WO2014042252A1 - ポリカーボネート系樹脂組成物、及び成形品 - Google Patents
ポリカーボネート系樹脂組成物、及び成形品 Download PDFInfo
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- WO2014042252A1 WO2014042252A1 PCT/JP2013/074889 JP2013074889W WO2014042252A1 WO 2014042252 A1 WO2014042252 A1 WO 2014042252A1 JP 2013074889 W JP2013074889 W JP 2013074889W WO 2014042252 A1 WO2014042252 A1 WO 2014042252A1
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- resin composition
- polyorganosiloxane
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- polycarbonate
- polycarbonate resin
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- UBDRBIAIXGJJJS-UHFFFAOYSA-N CC(C)(C)[NH+](C)[O-] Chemical compound CC(C)(C)[NH+](C)[O-] UBDRBIAIXGJJJS-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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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
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to a polycarbonate-based resin composition, a molded product formed by molding the resin composition, and a current breaker structure member for an automobile made of the molded product.
- ISO 12097-3 has a demand for impact tests at -35 ° C, 23 ° C, and 85 ° C. Further, when assuming extremely cold regions as in JIS D204, which is a JIS standard for automobile parts, a low temperature test at ⁇ 30 ° C. or ⁇ 40 ° C. is required. In order to satisfy these requirements, metals and ceramics are used for the casing of the gas circuit breaker for automobiles. However, in order to reduce the weight of an automobile and achieve fuel efficiency, it is necessary to replace a member made of metal or ceramic with a resin (resinization).
- a polycarbonate-polyorganosiloxane copolymer which is a polycarbonate material
- a resin material having high-temperature impact characteristics for example, Patent Document 2 discloses a resin composition containing an aromatic polycarbonate resin containing a polyorganosiloxane-acrylic composite rubber, a phosphorus flame retardant, and an anti-drip agent. ing.
- the polycarbonate resin composition using a phosphorus-based flame retardant has a problem that heat resistance is remarkably inferior in both short and long term.
- Patent Document 3 discloses a resin composition containing a polyorganosiloxane-acrylic composite rubber in an aromatic polycarbonate resin.
- this aromatic polycarbonate resin composition has improved initial low-temperature impact properties, but has a problem that the low-temperature impact properties after long-term high-temperature aging are extremely inferior.
- Patent Document 4 discloses a resin composition containing a polyorganosiloxane-acrylic composite rubber in a polyester and aromatic polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer.
- the polycarbonate resin composition using the polyester has a problem that the low-temperature impact characteristics are remarkably inferior to those using no polyester.
- Patent Document 5 discloses a resin composition containing a polyorganosiloxane-acrylic composite rubber in a polycarbonate resin composition containing a polycarbonate-polyorganosilosan copolymer.
- the preferred average number of repeating units of the origanosiloxane unit is not described, some examples have an average number of repeating n of 30.
- the low-temperature impact properties after long-term high-temperature aging of this polycarbonate-polyorganosiloxane copolymer have not been studied, and there is room for further improvement in the low-temperature impact properties.
- a polycarbonate resin composition containing a PC-POS copolymer is excellent in impact resistance in a low-temperature environment, but has a problem that its performance deteriorates after long-term high-temperature aging.
- the present invention relates to a polycarbonate-based resin composition having the characteristics of maintaining the low-temperature impact property of a PC-POS copolymer even after long-term high-temperature aging, a molded product formed by molding the resin composition, and the molded product
- An object of the present invention is to provide an automotive current breaker structural member.
- the present inventors have found that the above object can be achieved by blending a polyorganosiloxane-acrylic composite rubber with a polycarbonate-polyorganosiloxane copolymer having a specific number of repeating organosiloxane structural units.
- the present invention has been completed.
- the present invention is as follows.
- a polycarbonate resin composition comprising 1 to 5.5 parts by mass of (B) polyorganosiloxane-acrylic composite rubber and having a viscosity average molecular weight of 17,000 to 23,000 with respect to 100 parts by mass of the mixture.
- R 1 and R 2 each independently represents an alkyl group or alkoxy group having 1 to 6 carbon atoms
- X represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an alkylidene group having 2 to 8 carbon atoms.
- R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and Y represents a single bond Or an organic residue containing an aliphatic group or an aromatic group, and n represents an average number of repetitions.
- C an alkali metal salt and / or alkaline earth metal salt of an organic sulfonic acid
- D) a polytetrafluoroethylene-based anti-drip agent having a fibril-forming ability are blended with the above polycarbonate-based resin composition.
- the carbonate resin composition of the present invention comprises a polycarbonate-polyorganosiloxane copolymer, or a resin mixture comprising a polycarbonate-polyorganosiloxane copolymer and an aromatic polycarbonate other than the polycarbonate-polyorganosiloxane copolymer.
- the polyorganosiloxane-acrylic composite rubber since the polyorganosiloxane-acrylic composite rubber is blended, it has excellent impact resistance at low temperatures and has excellent low temperature impact strength even after high temperature aging.
- the present invention comprises (A) the structural unit represented by the above general formula (I) and the structural unit represented by the general formula (II), and the average of the organosiloxane constituent units in the general formula (II). 30 to 100% by mass of a polycarbonate-polyorganosiloxane copolymer (A-1) having a repeating number n of 50 to 500, and 0 to 70% by mass of an aromatic polycarbonate (A-2) other than (A-1)
- a polycarbonate-based resin composition containing 1 to 5.5 parts by weight of (B) polyorganosiloxane-acrylic composite rubber and having a viscosity average molecular weight of 17,000 to 23,000 with respect to 100 parts by weight of a certain resin mixture.
- each component of the polycarbonate-type resin composition of this invention is demonstrated.
- the PC-POS copolymer used in the present invention is a copolymer containing structural units represented by the above general formulas (I) and (II).
- the content of the structural unit represented by the general formula (I) is preferably 70 to 98% by mass, more preferably 85 to 97.5% by mass in the (A-1) PC-POS copolymer, Preferably, the content is 90 to 97% by mass.
- the content of the structural unit represented by the general formula (II) is preferably 2 to 30% by mass, more preferably 2.5 to 15% by mass in the (A-1) PC-POS copolymer. More preferably, it is 3 to 10% by mass, and further preferably 3 to 6.0% by mass.
- the content of the structural unit in (A-1) PC-POS is a value calculated by nuclear magnetic resonance (NMR) measurement.
- the average repeating number n of the organosiloxane structural unit in the general formula (II) is 50 to 500, more preferably 70 to 400, still more preferably 80 to 250, and still more preferably 85. ⁇ 190. If n is less than 50, the effect of improving impact properties at low temperatures is insufficient, and if it is 500 or less, there is no problem in the handling property of the polyorganosiloxane and there is no problem in the production of the PC-POS copolymer. It is preferable from the viewpoint.
- the value of the average repetition number n is a value calculated by nuclear magnetic resonance (NMR) measurement.
- the viscosity average molecular weight (Mv) of the PC-POS copolymer of component (A-1) is preferably 12,000 to 50,000, more preferably from the viewpoint of the balance between the strength and productivity of the molded product. Is 14,000 to 30,000, more preferably 16,000 to 25,000.
- the component (A-1) is combined with an aromatic polycarbonate (A-2) component other than (A-1) described later to form a resin mixture, the above-mentioned viscosity average molecular weight is preferable.
- the component -1) is used alone, it is preferable from the viewpoint of moldability to use a component in the range of 17,000 to 23,000.
- the (A-1) component PC-POS copolymer comprises a dihydric phenol represented by the following general formula (1), a polyorganosiloxane represented by the following general formula (2), phosgene, a carbonate ester, Alternatively, it is obtained by copolymerizing with chloroformate.
- R 1 and R 2 , X, a and b are the same as those in the general formula (I).
- R 3 to R 6 and Y are Same as the above general formula (II), n is 50 to 500, m is 0 or 1, Z is halogen, —R 7 OH, —R 7 COOH, —R 7 NH 2 , —COOH or —SH represents R 7 represents a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group which may have an alkoxy group on the ring, or an arylene group.
- the dihydric phenol represented by the general formula (1) used as a raw material for the PC-POS copolymer of the component (A-1) is not particularly limited. 2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) is preferred.
- dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4- Hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-) 3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-
- the polyorganosiloxane represented by the general formula (2) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, allylphenol, eugenol, isopropenylphenol, or the like having a predetermined polymerization degree n. It can be easily produced by hydrosilylation reaction at the end of the polyorganosiloxane chain having the above.
- the phenols are more preferably allylphenol or eugenol.
- Y in the general formula (II) of the component (A-1) is an organic residue derived from allylphenol or eugenol.
- Examples of the polyorganosiloxane represented by the general formula (2) include compounds represented by the following general formulas (3) to (11).
- R 3 to R 6 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms
- 6 represents an alkoxy group having 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
- n represents an average number of repeating organosiloxane structural units and represents a number from 50 to 500.
- R 8 represents an alkyl, alkenyl, aryl or aralkyl group
- c represents a positive integer, and is usually an integer of 1 to 6.
- a phenol-modified polyorganosiloxane represented by the general formula (3) is preferable.
- ⁇ , ⁇ -bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by the general formula (4), is represented by the general formula (5):
- the phenol-modified polyorganosiloxane can be produced by a known method. As a manufacturing method, the method shown below is mentioned, for example. First, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize ⁇ , ⁇ -dihydrogenorganopolysiloxane. At this time, ⁇ , ⁇ -dihydrogenorganopolysiloxane having a desired average repeating unit can be synthesized by changing the charging ratio of cyclotrisiloxane and disiloxane.
- this ⁇ , ⁇ -dihydrogenorganopolysiloxane is subjected to an addition reaction with a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol, to thereby obtain a desired compound.
- a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol
- a phenol-modified polyorganosiloxane having an average repeating unit can be produced.
