物はIrganox HP-136(商標、CIBA SPECIALTY CHEMICALS社製)として市販され、該化合物を利用できる。更に該化合物と各種のホスファイト化合物およびヒンダードフェノール化合物を混合した安定剤が市販されている。例えば上記社製のIrganox HP-2921が好適に例示される。本発明においてもかかる予め混合された安定剤を利用することもできる。ラクトン系安定剤の含有量は、A成分100重量部に対し、好ましくは0.0005~0.05重量部、より好ましくは0.001~0.03重量部である。
本発明のポリカーボネート樹脂組成物は、その成形時の生産性向上や成形品の寸法精度の向上を目的として、更に、脂肪酸エステル、ポリオレフィン系ワックス、シリコーン化合物、フッ素化合物(ポリフルオロアルキルエーテルに代表されるフッ素オイルなど)、パラフィンワックス、蜜蝋などの公知の離型剤を配合することもできる。本発明のポリカーボネート樹脂組成物は、良好な流動性を有することから圧力伝播が良好で、歪の均一化された成形品が得られる。一方で離型抵抗が大きくなるような複雑形状の成形品の場合、離型時における成形品の変形を招く恐れがある。上記特定の成分の配合は、かかる問題をポリカーボネート樹脂組成物の特性を損なうことなく解決するものである。
本発明のポリカーボネート樹脂組成物は更に各種の染顔料を含有し多様な意匠性を発現する成形品を提供できる。本発明で使用する染顔料としては、ペリレン系染料、クマリン系染料、チオインジゴ系染料、アンスラキノン系染料、チオキサントン系染料、紺青等のフェロシアン化物、ペリノン系染料、キノリン系染料、キナクリドン系染料、ジオキサジン系染料、イソインドリノン系染料、およびフタロシアニン系染料などを挙げることができる。更に本発明のポリカーボネート樹脂組成物はメタリック顔料を配合してより良好なメタリック色彩を得ることもできる。メタリック顔料としては、アルミ粉が好適である。また、蛍光増白剤やそれ以外の発光をする蛍光染料を配合することにより、発光色を生かした更に良好な意匠効果を付与することができる。
本発明のポリカーボネート樹脂組成物は熱線吸収能を有する化合物を含有することができる。かかる化合物としてはフタロシアニン系近赤外線吸収剤、ATO、ITO、酸化イリジウムおよび酸化ルテニウム、酸化イモニウムなどの金属酸化物系近赤外線吸収剤、ホウ化ランタン、ホウ化セリウムおよびホウ化タングステンなどの金属ホウ化物系や酸化タングステン系近赤外線吸収剤などの近赤外吸収能に優れた各種の金属化合物、ならびに炭素フィラーが好適に例示される。かかるフタロシアニン系近赤外線吸収剤としてはたとえば三井化学(株)製MIR-362が市販され容易に入手可能である。炭素フィラーとしてはカーボンブラック、グラファイト(天然、および人工のいずれも含む)およびフラーレンなどが例示され、好ましくはカーボンブラックおよびグラファイトである。これらは単体または2種以上を併用して使用することができる。フタロシアニン系近赤外線吸収剤の含有量は、A成分100重量部に対し、0.0005~0.2重量部が好ましく、0.0008~0.1重量部がより好ましく、0.001~0.07重量部がさらに好ましい。金属酸化物系近赤外線吸収剤、金属ホウ化物系近赤外線吸収剤および炭素フィラーの含有量は、本発明の樹脂組成物中、0.1~200ppm(重量割合)の範囲が好ましく、0.5~100ppmの範囲がより好ましい。
本発明のポリカーボネート樹脂組成物には、光拡散剤を配合して光拡散効果を付与することができる。かかる光拡散剤としては高分子微粒子、炭酸カルシウムの如き低屈折率の無機微粒子、およびこれらの複合物等が例示される。かかる高分子微粒子は、既にポリカーボネート樹脂の光拡散剤として公知の微粒子である。より好適には粒径数μmのアクリル架橋粒子およびポリオルガノシルセスキオキサンに代表されるシリコーン架橋粒子などが例示される。光拡散剤の形状は球形、円盤形、柱形、および不定形などが例示される。かかる球形は、完全球である必要はなく変形しているものを含み、かかる柱形は立方体を含む。好ましい光拡散剤は球形であり、その粒径は均一であるほど好ましい。光拡散剤の含有量は、A成分100重量部に対し、好ましくは0.005~20重量部、より好ましくは0.01~10重量部、更に好ましくは0.01~3重量部である。尚、光拡散剤は2種以上を併用することができる。
