KR101903214B1 - Polycarbonate resin composition and molding produced using same - Google Patents

Abstract

The present invention relates to a polycarbonate resin (A-1) comprising a polycarbonate-polyorganosiloxane copolymer (A-1) and an aromatic polycarbonate (A-2) other than (A-1) in a mass ratio of 5:95 to 100: (A) of 70 to 99.5% by mass and the graphene sheet (B) of 30 to 0.5% by mass, and a molded article obtained by molding the resin composition. The present invention provides a polycarbonate resin composition which provides a molded article excellent in flame retardance, rigidity, impact resistance, conductivity and molded appearance, and further, thermal conductivity, and a molded article having the above-described properties obtained by molding the resin composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polycarbonate resin composition,

The present invention relates to a polycarbonate resin composition and a molded article using the same. More particularly, the present invention relates to a polycarbonate resin composition which provides a molded article excellent in flame retardance, rigidity, impact resistance, conductivity and molded appearance, and furthermore, thermal conductivity, and a molded article having the above-described properties obtained by molding the resin composition .

BACKGROUND ART [0002] With the recent development of electronics technology, information processing apparatuses and electronic office equipment are rapidly spreading. With the spread of electronic devices, troubles such as electromagnetic interference caused by noise generated from electronic components on peripheral devices and malfunction due to static electricity increase, which is a big problem. In order to solve these problems, there has been a demand for a material having excellent conductivity and antistatic property. Further, along with the thinning of the product, additional high strength and flame retardancy have been demanded.

BACKGROUND ART Conventionally, a conductive polymer material in which a conductive filler or the like is blended with a polymer material having a low conductivity has been widely used. Metal fibers, metal powders, carbon black, carbon fibers and the like are generally used as the conductive filler. However, when metal fibers and metal powder are used as the conductive filler, there is obtained an excellent conductivity giving effect. However, There are drawbacks that can not be obtained. When carbon black is used as a conductive filler, conductive carbon black such as Ketjenblack, Balkan XC72 and acetylene black, which can achieve high conductivity by the addition of a small amount, is used, but they have poor dispersibility to resin. Since the dispersibility of carbon black affects the conductivity of the resin composition, a unique blending and mixing technique is required to obtain stable conductivity.

When carbon fiber is used as a conductive filler, a desired strength and elastic modulus can be obtained by ordinary reinforcing carbon fibers. However, in order to impart conductivity, a high filling is required, and the inherent physical properties of the resin are deteriorated.

Patent Document 1 discloses a technique for improving the conductivity and flame retardancy by blending carbon nanotubes in a polycarbonate-polyorganosiloxane copolymer (sometimes abbreviated as PC-PDMS), and Patent Document 2 discloses a technique in which graphite is added to polycarbonate And a technique of imparting thermal conductivity, and Patent Document 3 discloses a technique of blending functional graphene into a resin.

Japanese Patent Application Laid-Open No. 2003-221508 Japanese Laid-Open Patent Publication No. 2011-16937 Japanese Published Patent Publication No. 2010-506013

However, in the technique described in Patent Document 1, sufficient stiffness can not be sufficiently given, and further thin film flame-retarding requirements can not be coped with, so that it is not necessarily satisfactory enough.

Patent Document 2 discloses a technology for imparting thermal conductivity by blending graphite with polycarbonate. When the flame retardant is not used in combination, flame retardancy is not expressed, and there is no description about conductivity or rigidity. In Patent Document 2, there is no description of graphene which is the thickness of the nano order, and it is difficult to prepare graphene which is a nano-order thickness by using a conventional extruder, Was not reached. Patent Document 3 is a technique of blending a functional graphene. However, in a polycarbonate material, there is no description of graphene which is optimal for flame retardance and conductivity.

SUMMARY OF THE INVENTION The present invention has been made under such circumstances, and an object of the present invention is to provide a polycarbonate resin composition which provides a molded article excellent in flame retardance, rigidity, impact resistance, conductivity and molded appearance, and furthermore, thermal conductivity, and a molded article And to provide an image processing method and an image processing method.

As a result of diligent research to achieve the above object, the present inventors have found that when a polycarbonate organosiloxane copolymer containing a polyorganosiloxane block having a specific structural unit at a predetermined ratio and an aromatic polycarbonate other than , A resin composition containing a predetermined amount of a graphene sheet may be suitable for the purpose of the polycarbonate resin. The present invention has been completed based on this finding.

That is, the present invention provides the following (1) to (8).

(1) A polycarbonate resin having a mass ratio of a polycarbonate-polyorganosiloxane copolymer (A-1) and an aromatic polycarbonate (A-2) other than (A-1) in a ratio of 5:95 to 100: , 70 to 99.5 mass% of the graft copolymer (A), and 30 to 0.5 mass% of the graphene sheet (B).