- the component (A-2), which is an aromatic polycarbonate other than (A-1), contains a dihydric phenol compound and an organic solvent inactive to the reaction, in the presence of an alkaline aqueous solution.
- interfacial polymerization method in which polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to polymerize, or dihydric phenol compound is dissolved in pyridine or mixed solution of pyridine and inert solvent
- polymerization catalyst such as tertiary amine or quaternary ammonium salt
- dihydric phenol compound is dissolved in pyridine or mixed solution of pyridine and inert solvent
- the dihydric phenol compound used in the production of the component (A-2) aromatic polycarbonate is 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A), bis (4-hydroxyphenyl). Methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane Bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-t -Butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophen
- a molecular weight regulator, a terminal terminator or the like may be used as necessary. Any of these can be used as long as they are usually used for polymerization of polycarbonate resin.
- Specific molecular weight regulators include monohydric phenols such as phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, and p-isobutylphenol.
- monovalent carboxylic acid and derivatives thereof, and monovalent phenol can be used.
- a branched polycarbonate can be obtained by using a branching agent for the above dihydric phenol compound.
- the amount of the branching agent added is preferably 0.01 to 3 mol%, more preferably 0.1 to 1.0 mol%, based on the dihydric phenol compound.
- branching agent examples include 1,1,1-tris (4-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl ] Ethylidene] bisphenol, ⁇ , ⁇ ′, ⁇ ′′ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [ ⁇ -methyl- ⁇ - (4′-hydroxyphenyl) ethyl]- Examples thereof include compounds having three or more functional groups such as 4- [ ⁇ ′, ⁇ ′-bis (4 ′′ -hydroxyphenyl) ethyl] benzene, phloroglucin, trimellitic acid, and isatin bis (o-cresol).
- the content of (A-1) is 30 to 100% by mass, preferably 45 to 100% by mass, more preferably Is 60 to 100% by mass, and the content of (A-2) is 70 to 0% by mass, preferably 55 to 0% by mass, more preferably 40 to 0% by mass.
- the content of (A-1) is less than 30% by mass or the content of (A-2) exceeds 70% by mass, the content of the polyorganosiloxane block part in the (A) resin mixture is increased.
- the polyorganosiloxane-acrylic composite rubber used in the polycarbonate resin composition of the present invention has a core structure of rubber components intertwined so that acrylic components such as polyorganosiloxane and polyalkyl (meth) acrylate cannot be separated from each other. It is.
- the polyorganosiloxane used in the polyorganosiloxane-acrylic composite rubber is not particularly limited, but is preferably a polyorganosiloxane containing a vinyl polymerizable functional group.
- Such a polyorganosiloxane is obtained by, for example, polymerizing a mixture of a diorganosiloxane and a vinyl polymerizable functional group-containing siloxane, or a latex containing a siloxane-based crosslinking agent as necessary, at a high temperature using an acid catalyst. Can be manufactured.
- Examples of the diorganosiloxane used for the production of the polyorganosiloxane include a 3-membered or more diorganosiloxane-based cyclic body, and a 3- to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used alone or in combination of two or more.
- the vinyl polymerizable functional group-containing siloxane may contain vinyl polymerizable functional groups and can be bonded to diorganosiloxane via a siloxane bond, taking into account the reactivity with diorganosiloxane. Then, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable.
- ⁇ -methacryloyloxyethyldimethoxymethylsilane ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxypropylmethoxydimethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropylethoxydiethylsilane, methacryloyloxysilane such as ⁇ -methacryloyloxypropylethoxydiethoxymethylsilane and ⁇ -methacryloyloxybutyldiethoxymethylsilane, vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane, vinylphenylsilane such as p-vinylphenyldimethoxymethylsilane And ⁇ -mercaptopropyldimethoxymethylsilane, ⁇ -mercaptopropyltrimethoxy
- siloxane-based crosslinking agent trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane can be used.
- the polyorganosiloxane is produced by emulsifying a mixture of a diorganosiloxane and a vinyl polymerizable functional group-containing siloxane, or a mixture containing a siloxane-based crosslinking agent as necessary with an emulsifier and water.
- the latex is made into fine particles using a homomixer that makes fine particles by shearing force generated by high-speed rotation, or a homogenizer that makes fine particles using high-pressure generators, and then polymerized at a high temperature using an acid catalyst. This can be done by neutralizing the acid with a substance.
- an acid catalyst used for polymerization there are two methods for adding an acid catalyst used for polymerization, such as a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping a latex in which a siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant rate.
- a method in which the latex in which the siloxane mixture is finely divided is dropped into a high-temperature acid aqueous solution at a constant rate is preferably used.
- the emulsifier used in the production of the polyorganosiloxane is preferably an anionic emulsifier, and an emulsifier selected from sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is used.
- sodium alkylbenzene sulfonate and sodium lauryl sulfate are preferred.
- a method of mixing a siloxane mixture, an emulsifier, water and / or an acid catalyst there are mixing by high-speed stirring, mixing by a high-pressure emulsifier such as a homogenizer, etc., but the method using a homogenizer is a particle size of polyorganosiloxane latex This is a preferable method since the distribution of ⁇ is small.
- Examples of the acid catalyst used for polymerization of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more. Of these, aliphatic substituted benzene sulfonic acid is preferable, and n-dodecyl benzene sulfonic acid is particularly preferable because it is excellent in stabilizing action of the polyorganosiloxane latex.
- thermoplastic resin composition due to the emulsifier component of the polyorganosiloxane latex can be reduced.
- the polymerization temperature of the polyorganosiloxane is preferably 50 ° C. or higher, and more preferably 80 ° C. or higher.
- the polymerization time of the polyorganosiloxane is preferably 2 hours or more, more preferably 5 hours or more when the acid catalyst is mixed with the siloxane mixture, the emulsifier and water, and finely divided for polymerization.
- the latex in which the siloxane mixture is atomized is dropped into the aqueous solution, it is preferable to hold for about 1 hour after the completion of the latex dropping.
- the polymerization can be stopped by cooling the reaction solution and further neutralizing the latex with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like.
- the rubber component that is the core of the polyorganosiloxane-acrylic composite rubber used in the present invention is impregnated with a (meth) acrylate component comprising an alkyl (meth) acrylate and a polyfunctional (meth) acrylate in a polyorganosiloxane latex. Then, it can be produced by polymerization.
- alkyl (meth) acrylate examples include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate.
- a methacrylate is mentioned, These can be used individually or in combination of 2 or more types. In consideration of the impact resistance and molding gloss of the resin composition containing the graft copolymer, it is particularly preferable to use n-butyl acrylate.
- polyfunctional (meth) acrylates examples include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and the like. It can be used alone or in combination of two or more.
- a preferred polyfunctional (meth) acrylate considering the graft structure of the graft copolymer (acetone insoluble content, solution viscosity of acetone soluble component), allyl methacrylate and 1,3-butylene glycol dimethacrylate Combinations are listed.
- the rubber component (core) of the polyorganosiloxane-acrylic composite rubber composed of polyorganosiloxane and polyalkyl (meth) acrylate used in the present invention is an acrylic component such as alkyl (meth) acrylate in the latex of the polyorganosiloxane component.
- As a method of adding an acrylic compound such as alkyl (meth) acrylate there are a method of mixing with a latex of a polyorganosiloxane component at once and a method of dropping at a constant rate into a latex of a polyorganosiloxane component.
- a method of collectively mixing the latex of the polyorganosiloxane component is preferable.
- the radical polymerization initiator used for polymerization a peroxide, an azo initiator, or a redox initiator in which an oxidizing agent and a reducing agent are combined is used.
- a redox initiator is preferable, and a system in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite and hydroperoxide are combined is particularly preferable.
- the vinyl monomer is not particularly limited, and examples thereof include aromatic alkenyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and 2-ethylhexyl methacrylate, and methyl acrylate.
- acrylic acid esters such as ethyl acrylate and butyl acrylate, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Considering the impact resistance of the resin composition containing the polyorganosiloxane-acrylic composite rubber and the appearance of the molded product, it is preferable to use methyl methacrylate or acrylonitrile.
- the graft polymerization can be performed in one step or in multiple steps by adding a vinyl monomer to the rubber component latex and using a radical polymerization method.
- a radical polymerization initiator used for polymerization a peroxide, an azo initiator, or a redox initiator in which an oxidizing agent and a reducing agent are combined is used.
- a redox initiator is preferable, and a system in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite and hydroperoxide are combined is particularly preferable.
- Various chain transfer agents for adjusting the molecular weight and graft ratio of the graft polymer can be added to the vinyl monomer used in the graft polymerization.
- an emulsifier may be added to stabilize the polymerization latex and to control the average particle size of the graft copolymer.
- the emulsifier used is not particularly limited, but preferred examples thereof include a cationic emulsifier, an anionic emulsifier and a nonionic emulsifier, and more preferred examples include a sulfonate emulsifier or a sulfate emulsifier and a carboxylate. There are combinations with emulsifiers.
- the particle diameter of the polyorganosiloxane-acrylic composite rubber prepared as described above is not particularly limited, but the polycarbonate resin composition containing the polyorganosiloxane-acrylic composite rubber to be obtained is not particularly limited.
- the average particle size of the polyorganosiloxane-acrylic composite rubber is preferably in the range of 0.01 to 2 ⁇ m. When the average particle size is 0.01 ⁇ m or more and 2 ⁇ m or less, the impact resistance of the molded product obtained from the thermoplastic polycarbonate resin composition is good and the molded product surface appearance is good.
- the polyorganosiloxane-acrylic composite rubber is prepared by introducing the graft copolymer latex produced as described above into hot water in which a metal salt such as calcium chloride, calcium acetate, aluminum sulfate is dissolved.