本発明のポリカーボネート樹脂組成物には、光高反射用白色顔料を配合して光反射効果を付与することができる。かかる白色顔料としては二酸化チタン(特にシリコーンなど有機表面処理剤により処理された二酸化チタン)顔料が特に好ましい。かかる光高反射用白色顔料の含有量は、A成分100重量部に対し、3~30重量部が好ましく、8~25重量部がより好ましい。尚、光高反射用白色顔料は2種以上を併用することができる。
本発明のポリカーボネート樹脂組成物には、帯電防止性能が求められる場合があり、かかる場合帯電防止剤を含むことが好ましい。かかる帯電防止剤としては、例えば(1)ドデシルベンゼンスルホン酸ホスホニウム塩に代表されるアリールスルホン酸ホスホニウム塩、およびアルキルスルホン酸ホスホニウム塩などの有機スルホン酸ホスホニウム塩、並びにテトラフルオロホウ酸ホスホニウム塩の如きホウ酸ホスホニウム塩が挙げられる。該ホスホニウム塩の含有量はA成分100重量部に対し、5重量部以下が適切であり、好ましくは0.05~5重量部、より好ましくは1~3.5重量部、更に好ましくは1.5~3重量部の範囲である。
本発明のポリカーボネート樹脂組成物には、強化フィラーとして無機充填材の他に公知の有機繊維状充填材を配合することができる。ここで、有機繊維状充填材とはその形状が繊維状(棒状、針状、扁平状、またはその軸が複数の方向に伸びた形状をいずれも含む)である有機充填材である。
本発明のポリカーボネート樹脂組成物には、A成分、B成分以外の熱可塑性樹脂、エラストマー、その他の流動改質剤、抗菌剤、流動パラフィンの如き分散剤、光触媒系防汚剤およびフォトクロミック剤、イオン液体などを配合することができる。
本発明のポリカーボネート樹脂組成物を製造する方法に特に制限はなく、周知の方法を用いることができる。 例えばA成分、B成分および任意に他の添加剤を、V型ブレンダー、ヘンシェルミキサー、メカノケミカル装置、押出混合機などの予備混合手段を用いて充分に混合した後、必要に応じて押出造粒器やブリケッティングマシーンなどによりかかる予備混合物の造粒を行い、その後ベント式二軸押出機に代表される溶融混練機で溶融混練し、その後ペレタイザーによりペレット化する方法が挙げられる。
1.芳香族ポリカーボネート樹脂の評価
(i)粘度平均分子量(Mv)
次式にて算出される比粘度(ηSP)を20℃で塩化メチレン100mlに芳香族ポリカーボネート樹脂を溶解した溶液からオストワルド粘度計を用いて求め、
比粘度(ηSP)=(t-t0)/t0
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数]
求められた比粘度(ηSP)から次の数式により粘度平均分子量Mvを算出した。
ηSP/c=[η]+0.45×[η]2c (但し[η]は極限粘度)
[η]=1.23×10-4 Mv0.83
c=0.7
(i)表面外観
下記の方法で得られた50mm×100mm×厚み1mmの板状試験片の表面外観を目視観察し、以下の通りに評価した。評価結果を表1および表2に示す。なお、射出成形による外観不良は、シルバー、フローマークおよび表面外観のあれ等である。
〇:外観不良が確認されない。
△:射出成形により発生する外観不良が部分的に確認される。
×:射出成形により発生する外観不良が成形品表面全体に確認される。
(ii-i)めっき析出性