(2) The polycarbonate resin composition according to (1), wherein the graphene sheet (B) has a thickness of 5 to 10 nm and a size of 3 m or more.

(3) The polycarbonate-polyorganosiloxane copolymer (A-1) has a main chain containing a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) (2), wherein the polycarbonate resin composition contains 2 to 40 mass% of a polyorganosiloxane block comprising a structural unit represented by the following formula (1).

[Chemical Formula 1]

Wherein R ¹ and R ² are each independently an alkyl or alkoxy group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, an alkylidene group having 5 to 15 carbon atoms A cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO-, R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom or 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, Y represents an aliphatic or aromatic organic residue, n is an average number of repeating units, And a and b represent an integer of 0 to 4,

(4) The polycarbonate resin composition according to the above (3), wherein Y is an organic residue from allyl phenol or ogenol.

(5) The polycarbonate resin composition according to (3) or (4), wherein the structural unit represented by the general formula (I) is a structural unit derived from bisphenol A.

(6) The polycarbonate resin composition according to any one of (3) to (5), wherein all of R ³ and R ⁴ in the structural unit represented by the general formula (II) are methyl groups.

(7) The polymer composition according to any one of (1) to (6), wherein the polytetrafluoroethylene (C) is contained in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the total amount of the components (A) By weight of the polycarbonate resin composition.

(8) A molded article obtained by molding the polycarbonate resin composition according to any one of (1) to (7).

According to the present invention, it is possible to provide a polycarbonate resin composition which provides a molded article excellent in flame retardancy, rigidity, impact resistance, conductivity and molded appearance, and furthermore, thermal conductivity, and a molded article having the above-described properties obtained by molding the resin composition .

In addition, the molded article of the present invention has the above-described features and also does not cause contamination of semiconductors or the like due to dropping of carbon. Therefore, the molded article of the present invention can be used as a housing of electrical / electronic devices such as office automation equipment, , Parts, films, and automobile parts.

First, the polycarbonate resin composition of the present invention will be described.

[Polycarbonate resin composition]

The polycarbonate resin composition of the present invention is a polycarbonate resin composition wherein the mass ratio of the polycarbonate-polyorganosiloxane copolymer (A-1) and the aromatic polycarbonate (A-2) other than (A-1) is from 5:95 to 100: , 70 to 99.5% by mass of the polycarbonate resin (A) and 30 to 0.5% by mass of the graphene sheet (B).

Each component in the polycarbonate resin composition of the present invention will be described below.

[Polycarbonate-polyorganosiloxane copolymer (A-1)]

The polycarbonate-polyorganosiloxane copolymer (A-1) for use in the present invention contains a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II) It is preferable to contain 2 to 40 mass% of a polyorganosiloxane block comprising the structural unit represented by the general formula (II). In the present specification, the polycarbonate-polyorganosiloxane copolymer may be referred to as " PC-PDMS copolymer ".

(2)

Wherein R ¹ and R ² are each independently an alkyl or alkoxy group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms A cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO-, and 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 6 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, Y is an aliphatic or aromatic organic residue, n is an average number of repeating units of 1 to 600, a and b represent an integer of 0 to 4; The Y is preferably an organic residue from allyl phenol or oxygen. The n is preferably an integer of 1 to 500, more preferably 5 to 200 in view of the performance of the obtained polycarbonate resin composition.

In the PC-PDMS copolymer (A-1), the content of the polyorganosiloxane block is preferably from 2 to 40% by mass, more preferably from 3 to 25% by mass from the viewpoints of flame retardance and impact resistance More preferable.

In addition, R ³ and of the structural units from the viewpoint of performance of the obtained polycarbonate resin composition by the above general formula (Ⅰ) preferably have a structural unit represented by the structural units derived from bisphenol A, and the general formula (Ⅱ) R ⁴ are all methyl groups.

Generally, in order to exhibit impact resistance, the viscosity average molecular weight of the PC-PDMS copolymer (A-1) is large, but when the viscosity average molecular weight is large, molding of the thin wall member becomes difficult.

By raising the molding temperature, the viscosity of the resin composition can be lowered. However, in this case, the molding cycle becomes longer and the economical efficiency is lowered. In addition, if the temperature is excessively increased, the thermal stability of the resin composition deteriorates.

Therefore, the viscosity-average molecular weight of the PC-PDMS copolymer (A-1) is preferably 15000 to 24000, more preferably 16000 to 22500, and furthermore preferably 17000 to 21000.

If the viscosity average molecular weight is 15,000 or more, the strength of the molded article is sufficient. If the viscosity average molecular weight is 24,000 or less, the viscosity of the copolymer becomes small, so that the productivity at the time of production is good.