- the graft copolymer is separated by separating and solidifying, and is produced by collecting it in powder form.
- a polyorganosiloxane-acrylic composite rubber for example, commercially available products such as METABRENE SX-005, METABRENE SRK-200, METABRENE S-2030, METABRENE S-2006 manufactured by Mitsubishi Rayon Co., Ltd. can be used. .
- the content of (B) polyorganosiloxane-acrylic composite rubber is 1.0 to 5.5 parts by weight, preferably 1.5 to 5.0 parts by weight, based on 100 parts by weight of (A) resin mixture. Part, more preferably 2.0 to 5.0, still more preferably 2.0 to 4.5 parts by weight.
- the amount is less than 1.0 part by mass, the effect of low-temperature impact characteristics after long-term high-temperature aging is insufficient.
- it exceeds 5.5 parts by mass the inherent rigidity of the polycarbonate tends to decrease, that is, the physical property balance tends to deteriorate.
- an alkali metal salt and / or alkaline earth metal salt of an organic sulfonic acid (hereinafter also referred to as an alkali (earth) organic sulfonate metal salt). ) Can be blended.
- the organic sulfonic acid include perfluoroalkane sulfonic acid and polystyrene sulfonic acid.
- Various organic sulfonic acid alkali (earth) metal salts include organic sulfonic acid alkali metal salts and alkaline earth metal salts having at least one carbon atom.
- the alkali metal include sodium, potassium, rubidium, lithium and cesium
- examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. Of these, sodium, potassium and cesium salts are preferred.
- an alkali metal salt and / or an alkaline earth metal salt of perfluoroalkanesulfonic acid or polystyrenesulfonic acid is preferable.
- alkali (earth) metal salt of perfluoroalkanesulfonic acid include those represented by the following general formula (12).
- d represents an integer of 1 to 10
- M represents an alkaline metal such as lithium, sodium, potassium, rubidium and cesium, or an alkaline earth metal such as beryllium, magnesium, calcium, strontium and barium.
- E represents the valence of M.
- these metal salts for example, those described in Japanese Patent Publication No. 47-40445 are applicable.
- examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluoro Examples include hexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid. In particular, these potassium salts are preferably used.
- an organic sulfonate alkali (earth) metal salt other than the above-mentioned alkali (earth) metal salt of perfluoroalkane sulfonate can also be used.
- the acid alkali (earth) metal salt include alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, diphenylsulfonic acid, naphthalenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzene.
- alkali (earth) metal salts of organic sulfonic acids such as sulfonic acid, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid, naphthalene trisulfonic acid, and fluorine-substituted products thereof.
- diphenylsulfonic acid alkali (earth) Metal salt is one of those preferred with alkali metal or alkaline earth metal salt of perfluoroalkane sulfonic acid.
- alkali (earth) metal salt of polystyrene sulfonic acid examples include an alkali (earth) metal salt of a sulfonate group-containing aromatic vinyl resin represented by the following general formula (13).
- Q represents a sulfonate group
- R 9 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- s represents an integer of 1 to 5
- t represents a mole fraction, and 0 ⁇ t ⁇ 1.
- the sulfonate group of Q is an alkali metal salt and / or alkaline earth metal salt of sulfonic acid, and the metals include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium.
- Etc. R 9 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.
- s is an integer of 1 to 5, and t has a relationship of 0 ⁇ t ⁇ 1. Therefore, the sulfonate group Q may include a fully substituted or partially substituted aromatic ring.
- the content of the alkali (earth) metal salt of the organic sulfonic acid is 0.01 to 0.10 parts by mass, preferably 0.02 to 0.09 parts by mass with respect to 100 parts by mass of the (A) resin mixture. Part, more preferably 0.03 to 0.08 part by mass. This range is preferable because flame retardancy can be sufficiently improved.
- a polytetrafluoroethylene-based anti-drip agent having fibril forming ability is blended as the component (D) in order to give the polycarbonate-based resin composition an effect of preventing dripping and improve flame retardancy.
- the anti-drip agent polytetrafluoroethylene having a fibril forming ability can be used.
- the “fibril forming ability” means that fibers are bonded to each other by an external action such as a shearing force. Indicates a tendency to
- Polytetrafluoroethylene having a fibril-forming ability has an extremely high molecular weight, and is usually a number average molecular weight determined from a standard specific gravity of 500,000 or more, preferably 500,000 to 15 million, more preferably 1 million to 10 million.
- PTFE is, for example, tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide, at a pressure of 6.9 to 690 kPa (1 to 100 psi), at a temperature of 0 to 200 ° C., preferably It can be obtained by polymerization at 20 to 100 ° C.
- fluorinated olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether, and perfluoroalkyl (meth) are used as the copolymerization component.
- Fluorine-containing alkyl (meth) acrylates such as acrylate can be used.
- the content of such a copolymer component is preferably 10% by mass or less with respect to tetrafluoroethylene in polytetrafluoroethylene.
- the polytetrafluoroethylene is preferably PTFE particles from the viewpoint of being uniformly dispersed in the polycarbonate.
- the particle diameter of the PTFE particles is usually 10 ⁇ m or less, preferably 0.05 to 1.0 ⁇ m.
- Examples of commercially available PTFE having fibril-forming ability include Teflon (registered trademark) 6-J (trade name, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1 and Polyflon F-103 (trade name, Daikin).
- the content of the anti-drip agent is 0.1 to 1.0 part by weight, preferably 0.2 to 0.9 part by weight, and more preferably 0.3 to 100 parts by weight of the resin mixture (A). 0.8 parts by mass.
- the amount is less than 0.1 parts by mass, the flame retardancy cannot be sufficiently improved.
- it exceeds 1.0 mass part it may become a factor which a low temperature impact characteristic falls.
- the polytetrafluoroethylene-based anti-drip agent used as the component (D) is a mixed powder composed of polytetrafluoroethylene particles and organic polymer particles from the viewpoint of the appearance and physical properties of the molded product.
- the mixed powder will be described below.
- the particle diameter of the polytetrafluoroethylene particles in the mixed powder composed of the polytetrafluoroethylene particles and the organic polymer particles is usually 10 ⁇ m or less, preferably 0.05 to 1.0 ⁇ m.
- the polytetrafluoroethylene particles are prepared, for example, as an aqueous dispersion dispersed in water containing an emulsifier and the like. This aqueous dispersion of polytetrafluoroethylene particles is obtained by emulsion polymerization of a tetrafluoroethylene monomer using a fluorine-containing surfactant.
- Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether as copolymerization components, as long as the properties of polytetrafluoroethylene are not impaired during the emulsion polymerization of polytetrafluoroethylene particles, Fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used.
- the content of the copolymer component is preferably 10% by mass or less with respect to tetrafluoroethylene in the polytetrafluoroethylene particles.
- the organic polymer particles used by mixing with the polytetrafluoroethylene particles are not particularly limited, but from the viewpoint of dispersibility of the polytetrafluoroethylene particles when blended in the (A) resin mixture. It is preferable that the resin has an affinity for the polycarbonate resin.
- monomers for producing organic polymer particles include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene.
- Styrene monomers such as 2,4-dimethylstyrene and ⁇ -methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate , Alkyls such as dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate (Meth) acrylate monomers; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxy
- an alkyl (meth) acrylate monomer is preferred.
- organic polymer particles can be obtained.
- the said monomer can be used 1 type or in mixture of 2 or more types.
- the organic polymer particles particles made of an alkyl (meth) acrylate copolymer are preferable.
- the organic polymer particles are prepared, for example, as an aqueous dispersion of organic polymer particles.
- the method for producing the aqueous dispersion of organic polymer particles is not particularly limited, and examples thereof include an emulsion polymerization method using an ionic emulsifier and a soap-free emulsion polymerization method using an ionic polymerization initiator.
- the ionic emulsifier any of an anionic emulsifier, a cationic emulsifier and an amphoteric ionic emulsifier can be used.
- a nonionic emulsifier can also be used together with these ionic emulsifiers.
- anionic emulsifiers include fatty acid salts, higher alcohol sulfate esters, liquid fatty oil sulfate esters, aliphatic amine and aliphatic amide sulfates, aliphatic alcohol phosphate esters, and dibasic fatty acid ester sulfonates. And fatty acid amide sulfonates, alkyl allyl sulfonates, and naphthalene sulfonates of formalin condensates.
- the cationic emulsifier include aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts.
- amphoteric emulsifiers examples include alkyl betaines.
- anionic properties such as persulfate (for example, potassium persulfate or ammonium persulfate), azobis (isobutyronitrile sulfonate), 4,4′-azobis (4-cyanovaleric acid), etc.
- Polymerization initiator 2,2′-azobis (amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ′ -Cationic polymerization initiators such as azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobisisobutyramide dihydrate.
- the particle diameter d of the organic polymer particles of the present invention is not particularly limited. From the viewpoint of the stability of the aggregated state with the polytetrafluoroethylene particles, the particle diameter d of the polytetrafluoroethylene particles is as follows. A range of formulas is preferred. [Equation 1] 0.1D ⁇ d ⁇ 10D
- the mixed powder composed of the polytetrafluoroethylene particles and the organic polymer particles is prepared by, for example, mixing the aqueous dispersion of the polytetrafluoroethylene particles and the aqueous dispersion of the organic polymer particles, and then a method described later. It is obtained by pulverizing.
- This mixed powder includes aggregated particles in which polytetrafluoroethylene particles and organic polymer particles are aggregated due to a difference in surface charge, and individual particles that remain without being aggregated.
- Agglomerated particles have a structure in which polytetrafluoroethylene particles and organic polymer particles are integrated, but there are various morphologies depending on the mixing ratio and particle diameter of both particles.
- a nonionic emulsifier may be adsorbed on the surfaces of the polytetrafluoroethylene particles and / or the organic polymer particles before mixing.