下記の方法で得られた50mm×100mm×厚み1mmの板状試験片を用い下記条件にてめっきを行った。めっき析出性は所定時間内にめっきされた金属薄膜の厚みを目視にて判断し、以下の通りに評価した。評価結果を表1および表2に示す。なお、比較例1-3および2-3は表面外観が不良のため評価できなかった。
◎:金属薄膜が全体的に均一に厚く乗っている。
○:金属薄膜が厚く乗っているが、やや不均一である。
△:金属薄膜は乗っているがムラがある。(実用レベル)
×:金属薄膜がわずかにのっている。(実用レベル未達)
××:金属薄膜がほとんど乗っていない。
下記の方法で得られた50mm×100mm×厚み1mmの板状試験片を用い下記条件にてめっきを行った。めっき密着性は所定時間内にめっきされた金属薄膜と樹脂との密着性評価のため碁盤目剥離試験を実施し、以下の通りに評価した。なお碁盤目剥離試験は「JISK5600 塗料一般試験方法」の4-6に準拠して実施した。評価結果を表1および表2に示す。なお、比較例3および4は表面外観が不良のため評価できなかった。また、比較例2-1、2-2、2-6および2-7はめっき析出性不足のため評価できなかった。
○:剥離発生なし。
×:剥離発生あり。
(板状試験片の作成)
芳香族ポリカーボネート樹脂、ポリカーボネート-ポリジオルガノシロキサン共重合樹脂、レーザー照射立体回路成形用添加剤、無機充填材およびその他の各種添加剤を表1~表4に記載の各配合量でブレンダーにて混合した後、ベント式二軸押出機を用いて溶融混練してペレットを得た。使用する各種添加剤は、それぞれ配合量の10~100倍の濃度を目安に予め芳香族ポリカーボネート樹脂との予備混合物を作成した後、ブレンダーによる全体の混合を行った。押出は径30mmφのベント式二軸押出機((株)日本製鋼所TEX30α-38.5BW-3V)を使用し、スクリュー回転数230rpm、吐出量25kg/h、ベントの真空度3kPaで、押出温度は第一供給口から第二供給口まで270℃、第二供給口からダイス部分まで280℃として溶融混練しペレットを得た。芳香族ポリカーボネート樹脂、ポリカーボネート-ポリジオルガノシロキサン共重合樹脂、レーザー照射立体回路成形用添加剤、無機充填材およびその他の各種添加剤の混合物は第一供給口から押出機に供給した。ここでいう第一供給口とはダイスから最も離れた供給口である。得られたペレットを12
0℃で5時間、熱風循環式乾燥機にて乾燥した後に、射出成形機(住友重機械工業(株)製 SG-150U)によりシリンダー温度280℃、金型温度80℃の成形条件で、評価用の試験片を成形した。
成形品のめっき性評価は以下に示す条件に従ってめっきを施したのちに実施した。得られた試験片をキーエンス製MDX-2000を用いて1064nmのYAGレーザーにてパルス周波数80kHz、走査速度2m/s、出力1.45W、レーザースポット径60μm、オーバーラップ30μmの条件にて幅5mmの印字を行った後、下記の操作を実施した。
(a)脱脂(45℃で5分間) OPCクリーナーMIC* 150ml/L
(b)超音波水洗(室温で2分間)
(c)無電解銅(55℃、10分)OPCカッパーMIC-ST*
(d)水洗(1分)
(e)活性化(30℃、1分間) ICPアクセラ200ml/L、35%塩酸85ml/L
(f)水洗(1分)
(g)無電解ニッケル(80℃、10分間)ICP二コロンGM-M 120ml/L、ICP二コロンGM-1 50ml/L
(h)乾燥
(処理液で*印の処理液は奥野製薬工業(株)の商品名である。)
(A成分)
A-1-1:芳香族ポリカーボネート樹脂[粘度平均分子量22,400のポリカーボネート樹脂粉末、帝人(株)製、パンライトL-1225WP(製品名)]
A-2-1:ポリカーボネート-ポリジオルガノシロキサン共重合樹脂[ポリジオルガノシロキサンブロックの含有量:8重量%、平均シロキサン重合度(p+q):37、ポリジオルガノシロキサンドメインの平均サイズ:10nm]