- the nonionic emulsifier is not particularly limited, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, dialkylphenoxy poly (ethyleneoxy) ethanol, polyvinyl alcohol, polyacrylic acid, and alkyl cellulose.
- aqueous dispersion mixed as described above is poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salted out, solidified, and then dried or spray-dried. can do.
- a monomer having an ethylenically unsaturated bond can be emulsion-polymerized in the above aqueous dispersion of polytetrafluoroethylene particles, and powdered by coagulation or spray drying.
- Examples of the ethylenically unsaturated monomer to be emulsion-polymerized in the aqueous dispersion include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene, Styrene monomers such as 2,4-dimethylstyrene and ⁇ -methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, Alkyl (meth) acrylate monomers such as dodecyl methacrylate, cyclohexyl acrylate
- mixed powders composed of polytetrafluoroethylene particles and organic polymer particles include, for example, A-3750 and A-3800 (trade names, manufactured by Mitsubishi Rayon Co., Ltd.), SN3300B7 (trade names, Shine Polymer) Manufactured) and the like.
- polyorganosiloxane is further contained as the component (E) in order to prevent deterioration of the resin composition and maintain properties such as mechanical strength, stability and heat resistance.
- Such polyorganosiloxane is not particularly limited, and examples thereof include alkyl hydrogen silicone and alkoxy silicone. Examples of the alkyl hydrogen silicone include methyl hydrogen silicone and ethyl hydrogen silicone. On the other hand, examples of the alkoxysilicone include methoxysilicone and ethoxysilicone.
- an alkoxysilicone is particularly preferable, and specifically, a silicone compound containing an alkoxysilyl group in which an alkoxy group is bonded to a silicon atom directly or via a divalent hydrocarbon group.
- Cyclic, network, and partially branched linear polyorganosiloxane, and linear polyorganosiloxane is particularly preferable.
- polyorganosiloxane having a molecular structure in which an alkoxy group is bonded to the silicone main chain via a methylene chain is preferable.
- component (E) for example, commercially available SH1107, SR2402, BY16-160, BY16-161, BY16-160E, BY16-161E manufactured by Toray Dow Corning Co., Ltd. is preferably used. it can.
- the content of (E) polyorganosiloxane is preferably 0.05 to 0.30 parts by mass, more preferably 0.05 to 0.20 parts by mass, and still more preferably 100 parts by mass of the resin mixture (A). Is 0.07 to 0.15 parts by mass. If it is 0.05 mass part or more, deterioration of polycarbonate resin will not occur easily and the fall of the molecular weight of resin can be suppressed. Moreover, if it is 0.30 mass part or less, since the balance of economical efficiency is favorable, since silver does not generate
- the polycarbonate-based resin composition of the present invention is conventionally added to the polycarbonate-based resin composition as necessary as long as the effects of the present invention are not impaired.
- Various known additives can be blended. These additives include antioxidants, reinforcing materials, fillers, stabilizers, UV absorbers, antistatic agents, lubricants, mold release agents, dyes, pigments, other flame retardants and elastomers for improving impact resistance, etc. Is mentioned.
- the content of these additives is usually 0 to 1 part by mass, preferably about 0.01 to 0.5 part by mass, with respect to 100 parts by mass of the (A) resin mixture.
- a phosphorus-based antioxidant and / or a phenol-based antioxidant is preferably used.
- phosphite-based antioxidants such as tris (2,4-di-t-butylphenyl) phosphite are suitable for thermal stability during high temperature molding and long-term thermal stability of molded products. It is preferable in terms of improvement.
- These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type, and as a compounding quantity, it is 0.01 with respect to 100 mass parts of resin mixture of (A) component. About 1 to 1 part by mass, preferably 0.1 to 0.3 part by mass, more preferably 0.05 to 0.3 part by mass.
- the blending amount is within this range, the thermal stability in the molding process and the long-term thermal stability of the molded product can be maintained, and it is difficult to cause a decrease in molecular weight.
- an antioxidant is used. However, there is a tendency that the adverse effect on the polycarbonate of the decomposition product produced due to heat, moisture, etc. is increased.
- a molded article made of the polycarbonate resin composition of the present invention can be obtained by molding and kneading the above components.
- each of the obtained polycarbonate resin compositions has a viscosity average molecular weight of 17,000 to 23,000, preferably 18,000 to 22,000.
- the blending ratio of the components particularly the viscosity average molecular weight of the (A-1) component of the polycarbonate-polyorganosiloxane copolymer and the aromatic polycarbonate (A-2) component other than the (A-1) component, It is necessary to adjust the blending ratio.
- the viscosity average molecular weight of the polycarbonate resin composition within this range, the flowability at the time of melting can be ensured, and a polycarbonate resin composition having excellent moldability can be obtained.
- the kneading method is not particularly limited, and examples thereof include a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder, and the like.
- the heating temperature at the time of kneading is usually selected in the range of 240 to 330 ° C., preferably 250 to 320 ° C.
- molding method conventionally known various molding methods can be used, for example, injection molding method, injection compression molding method, extrusion molding method, blow molding method, press molding method, vacuum molding method and foam molding method. It is done.
- the components other than the polycarbonate resin can be added in advance as a master batch with melt-kneading with the polycarbonate resin or other thermoplastic resin.
- the molded object of this invention is preferably pelletized and injection molded, and special molding methods such as general injection molding method or injection compression molding method and gas assist molding method can be used, and various molded products can be produced.
- molding technique which improves external appearance, such as a heat cycle shaping
- flame retarding is calculated
- the heat transfer efficiency from the heat source can be increased, and this is an effective method when a high heat source is provided.
- injection compression molding or high pressure or ultra high pressure injection molding, and partial compression molding or the like is used for molding a molded product having a partial thin portion. You can also.
- the polycarbonate resin composition of the present invention is excellent in impact resistance at low temperatures and can be molded into molded articles having excellent impact resistance even after high temperature aging, so that it is used as a component of current breakers used in automobiles and the like. be able to.
- a polycarbonate-polyorganosiloxane copolymer of component (A-1) was produced as follows.
- Production Example 1 [Production of Polycarbonate-Polydimethylsiloxane Copolymer (Si-PC-1)] (1) Synthesis of Polycarbonate Oligomer To a 5.6 mass% aqueous sodium hydroxide solution, 2000 mass ppm of sodium dithionite is added to bisphenol A (BPA) to be dissolved later, and the bisphenol A concentration is 13. Bisphenol A was dissolved so as to be 5% by mass to prepare a sodium hydroxide aqueous solution of bisphenol A.
- BPA bisphenol A
- This aqueous sodium hydroxide solution of bisphenol A was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 40 L / hr, methylene chloride at a flow rate of 15 L / hr, and a flow rate of 4.0 kg / hr.
- the tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.
- the reaction solution exiting the tubular reactor was continuously introduced into a 40-liter baffled tank reactor equipped with a receding blade, and bisphenol A sodium hydroxide aqueous solution was further added at 2.8 L / hr, 25
- the reaction was performed by adding a mass% aqueous sodium hydroxide solution at 0.07 L / hr, water at 17 L / hr, and a 1 mass% triethylamine aqueous solution at a flow rate of 0.64 L / hr.
- the reaction liquid overflowing from the tank reactor was continuously extracted and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
- the concentration of the polycarbonate oligomer thus obtained was 329 g / L, and the chloroformate group concentration was 0.74 mol / L.
- a methylene chloride solution of pt-butylphenol (PTBP) (138 g of PTBP dissolved in 2.0 L of methylene chloride), an aqueous sodium hydroxide solution of BPA (577 g of NaOH and 2.0 g of sodium dithionite) in water 8 (A solution obtained by dissolving 1012 g of BPA in an aqueous solution dissolved in 4 L) was added, and a polymerization reaction was carried out for 50 minutes. For dilution, 10 L of methylene chloride was added and stirred for 10 minutes.
- PTBP pt-butylphenol
- the organic phase was separated into an organic phase containing a polycarbonate-polydimethylsiloxane copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
- the methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained was sequentially washed with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid with respect to the solution. Washing with pure water was repeated until the electrical conductivity in the aqueous phase became 0.01 ⁇ S / m or less.
- the methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure.
- the amount of PDMS residue (PDMS copolymerization amount) determined by nuclear magnetic resonance (NMR) of the obtained polycarbonate-polydimethylsiloxane copolymer was 6.0% by mass, measured according to ISO 1628-4 (1999).
- composition, viscosity number, and viscosity average molecular weight Mv of the obtained polycarbonate-polydimethylsiloxane copolymer are shown in Table 1.
- Examples 1 to 6 and Comparative Examples 1 to 6 Each component was mix
- tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF, trade name “Irgafos168”) was used as an antioxidant in an amount of 0 with respect to 100 parts by mass of component (A). 10 parts by mass were mixed and melt-kneaded at a resin temperature of 280 ° C. using a vented twin screw extruder (manufactured by Toshiba Machine Co., Ltd., model name “TEM-35B”) to obtain pellets of each polycarbonate resin composition .
- TEM-35B vented twin screw extruder
- the polycarbonate resin composition pellets were injection molded using a molding machine under the molding conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain test pieces. Using the obtained test pieces, the impact strength, combustibility, and elastic modulus at 23 ° C. and ⁇ 40 ° C. were measured by the following method. The results are shown in Table 2.
- A-1) Polycarbonate-polyorganosiloxane copolymer Polycarbonate-polydimethylsiloxane copolymer produced in Production Examples 1 to 3 (Si-PC-1 to 3)
- the physical property evaluation in this invention evaluated each characteristic of resin with the following method using the granulated pellet obtained by the Example and the comparative example.
- Fluidity (Q value) measurement The obtained pellets were dried at 120 ° C. for 5 hours, and then Q value (flow value) [unit: 10 ⁇ 2 mL / sec] was measured.