A-2-2:ポリカーボネート-ポリジオルガノシロキサン共重合樹脂[ポリジオルガノシロキサンブロックの含有量:4重量%、平均シロキサン重合度(p+q):50、ポリジオルガノシロキサンドメインの平均サイズ:30nm]
A-2-3:ポリカーボネート-ポリジオルガノシロキサン共重合樹脂[ポリジオルガノシロキサンブロックの含有量:12重量%、平均シロキサン重合度(p+q):70、ポリジオルガノシロキサンドメインの平均サイズ:60nm]
A-2-4:ポリカーボネート-ポリジオルガノシロキサン共重合樹脂[ポリジオルガノシロキサンブロックの含有量:0.1重量%、平均シロキサン重合度(p+q):20、ポリジオルガノシロキサンドメインの平均サイズ:2nm]
A-2-5:ポリカーボネート-ポリジオルガノシロキサン共重合樹脂[ポリジオルガノシロキサンブロックの含有量:10重量%、平均シロキサン重合度(p+q):200、ポリジオルガノシロキサンドメインの平均サイズ:120nm]
B-1:銅/クロム酸化物 [ShepherdColorJapan,Inc.製、Black1G(商品名)]
B-2:酸化アンチモンスズ [Keeling&Walker社製、StanostatCP5C(商品名)]
B-3:三酸化アンチモン[日本精鉱(株)社製、STOX-M(商品名)]
B-4:酸化チタン/スズ-アンチモン系酸化物 [三菱マテリアル(株)社製、W-1(商品名)]
B-5:アルミニウムドープ酸化亜鉛 [ハクスイテック(株)社製、23K(商品名)]
C-1:ガラス繊維[日東紡績(株)製、CS-3PE-455(商品名)]
C-2:ガラスフレーク[日本板硝子(株)製、MEG160FYX(商品名)]
C-3:タルク[(株)勝光山工業所製、ビクトリライトTK-RC(製品名)]
C-4:マイカ[(株)山口雲母工業所製、A-41(製品名)]
C-5:ワラストナイト[キンセイマティック(株)製、SH-1250(商品名)]
C-6:炭素繊維[帝人(株)製、HT C493(製品名)]
C-7:カーボンブラック[越谷化成工業(株)製、RB-90003S(商品名)]
C-8:酸化チタン[レジノカラー(株)製、DCF-T-17007(商品名)]
STB-1:ヒンダードフェノール系酸化防止剤[BASF(株)製、Irganox1076(商品名)]
STB-2:ホスファイト系安定剤[BASF(株)製、Irgafos168(商品名)]
L:ペンタエリスリトール脂肪酸エステル系離型剤[理研ビタミン(株)製、リケスターEW-400(商品名)]
Claims (7)
- (A)芳香族ポリカーボネート樹脂(A-1成分)0~99.9重量%およびポリカーボネート-ポリジオルガノシロキサン共重合樹脂(A-2成分)0.1~100重量%からなる樹脂成分(A成分)100重量、及び
(B)レーザー照射立体回路形成用添加剤(B成分)1~50重量部
を含有し、
A-2成分が、下記式(1)で表されるポリカーボネートブロックおよび下記式(3)で表されるポリジオルガノシロキサンブロックからなり、かつポリカーボネートポリマーのマトリックス中にポリジオルガノシロキサンドメインが分散した凝集構造であり、該ポリジオルガノシロキサンドメインの平均サイズが5~100nmであるポリカーボネート-ポリジオルガノシロキサン共重合樹脂であることを特徴とするポリカーボネート樹脂組成物。
(上記一般式(1)において、R1及びR2は夫々独立して水素原子、ハロゲン原子、炭素原子数1~18のアルキル基、炭素原子数1~18のアルコキシ基、炭素原子数6~20のシクロアルキル基、炭素原子数6~20のシクロアルコキシ基、炭素原子数2~10のアルケニル基、炭素原子数6~14のアリール基、炭素原子数6~14のアリールオキシ基、炭素原子数7~20のアラルキル基、炭素原子数7~20のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシ基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、a及びbは夫々1~4の整数であり、Wは単結合もしくは下記一般式(2)で表される基からなる群より選ばれる少なくとも一つの基である。)