- the amount of molten resin (mL / sec) flowing out from a nozzle having a diameter of 1 mm and a length of 10 mm was measured in accordance with JISK7210 under a pressure of 280 ° C. and 15.7 MPa.
- the Q value represents the amount of outflow per unit time, and the larger the value, the higher the fluidity.
- (3) Formability Formability was evaluated according to the following criteria in consideration of the Q value indicating fluidity. ⁇ (Good): Q value is 5 or more ⁇ (Bad): Q value is less than 5 (4) Izod impact test (no aging) A notched Izod impact test was conducted at 23 ° C. and ⁇ 40 ° C.
- Izod impact test (with aging) After aging at 105 ° C. for 400 hours using a hot-air circulating oven and further allowing to stand at 23 ° C. for 4 hours, a notched Izod impact test was conducted at 23 ° C. and ⁇ 40 ° C. in accordance with ASTM D256. . Regardless of aging or not, those having an Izod impact value of not less than 400 J / m at 23 ° C. and ⁇ 40 ° C. are good.
- Flammability A vertical combustion test was performed using test pieces (length 12.7 mm, width 12.7 mm, thickness 1.5 mm) prepared in accordance with UL standard 94, and V-0, It was classified into V-1 and V-2 and evaluated. (7) Flexural modulus A bending test was performed according to ASTM D790.
- the polycarbonate resin compositions of Examples 1 to 6 comprising a polycarbonate-polyorganosiloxane copolymer having a specific number of repeating organosiloxane structural units and a polyorganosiloxane-acrylic composite rubber.
- a polycarbonate-polyorganosiloxane copolymer having a specific number of repeating organosiloxane structural units and a polyorganosiloxane-acrylic composite rubber In addition to being excellent in low temperature impact resistance, it can be seen that it is excellent in impact resistance after high temperature aging.
- Comparative Example 1 containing no polyorganosiloxane-acrylic composite rubber is inferior in impact resistance after high-temperature aging, and in Comparative Example 2 where the viscosity average molecular weight of the resin mixture exceeds 23,000, the Q value is small. , The moldability becomes worse.
- Comparative Example 3 in which the number of repeating organosiloxane units in the polycarbonate-polyorganosiloxane copolymer is small, and in Comparative Examples 4 and 5 in which an aromatic polycarbonate is used without using a polycarbonate-polyorganosiloxane copolymer, It can be seen that both the low temperature impact resistance and the impact resistance after high temperature aging are reduced. Further, when the amount of the polyorganosiloxane-acrylic composite rubber compounded as the component (B) is large, as can be seen from Comparative Example 6, the low temperature impact resistance and the impact resistance after high temperature aging are satisfactory. The elastic modulus becomes low and a polycarbonate resin composition satisfying all the characteristics cannot be obtained.
- the polycarbonate resin composition of the present invention is excellent in impact resistance at low temperatures and has excellent low temperature impact strength even after high temperature aging.
- the molded article of the polycarbonate resin composition of the present invention is useful for a current breaker structure member for automobiles and the like.
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Abstract
Description
自動車に設置されるインフレーター使用ガス圧式電気回路遮断器は、ISO12097試験やこれに準拠した自動車メーカー独自の試験の要求を満足しなければならない。例えば、ISO12097-3には-35℃、23℃、85℃での衝撃試験の要求が有る。また、自動車部品のJIS規格であるJISD204にあるように極寒地を想定する場合、-30℃又は-40℃での低温試験が要求される。このような要求を満足させる為に自動車用ガス圧式電気回路遮断器の筐体には、金属やセラミックが使用されている。しかし、自動車を軽量化し省燃費化を達成する為には、金属やセラミックからなる部材を樹脂製に置き換えること(樹脂化)が課題となる。樹脂化に当たっては、耐熱性が100℃以上の一般的なエンジニアリングプラスチックであれば、85℃での環境下の試験要求には満足できるが、同時に-35~-40℃といった低温環境下での試験要求も満足することが求められる。また、それだけではなく、高度な環境特性(例えば100℃以上の長期耐熱(耐高温エージング)性)や万一の発火の際に備えて高度な難燃性が要求される場合もある。
このようなPC-POS共重合体として、例えば、特許文献2には、芳香族ポリカーボネート樹脂にポリオルガノシロキサン-アクリル系複合ゴム、リン系難燃剤、滴下防止剤を含有する樹脂組成物が開示されている。しかしながら、リン系難燃剤を使用したポリカーボネート樹脂組成物は短期、長期ともに耐熱性が著しく劣るという問題があった。
特許文献4には、ポリカーボネート-ポリオルガノシロキサン共重合体を含むポリエステル及び芳香族ポリカーボネートの樹脂組成物にポリオルガノシロキサン-アクリル系複合ゴムを含有する樹脂組成物が開示されている。しかしながら、ポリエステルを使用したポリカーボネート樹脂組成物はポリエステルを使用しないものよりも低温衝撃特性は著しく劣るという問題があった。また、ポリカーボネート-ポリオルガノシロキサン共重合体の好ましいオリガノシロキサン構成単位の平均繰り返し数nは40~60であることが記載されているものの、このポリカーボネート-ポリオルガノシロキサン共重合体の低温衝撃特性は不十分であり、長期高温エージング後の低温衝撃特性も検討されていない。
特許文献5には、ポリカーボネート-ポリオルガノシロサン共重合体を含むポリカーボネートの樹脂組成物にポリオルガノシロキサン-アクリル系複合ゴムを含有する樹脂組成物が開示されている。好ましいオリガノシロキサン構成単位の平均繰り返し数は記載されていないが、実施例は平均繰り返し数nが30のものがある。しかし、このポリカーボネート-ポリオルガノシロキサン共重合体の長期高温エージング後の低温衝撃特性は検討されておらず、低温衝撃特性にはさらなる改善の余地がある。
本発明は、長期高温エージング後もPC-POS共重合体が有する低温衝撃特性を維持する特性をもつポリカーボネート系樹脂組成物、及び、その樹脂組成物を成形してなる成形品、並びにその成形品からなる自動車用電流遮断器構造部材を提供することを目的とする。
(1)(A)一般式(I)で表される構造単位及び一般式(II)で表される構造単位を有し、かつ、一般式(II)におけるオルガノシロキサン構成単位の平均繰り返し数nが50~500であるポリカーボネート-ポリオルガノシロキサン共重合体(A-1)30~100質量%、及び、(A-1)以外の芳香族ポリカーボネート(A-2)0~70質量%である樹脂混合物100質量部に対して、(B)ポリオルガノシロキサン-アクリル系複合ゴム1~5.5質量部を含み、粘度平均分子量が17000~23000である、ポリカーボネート系樹脂組成物。
また、上記のポリカーボネート系樹脂組成物には、(C)有機スルホン酸のアルカリ金属塩及び/又はアルカリ土類金属塩や、(D)フィブリル形成能を有するポリテトラフルオロエチレン系ドリップ防止剤を配合することができ、これらを含有することで難燃性がさらに向上したポリカーボネート系樹脂組成物とすることができる。さらに、上記のポリカーボネート系樹脂組成物には、(E)ポリオルガノシロキサンを配合することもでき、これにより、樹脂組成物の劣化を防止し、機械的強度や耐熱性などが維持されたポリカーボネート系樹脂組成物とすることもできる。
(2)上記のポリカーボネート系樹脂組成物を成形してなる成形品。
(3)上記の成形品を含む電流遮断器構造部材。
本発明で用いられるPC-POS共重合体は、上記の一般式(I)及び(II)で表される構成単位を含む共重合体である。上記一般式(I)で表される構成単位の含有量は、(A-1)PC-POS共重合体中、好ましくは70~98質量%、より好ましくは85~97.5質量%、更に好ましくは90~97質量%である。また、上記一般式(II)で表される構成単位の含有量は、(A-1)PC-POS共重合体中、好ましくは2~30質量%、より好ましくは2.5~15質量%、更に好ましくは3~10質量%、更に好ましくは3~6.0質量%である。2質量%以上であれば耐衝撃強さ向上の効果が十分であり、一方、30質量%以下であれば十分な耐熱性を有する。なお、(A-1)PC-POS中の構成単位の含有量は、核磁気共鳴(NMR)測定により算出された値である。
ビスフェノールA以外の二価フェノールとしては、例えば、ビス(4-ヒドロキシフェニル)メタン、1,1-ビス(4-ヒドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシフェニル)ブタン、2,2-ビス(4-ヒドロキシフェニル)オクタン、ビス(4-ヒドロキシフェニル)フェニルメタン、ビス(4-ヒドロキシフェニル)ジフェニルメタン、2,2-ビス(4-ヒドロキシ-3-メチルフェニル)プロパン、ビス(4-ヒドロキシフェニル)ナフチルメタン、1,1-ビス(4-ヒドロキシ-t-ブチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3-ブロモフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3-クロロフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジクロロフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジブロモフェニル)プロパン等のビス(ヒドロキシアリール)アルカン類、1,1-ビス(4-ヒドロキシフェニル)シクロペンタン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)-3,5,5-トリメチルシクロヘキサン、2,2-ビス(4-ヒドロキシフェニル)ノルボルナン、1,1-ビス(4-ヒドロキシフェニル)シクロドデカン等のビス(ヒドロキシアリール)シクロアルカン類、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシ-3,3’-ジメチルフェニルエーテル等のジヒドロキシアリールエーテル類、4,4’-ジヒドロキシジフェニルスルフィド、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルフィド等のジヒドロキシジアリールスルフィド類、4,4’-ジヒドロキシジフェニルスルホキシド、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルホキシド等のジヒドロキシジアリールスルホキシド類、4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジヒドロキシ-3,3’-ジメチルジフェニルスルホン等のジヒドロキシジアリールスルホン類、4,4’-ジヒドロキシジフェニル等のジヒドロキシジフェニル類、9,9-ビス(4-ヒドロキシフェニル)フルオレン、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン等のジヒドロキシジアリールフルオレン類、1,3-ビス(4-ヒドロキシフェニル)アダマンタン、2,2-ビス(4-ヒドロキシフェニル)アダマンタン、1,3-ビス(4-ヒドロキシフェニル)-5,7-ジメチルアダマンタン等のジヒドロキシジアリールアダマンタン類、4,4’-[1,3-フェニレンビス(1-メチルエチリデン)]ビスフェノール、10,10-ビス(4-ヒドロキシフェニル)-9-アントロン、1,5-ビス(4-ヒドロキシフェニルチオ)-2,3-ジオキサペンタン等が挙げられる。
これらの二価フェノールは、単独で又は二種以上を混合して用いてもよい。
これらの中でも、重合の容易さの観点においては、一般式(3)に示すフェノール変性ポリオルガノシロキサンが好ましい。また、入手の容易さの観点においては、一般式(4)に示す化合物中の一種であるα,ω-ビス[3-(o-ヒドロキシフェニル)プロピル]ポリジメチルシロキサン、一般式(5)に示す化合物中の一種であるα,ω-ビス[3-(4-ヒドロキシ-2-メトキシフェニル)プロピル]ポリジメチルシロキサンが好ましい。
まず、シクロトリシロキサンとジシロキサンとを酸性触媒存在下で反応させ、α,ω-ジハイドロジェンオルガノポリシロキサンを合成する。このとき、シクロトリシロキサンとジシロキサンとの仕込み比を変えることで所望の平均繰り返し単位を持つα,ω-ジハイドロジェンオルガノポリシロキサンを合成することができる。次いで、ヒドロシリル化反応用触媒の存在下に、このα,ω-ジハイドロジェンオルガノポリシロキサンにアリルフェノールやオイゲノール等の不飽和脂肪族炭化水素基を有するフェノール化合物を付加反応させることで、所望の平均繰り返し単位を有するフェノール変性ポリオルガノシロキサンを製造することができる。
また、この段階では、低分子量の環状ポリオルガノシロキサンや過剰量の上記フェノール化合物が不純物として残存するために、減圧下で加熱し、これらの低分子化合物を留去することが好ましい。
本発明のポリカーボネート系樹脂組成物において、(A-1)以外の芳香族ポリカーボネートである(A-2)成分は、反応に不活性な有機溶媒、アルカリ水溶液の存在下、二価フェノール系化合物及びホスゲンを反応させた後、第三級アミンもしくは第四級アンモニウム塩等の重合触媒を添加して重合させる界面重合法や、二価フェノール系化合物をピリジン又はピリジンと不活性溶媒の混合溶液に溶解し、ホスゲンを導入し直接製造するピリジン法等従来の芳香族ポリカーボネートの製造法により得られるものが使用できる。
これらの二価フェノールは、単独で又は二種以上を混合して用いてもよい。
これらの一価フェノールの中では、p-t-ブチルフェノール、p-クミルフェノール、p-フェニルフェノール等が好ましい。また、これらの化合物は、単独で又は二種以上の化合物を併用して用いることができる。
分岐化剤としては、例えば、1,1,1-トリス(4-ヒドロキシフェニル)エタン、4,4’-[1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エチリデン]ビスフェノール、α,α’,α”-トリス(4-ヒドロキシフェニル)-1,3,5-トリイソプロピルベンゼン、1-[α-メチル-α-(4’-ヒドロキシフェニル)エチル]-4-[α’,α’-ビス(4”-ヒドロキシフェニル)エチル]ベンゼン、フロログルシン、トリメリット酸、イサチンビス(o-クレゾール)等の官能基を3つ以上有する化合物が挙げられる。
(A-1)の含有量が30質量%未満、もしくは(A-2)の含有量が70質量%を超えた場合、(A)樹脂混合物中のポリオルガノシロキサンブロック部分の含有量を多くし、低温衝撃強度を向上させるために、(A-1)成分の製造時に、一般式(II)で表される構成単位を含むポリオルガノシロキサンブロック部分の含有量を多くする必要がある。しかし、(A-1)成分の製造時に当該含有量を多くすると、重合工程で反応の均一性が低下することがあり、また重合物の洗浄工程で重合物と洗浄水との分離性が悪化することがあるため、(A-1)成分の生産性が大きく低下する。
本発明のポリカーボネート系樹脂組成物に用いるポリオルガノシロキサン-アクリル系複合ゴムは、ポリオルガノシロキサン及びポリアルキル(メタ)アクリレートなどのアクリル成分が互いに分離できないように絡み合ったゴム成分のコア構造を有するものである。ポリオルガノシロキサン-アクリル系複合ゴムに用いられるポリオルガノシロキサンは、特に限定されるものではないが、好ましくはビニル重合性官能基を含有するポリオルガノシロキサンである。かかるポリオルガノシロキサンは、例えば、ジオルガノシロキサンとビニル重合性官能基含有シロキサンからなる混合物またはさらに必要に応じてシロキサン系架橋剤を含むラテックスを、酸触媒を用いて高温下で重合させることにより、製造することができる。
また、ポリオルガノシロキサンの製造の際に用いる乳化剤としては、アニオン系乳化剤が好ましく、アルキルベンゼンスルホン酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸エステルナトリウム等の中から選ばれる乳化剤が使用される。特にアルキルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等が好ましい。
重合の停止は、反応液を冷却し、さらにラテックスを水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等のアルカリ性物質により中和することによって行うことができる。
このようなポリオルガノシロキサン-アクリル系複合ゴムとしては、例えば、三菱レイヨン社製のメタブレンSX-005、メタブレンSRK-200、メタブレンS-2030、メタブレンS-2006等の市販品を利用することもできる。
本発明では、難燃性を向上させるために、(C)成分として、有機スルホン酸のアルカリ金属塩及び/又はアルカリ土類金属塩(以下、有機スルホン酸アルカリ(土類)金属塩、ともいう)を配合することができる。
有機スルホン酸としては、パーフルオロアルカンスルホン酸やポリスチレンスルホン酸等が挙げられる。
有機スルホン酸アルカリ(土類)金属塩としては、種々のものが挙げられるが、少なくとも一つの炭素原子を有する有機スルホン酸アルカリ金属塩やアルカリ土類金属塩である。
アルカリ金属としては、ナトリウム、カリウム、ルビジウム、リチウム及びセシウム等が挙げられ、アルカリ土類金属としては、ベリリウム、マグネシウム、カルシウム、ストロンチウム及びバリウム等が挙げられる。これら中でも、ナトリウム、カリウム及びセシウムの塩が好ましい。
パーフルオロアルカンスルホン酸のアルカリ(土類)金属塩として、下記一般式(12)で表されるものが挙げられる。
これらの金属塩としては、例えば、特公昭47-40445号公報に記載されているものが該当する。
ここで、Qのスルホン酸塩基は、スルホン酸のアルカリ金属塩及び/又はアルカリ土類金属塩であり、金属としては、ナトリウム、カリウム、リチウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム及びバリウム等が挙げられる。
また、R9は、水素原子又は炭素数1~10の炭化水素基であるが、好ましくは水素原子又はメチル基である。
sは1~5の整数であり、tは、0<t≦1の関係である。そのため、スルホン酸塩基Qは、芳香環に対して、全置換したもの、部分置換したものを含んでもよい。