(上記一般式(2)においてR11,R12,R13,R14,R15,R16,R17及びR18は夫々独立して水素原子、炭素原子数1~18のアルキル基、炭素原子数6~14のアリール基及び炭素原子数7~20のアラルキル基からなる群から選ばれる基を表し、R19及びR20は夫々独立して水素原子、ハロゲン原子、炭素原子数1~18のアルキル基、炭素原子数1~10のアルコキシ基、炭素原子数6~20のシクロアルキル基、炭素原子数6~20のシクロアルコキシ基、炭素原子数2~10のアルケニル基、炭素原子数6~14のアリール基、炭素原子数6~10のアリールオキシ基、炭素原子数7~20のアラルキル基、炭素原子数7~20のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシ基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、cは1~10の整数、dは4~7の整数である。)
(上記一般式(3)において、R3、R4、R5、R6、R7及びR8は、各々独立に水素原子、炭素数1~12のアルキル基又は炭素数6~12の置換若しくは無置換のアリール基であり、R9及びR10は夫々独立して水素原子、ハロゲン原子、炭素原子数1~10のアルキル基、炭素原子数1~10のアルコキシ基であり、e及びfは夫々1~4の整数であり、pは自然数であり、qは0又は自然数であり、p+qは4以上150以下の自然数である。Xは炭素数2~8の二価脂肪族基である。) - A成分100重量部に対し、(C)無機充填材(C成分)1~150重量部を含有することを特徴とする請求項1に記載のポリカーボネート樹脂組成物。
- A-2成分中の上記式(3)で表されるポリジオルガノシロキサンブロックの含有量が0.05~50.0重量%であることを特徴とする請求項1または2に記載のポリカーボネート樹脂組成物。
- B成分が、少なくとも2種の金属を含むレーザー照射立体回路成形用添加剤であることを特徴とする請求項1~3のいずれか一項に記載のポリカーボネート樹脂組成物。
- C成分が、ガラス、炭素繊維およびケイ酸塩鉱物からなる群より選ばれる少なくとも1種の無機充填材であることを特徴とする請求項2に記載のポリカーボネート樹脂組成物。
- 請求項1~5のいずれか一項に記載のポリカーボネート樹脂組成物を成形してなる樹脂成形品。
- 請求項6に記載の樹脂成形品の表面にめっき層を積層した樹脂成形品。
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| WO2021090824A1 (ja) * | 2019-11-06 | 2021-05-14 | 三菱エンジニアリングプラスチックス株式会社 | レーザーダイレクトストラクチャリング用樹脂組成物、成形品、および、メッキ付き成形品の製造方法 |
| WO2022075328A1 (ja) * | 2020-10-06 | 2022-04-14 | 帝人株式会社 | ポリカーボネート樹脂組成物及び通信機器用回路成形品 |
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| WO2021090824A1 (ja) * | 2019-11-06 | 2021-05-14 | 三菱エンジニアリングプラスチックス株式会社 | レーザーダイレクトストラクチャリング用樹脂組成物、成形品、および、メッキ付き成形品の製造方法 |
| WO2022075328A1 (ja) * | 2020-10-06 | 2022-04-14 | 帝人株式会社 | ポリカーボネート樹脂組成物及び通信機器用回路成形品 |
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