本発明では、ポリカーボネート系樹脂組成物に溶融滴下防止効果を付与し、難燃性を向上させるために、(D)成分として、フィブリル形成能を有するポリテトラフルオロエチレン系のドリップ防止剤を配合することもできる。
ドリップ防止剤としては、フィブリル形成能を有するポリテトラフルオロエチレンを用いることができ、ここで、「フィブリル形成能」とは、せん断力等の外的作用により、樹脂同士が結合して繊維状になる傾向を示すことをいう。
当該重合の際、ポリテトラフルオロエチレンの特性を損なわない範囲で、共重合成分としてヘキサフルオロプロピレン、クロロトリフルオロエチレン、フルオロアルキルエチレン及びパーフルオロアルキルビニルエーテル等の含フッ素オレフィン、パーフルオロアルキル(メタ)アクリレート等の含フッ素アルキル(メタ)アクリレートを用いることができる。このような共重合成分の含有量は、ポリテトラフルオロエチレン中のテトラフルオロエチレンに対して、好ましくは10質量%以下である。
フィブリル形成能を有するPTFEの市販品としては、例えば、テフロン(登録商標)6-J(商品名、三井・デュポンフロロケミカル株式会社製)、ポリフロンD-1及びポリフロンF-103(商品名、ダイキン工業株式会社製)、CD-076及びCD-097(商品名、旭硝子株式会社製)、アルゴフロンF5(商品名、モンテフルオス社製)及びポリフロンMPA、ポリフロンFA-100(商品名、ダイキン工業株式会社製)等が挙げられる。
これらのPTFEは、単独で又は2種以上を組合せて使用することができる。
このような、(D)成分として用いるポリテトラフルオロエチレン系ドリップ防止剤としては、成形品の外観や物性の観点からポリテトラフルオロエチレン粒子及び有機系重合体粒子からなる混合粉体であることが好ましく、以下にこの混合粉体について説明する。
ポリテトラフルオロエチレン粒子は、例えば乳化剤等を含んだ水に分散した、水性分散液として調製される。このポリテトラフルオロエチレン粒子の水性分散液は、含フッ素界面活性剤を用い、テトラフルオロエチレンモノマーを乳化重合することにより得られる。
ポリテトラフルオロエチレン粒子の乳化重合の際、ポリテトラフルオロエチレンの特性を損なわない範囲で、共重合成分としてヘキサフルオロプロピレン、クロロトリフルオロエチレン、フルオロアルキルエチレン及びパーフルオロアルキルビニルエーテル等の含フッ素オレフィン、パーフルオロアルキル(メタ)アクリレート等の含フッ素アルキル(メタ)アクリレートを用いることができる。
また、ポリテトラフルオロエチレン粒子と混合して用いる有機系重合体粒子としては、特に制限されるものではないが、(A)樹脂混合物に配合する際のポリテトラフルオロエチレン粒子の分散性の観点から、ポリカーボネート樹脂に親和性を有するものであることが好ましい。
これらの単量体を重合することにより、有機系重合体粒子が得られる。上記単量体は、1種又は2種以上混合して用いることができる。有機系重合体粒子としては、アルキル(メタ)アクリレート系共重合体からなる粒子が好ましい。
イオン性乳化剤としては、アニオン性乳化剤、カチオン性乳化剤及び両性イオン乳化剤のいずれも用いることができる。又、これらのイオン性乳化剤と共に、ノニオン性乳化剤を併用することもできる。
アニオン性乳化剤としては、脂肪酸塩類、高級アルコール硫酸エステル塩類、液体脂肪油硫酸エステル塩類、脂肪族アミン及び脂肪族アミドの硫酸塩類、脂肪族アルコールリン酸エステル塩類、二塩基性脂肪酸エステルのスルホン酸塩類、脂肪酸アミドスルホン酸塩類、アルキルアリルスルホン酸塩類及びホルマリン縮合物のナフタリンスルホン酸塩類等を挙げることができる。
カチオン性乳化剤としては、脂肪族アミン塩類、第四アンモニウム塩類及びアルキルピリジニウム塩等を挙げることができる。
両性乳化剤としては、アルキルベタイン等を挙げることができる。
イオン性重合開始剤としては、過硫酸塩(例えば、過硫酸カリウムや過硫酸アンモニウム)、アゾビス(イソブチロニトリルスルホン酸塩)、4,4’-アゾビス(4-シアノ吉草酸)等のアニオン性重合開始剤、2,2’-アゾビス(アミジノプロパン)二塩酸塩、2,2’-アゾビス[2-(5-メチル-2-イミダゾリン-2-イル)プロパン]二塩酸塩、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]二塩酸塩、2,2’-アゾビスイソブチルアミド二水和物等のカチオン性重合開始剤を挙げることができる。
[数1]
0.1D<d<10D
凝集粒子は、ポリテトラフルオロエチレン粒子と有機系重合体粒子とが一体となった構造を有するが、そのモルフォロジーは両粒子の混合比や粒子径により様々なものがある。即ち、ポリテトラフルオロエチレン粒子の周りを有機系重合体が取り囲んだ形態、その反対に有機系重合体粒子の周りをポリテトラフルオロエチレン粒子が取り囲んだ形態及び1つの粒子に対して数個の粒子が凝集した形態等が存在する。
ノニオン性乳化剤としては、特に制限はなく、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ジアルキルフェノキシポリ(エチレンオキシ)エタノール、ポリビニルアルコール、ポリアクリル酸及びアルキルセルロース等を挙げることができる。
また、上記のポリテトラフルオロエチレン粒子の水性分散液中で、エチレン性不飽和結合を有する単量体を乳化重合して、凝固又はスプレードライにより粉体化することもできる。
本発明では、樹脂組成物の劣化を防止し、機械的強度や安定性、耐熱性等の特性を維持するために、更に(E)成分として、ポリオルガノシロキサンを含有することが好ましい。
このようなポリオルガノシロキサンとしては、特に限定はされないが、例えば、アルキル水素シリコーン、アルコキシシリコーン等が挙げられる。
アルキル水素シリコーンとしては、例えば、メチル水素シリコーン、エチル水素シリコーン等が挙げられる。一方、アルコキシシリコーンとしては、例えば、メトキシシリコーン、エトキシシリコーン等が挙げられる。
このような(E)成分としては、例えば、市販の東レ・ダウコーニング(株)製のSH1107、SR2402、BY16-160、BY16-161、BY16-160E、BY16-161E等を好適に使用することができる。
本発明のポリカーボネート系樹脂組成物には、上述の(A)~(E)成分の他、本発明の効果を損なわない範囲で、必要に応じて、従来、ポリカーボネート系樹脂組成物に添加される公知の種々の添加剤を配合することができる。これらの添加剤としては酸化防止剤、補強材、充填剤、安定剤、紫外線吸収剤、帯電防止剤、滑剤、離型剤、染料、顔料、その他の難燃剤や耐衝撃性改良用のエラストマー等が挙げられる。
これらの添加剤の含有量は、(A)樹脂混合物100質量部に対して、通常0~1質量部、好ましくは0.01~0.5質量部程度である。
これらの酸化防止剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよく、配合量としては、(A)成分の樹脂混合物100質量部に対して、0.01~1質量部程度であり、好ましくは0.1~0.3質量部、より好ましくは0.05~0.3質量部である。
配合量がこの範囲にあると、成形工程などでの熱安定性、成形品の長期熱安定性を維持でき、分子量低下を引き起こし難く、また、配合量が1質量部を超えると、酸化防止剤が熱や湿気等が原因で生成した分解物のポリカーボネートへ及ぼす悪影響が大きくなる傾向が認められる。
本発明のポリカーボネート系樹脂組成物からなる成形品は、上述の各成分を配合し、混練したものを成形することで得られる。
本発明のポリカーボネート系樹脂組成物を製造する際には、得られるポリカーボネート系樹脂組成物の粘度平均分子量が17,000~23,000、好ましくは、18,000~22,000となるように各成分の配合割合、特にポリカーボネート-ポリオルガノシロキサン共重合体の(A-1)成分と(A-1)成分以外の芳香族ポリカーボネート(A-2)成分とが有する粘度平均分子量を考慮し、これらの配合割合を調整することが必要である。ポリカーボネート系樹脂組成物の粘度平均分子量をこの範囲のものとすることで、溶融時の流れ性が確保でき、成形性に優れたポリカーボネート系樹脂組成物とすることができる。
また、本願発明の成形体を外観部材として使用する場合には、ヒートサイクル成形法、高温金型、断熱金型等の外観を向上させる成形技術を用いることが好ましい。
また、部品に難燃化が求められる場合は、難燃性を有する樹脂材料との積層成形、二色成形等の成形技術を用いることが好ましい。
金属部品のインサート成形、アウトサート成形を行うことにより発熱源からの熱伝達効率を高めることができるので、高発熱源を有する場合には有効な方法となる。
大型薄肉の射出成形品を得るためには、射出圧縮成形や高圧又は超高圧の射出成形を用いることが好ましく、部分的な薄肉部を有する成形品の成形には、部分圧縮成形等を用いることもできる。
製造例1
[ポリカーボネート-ポリジメチルシロキサン共重合体(Si-PC-1)の製造]
(1)ポリカーボネートオリゴマーの合成
5.6質量%水酸化ナトリウム水溶液に、後から溶解するビスフェノールA(BPA)に対して2000質量ppmの亜二チオン酸ナトリウムを加え、これにビスフェノールA濃度が13.5質量%になるようにビスフェノールAを溶解し、ビスフェノールAの水酸化ナトリウム水溶液を調製した。
このビスフェノールAの水酸化ナトリウム水溶液を40L/hr、塩化メチレンを15L/hrの流量で、ホスゲンを4.0kg/hrの流量で内径6mm、管長30mの管型反応器に連続的に通した。管型反応器はジャケット部分を有しており、ジャケットに冷却水を通して反応液の温度を40℃以下に保った。
管型反応器を出た反応液は後退翼を備えた内容積40Lのバッフル付き槽型反応器へ連続的に導入され、ここに更にビスフェノールAの水酸化ナトリウム水溶液を2.8L/hr、25質量%水酸化ナトリウム水溶液を0.07L/hr、水を17L/hr、1質量%トリエチルアミン水溶液を0.64L/hrの流量で添加して反応を行った。槽型反応器から溢れ出る反応液を連続的に抜き出し、静置することで水相を分離除去し、塩化メチレン相を採取した。
このようにして得られたポリカーボネートオリゴマーの濃度は329g/L、クロロホーメート基濃度は0.74mol/Lであった。
邪魔板、パドル型攪拌翼及び冷却用ジャケットを備えた50L槽型反応器に上記で製造したポリカーボネートオリゴマー溶液15L、塩化メチレン9.0L、ジメチルシロキサン単位の繰返し数が90である2-アリルフェノール末端変性ポリジメチルシロキサン(PDMS)393g及びトリエチルアミン8.8mLを仕込み、攪拌下でここに6.4質量%水酸化ナトリウム水溶液1389gを加え、10分間ポリカーボネートオリゴマーとアリルフェノール末端変性PDMSとの反応を行った。
この重合液に、p-t-ブチルフェノール(PTBP)の塩化メチレン溶液(PTBP138gを塩化メチレン2.0Lに溶解したもの)、BPAの水酸化ナトリウム水溶液(NaOH577gと亜ジチオン酸ナトリウム2.0gを水8.4Lに溶解した水溶液にBPA1012gを溶解させたもの)を添加し50分間重合反応を行った。
希釈のため塩化メチレン10Lを加え10分間攪拌した後、ポリカーボネート-ポリジメチルシロキサン共重合体を含む有機相と過剰のBPA及びNaOHを含む水相に分離し、有機相を単離した。
こうして得られたポリカーボネート-ポリジメチルシロキサン共重合体の塩化メチレン溶液を、その溶液に対して順次、15容積%の0.03mol/LNaOH水溶液、0.2モル/L塩酸で洗浄し、次いで洗浄後の水相中の電気伝導度が0.01μS/m以下になるまで純水で洗浄を繰り返した。
洗浄により得られたポリカーボネート-ポリジメチルシロキサン共重合体の塩化メチレン溶液を濃縮・粉砕し、得られたフレークを減圧下120℃で乾燥した。
得られたポリカーボネート-ポリジメチルシロキサン共重合体の核磁気共鳴(NMR)により求めたPDMS残基量(PDMS共重合量)は6.0質量%、ISO1628-4(1999)に準拠して測定した粘度数は47.5、粘度平均分子量Mv=17700であった。
[ポリカーボネート-ポリジメチルシロキサン共重合体(Si-PC-2)及び(Si-PC-3)の製造]
ポリジメチルシロキサンの種類(式(II)で表される構成単位中のシロキサン基の平均繰返し数nを変えたもの)、ポリジメチルシロキサンの使用量、p-t-ブチルフェノールの使用量を表1に記載の通りに変更し、製造例1と同様にして(Si-PC-2)及び(Si-PC-3)を合成した。
表2に示す割合で各成分を配合して、ポリカーボネート系樹脂組成物を調製した。調製する際に、酸化防止剤として、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト(BASF社製、商品名「Irgafos168」)を、(A)成分100質量部に対して、0.10質量部混合し、ベント付き二軸押出機(東芝機械(株)製、機種名「TEM-35B」)によって樹脂温度280℃で溶融混練し、各ポリカーボネート系樹脂組成物のペレットを得た。
このポリカーボネート系樹脂組成物ペレットを、射出成形機を用い、シリンダー温度280℃、金型温度80℃の成形条件で射出成形し、試験片を得た。
得られた試験片を用いて、次に示す方法で、23℃及び-40℃における耐衝撃強度、燃焼性、弾性率の測定を行った。その結果を表2に示す。
(A-1)ポリカーボネート-ポリオルガノシロキサン共重合体
製造例1~3で製造したポリカーボネート-ポリジメチルシロキサン共重合体(Si-PC-1~3)
(A-2)(A-1)以外の芳香族ポリカーボネート樹脂
1)タフロンFN2200A(商品名、出光興産(株)製、p-t-ブチルフェノールを末端基に有するBPAポリカーボネート、粘度平均分子量Mv=21500)
2)タフロンFN2600A(商品名、出光興産(株)製、p-t-ブチルフェノールを末端基に有するBPAポリカーボネート、粘度平均分子量Mv=25500)
3)ノバレックス7030PJ(商品名、三菱エンジニアリングプラスチックス(株)製、p-t-ブチルフェノールを末端基に有するBPAポリカーボネート、粘度平均分子量Mv=29000)
(B)ポリオルガノシロキサン-アクリル系複合ゴム
B-1)メタブレンSX-005(商品名、三菱レイヨン(株)製、コアがポリオルガノシロキサンとn-ブチルアクリレート、シェルがメチルメタクリレートからなるポリオルガノシロキサン-アクリル系複合ゴム)
B-2)メタブレンSRK-200(商品名、三菱レイヨン(株)製、コアがポリオルガノシロキサンとn-ブチルアクリレート、シェルがスチレン及びアクリロニトリルからなるポリオルガノシロキサン-アクリル系複合ゴム)
(C)エフトップKFBS(商品名、三菱マテリアル電子化成株式会社(株)、パーフルオロブタンスルホン酸カリウム)
(D)メタブレンA-3800(商品名、三菱レイヨン(株)製、ポリテトラフルオロエチレン粒子及び有機系重合体粒子からなる混合粉体)
(E)BY16-161(商品名、東レ・ダウコーニング(株)製、メトキシ基が2価炭化水素基を介してケイ素原子に結合したメトキシシリル基を含むポリシロキサン)。
(物性評価)
(1)粘度平均分子量(Mv)
20℃における塩化メチレン溶液の極限粘度〔η〕を測定し、Schnellの式(〔η〕=1.23×10-5×Mv0.83)より算出した。
(2)流動性(Q値)測定
得られたペレットを120℃で5時間乾燥した後、Q値(流れ値)〔単位;10-2mL/sec〕測定を行った。
高架式フローテスターを用い、JISK7210に準拠し、280℃、15.7MPaの圧力下にて、直径1mm、長さ10mmのノズルより流出する溶融樹脂量(mL/sec)を測定した。
Q値は、単位時間当たりの流出量を表しており、数値が大きいほど、流動性が高いことを示す。
(3)成形性
成形性は、流動性を示すQ値を参酌し、次の基準に従って評価した。
○(良好):Q値が5以上
×(不良):Q値が5未満
(4)Izod衝撃試験 (エージングなし)
ASTM D256に準じ、23℃及び-40℃にてノッチ付アイゾッド衝撃試験を行った。
(5)Izod衝撃試験 (エージングあり)
熱風循環式オーブンを使用し105℃にて400時間エージングさせた後、さらに23℃にて4時間放置させた後にASTM D256に準じ、23℃及び-40℃にてノッチ付アイゾッド衝撃試験を行った。
エージング有無に関わらず23℃及び-40℃におけるIzod衝撃値が400J/m以上のものが良好である。
(6)燃焼性
UL規格94に準じて作製した、試験片(長さ12.7mm、幅12.7mm、厚さ1.5mm)の試験片を用いて垂直燃焼試験を行い、V-0、V-1、V-2に分類して評価した。
(7)曲げ弾性率
ASTM D790に準じ、曲げ試験を行った。
Claims (10)
- (A)一般式(I)で表される構造単位及び一般式(II)で表される構造単位を有し、かつ、一般式(II)におけるオルガノシロキサン構成単位の平均繰り返し数nが50~500であるポリカーボネート-ポリオルガノシロキサン共重合体(A-1)30~100質量%、及び、(A-1)以外の芳香族ポリカーボネート(A-2)0~70質量%である樹脂混合物100質量部に対して、(B)ポリオルガノシロキサン-アクリル系複合ゴム1~5.5質量部を含み、粘度平均分子量が17000~23000である、ポリカーボネート系樹脂組成物。
- Yがアリルフェノールまたはオイゲノールからの有機残基である請求項1に記載のポリカーボネート系樹脂組成物。
- 一般式(I)で表される構造単位が、ビスフェノールAから誘導された構造単位である請求項1又は2に記載のポリカーボネート系樹脂組成物。
- 一般式(II)で表される構造単位中のR3~R6がすべてメチル基である請求項1~3のいずれかに記載のポリカーボネート系樹脂組成物。
- ポリオルガノシロキサン-アクリル系複合ゴム(B)は、コアがポリオルガノシロキサンと、ポリアルキル(メタ)アクリレートから構成され、シェルが1種類以上のビニル系単量体がグラフト重合された複合ゴムである請求項1~4のいずれかに記載のポリカーボネート系樹脂組成物。
- 更に、(A)成分100質量部に対して、(C)有機スルホン酸のアルカリ金属塩及び/又はアルカリ土類金属塩0.01~0.10質量部、及び/又は(D)フィブリル形成能を有するポリテトラフルオロエチレン系のドリップ防止剤0.1~1.0質量部を含む請求項1~5のいずれかに記載のポリカーボネート系樹脂組成物。
- フィブリル形成能を有するポリテトラフルオロエチレン系のドリップ防止剤(D)がポリテトラフルオロエチレン粒子及び有機系重合体粒子からなる混合粉体である請求項6に記載のポリカーボネート系樹脂組成物。
- 更に、(A)成分100質量部に対して、(E)ポリオルガノシロキサンを0.05~0.30質量部含有する、請求項1~7のいずれかに記載のポリカーボネート系樹脂組成物。
- 請求項1~8のいずれかに記載のポリカーボネート系樹脂組成物を成形してなる成形品。
- 請求項9に記載の成形品を含む電流遮断器構造部材。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13836938.4A EP2896655B1 (en) | 2012-09-14 | 2013-09-13 | Polycarbonate resin composition and molded article |
CN201380047518.4A CN104619775B (zh) | 2012-09-14 | 2013-09-13 | 聚碳酸酯系树脂组合物及成型品 |
US14/426,877 US9617422B2 (en) | 2012-09-14 | 2013-09-13 | Polycarbonate resin composition and molded article |
KR1020157005772A KR102075889B1 (ko) | 2012-09-14 | 2013-09-13 | 폴리카보네이트계 수지 조성물, 및 성형품 |
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JP (1) | JP6200137B2 (ja) |
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US9969841B2 (en) | 2014-12-04 | 2018-05-15 | Lg Chem, Ltd. | Copolycarbonate and composition comprising the same |
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WO2016203916A1 (ja) * | 2015-06-17 | 2016-12-22 | 出光興産株式会社 | ポリカーボネート系樹脂組成物の製造方法 |
JP5914737B1 (ja) * | 2015-08-12 | 2016-05-11 | 出光興産株式会社 | ポリカーボネート樹脂組成物及びその成形体 |
EP3354677B1 (en) * | 2015-08-27 | 2020-04-29 | Idemitsu Kosan Co., Ltd. | Method for producing polycarbonate-polyorganosiloxane copolymer |
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Publication number | Publication date |
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KR20150058183A (ko) | 2015-05-28 |
EP2896655A4 (en) | 2016-05-11 |
JP6200137B2 (ja) | 2017-09-20 |
EP2896655A1 (en) | 2015-07-22 |
TW201420673A (zh) | 2014-06-01 |
TWI593748B (zh) | 2017-08-01 |
CN104619775B (zh) | 2016-08-17 |
US20150210854A1 (en) | 2015-07-30 |
CN104619775A (zh) | 2015-05-13 |
KR102075889B1 (ko) | 2020-02-11 |
US9617422B2 (en) | 2017-04-11 |
EP2896655B1 (en) | 2017-05-03 |
JP2014058607A (ja) | 2014-04-03 |
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