The PC-PDMS copolymer (A-1) is obtained by reacting a divalent phenol represented by the following general formula (1), a polyorganosiloxane represented by the following general formula (2), a phosgene, a carbonate ester or a chloroformate, Is obtained by using a molecular weight regulator used in accordance with the present invention.

(3)

In the general formula (1), R ^{1 to} R ² , X, a and b are the same as in the general formula (I), and R ³ to R ⁶ , Y and n in the general formula (2) R ⁷ represents a halogen, -R ⁷ OH, -R ⁷ COOH, -R ⁷ NH ₂ , -COOH or -SH, R ⁷ represents a linear, branched, or cyclic alkyl group, Branched alkylene group, aryl-substituted alkylene group, aryl-substituted alkylene group which may have an alkoxy group on the ring, and arylene group.

In the polycarbonate resin composition of the present invention, the divalent phenol represented by the general formula (1) used in the raw material of the PC-PDMS copolymer (A-1) is not particularly limited, but 2,2-bis 4-hydroxyphenyl) propane (commonly known as bisphenol A) is preferable. When bisphenol A is used as the bifunctional phenol, a PC-PDMS copolymer having X in the general formula (I) is an isopropylidene group and a = b = 0.

Examples of the dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, Propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, Bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and 2,2- (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (Hydroxyaryl) cycloalkanes such as hexane, 2,2-bis (4-hydroxyphenyl) norbornane and 1,1-bis (4-hydroxyphenyl) cyclododecane, Dihydroxyphenyl ether, and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; dihydroxyaryl ethers such as 4,4'-dihydroxydiphenyl sulfide, 4,4'- Dihydroxy-3,3'-dimethyldiphenyl sulfide and the like, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxydiaryl sulfoxides such as dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone; Dihydroxydiphenyls such as dihydroxydiarylsulfone, 4,4'-dihydroxydiphenyl, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis -3-methylphenyl) fluorene, and the like, Bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2- 4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4 '- [1,3-phenylenebis (1-methylethylidene)] bisphenol, 10 , 10-bis (4-hydroxyphenyl) -9-anthrone, and 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene.

These divalent phenols may be used alone or in combination of two or more.

The polyorganosiloxane represented by the general formula (2) is preferably a polyol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, allylphenol, Can be easily produced by subjecting the terminal of the siloxane chain to hydrosilaneation reaction. More preferably, the phenol is allylphenol or ogenol. In this case, Y in the general formula (II) of the component (A-1) is an organic residue derived from allylphenol or augenol.

As the polyorganosiloxane represented by the general formula (2), it is preferable that all of R ³ and R ⁴ are methyl groups, and for example, the following compounds represented by the following general formulas (3) to (11) can be given.

[Chemical Formula 4]

In the 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, an alkoxy group having 1 to 6 carbon atoms Or an aryl group having 6 to 12 carbon atoms, and n represents an average number of repeating units of the organosiloxane structural unit, R ⁸ represents an alkyl, alkenyl, aryl or aralkyl group, and c represents a positive integer, and is ordinarily an integer of 1 to 6.

Of these, phenol-modified polyorganosiloxanes represented by the general formula (3) are preferable from the viewpoint of easiness of polymerization. From the viewpoint of ease of availability, it is preferred to use α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, which is one of the compounds represented by the general formula (4) Bis [3- (4-hydroxy-2-methoxyphenyl) propyl] polydimethylsiloxane is preferable.

The phenol-modified polyorganosiloxane can be prepared by a known method. The production method includes, for example, the following methods.

First, an?,? - dihydrogen organopolysiloxane is synthesized by reacting cyclotrisiloxane and disiloxane in the presence of an acidic catalyst. At this time, by changing the injection ratio of the cyclotrisiloxane and the disiloxane, an α, ω-dihydrogen organopolysiloxane having a desired average repeating unit can be synthesized. Subsequently, a phenol compound having an unsaturated aliphatic hydrocarbon group, such as allylphenol or augenol, is added to the?,? - dihydrogen organopolysiloxane in the presence of a catalyst for hydrosilylation reaction, A phenol-modified polyorganosiloxane can be produced.

In this step, since the cyclic polyorganosiloxane having a low molecular weight and the phenol compound in an excessive amount remain as impurities, it is preferable to heat them under reduced pressure to distill off these low molecular compounds.

[Aromatic polycarbonate (A-2) other than (A-1)]]

In the polycarbonate resin composition of the present invention, the component (A-2), which is an aromatic polycarbonate other than the component (A-1), can be produced by reacting a divalent phenol compound and phosgene And then adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt to effect polymerization, or an interfacial polymerization method in which a divalent phenol compound is dissolved in a mixed solution of pyridine or pyridine and an inert solvent, and phosgene is introduced And a pyridine method in which the aromatic polycarbonate is directly produced by a conventional method.

Examples of the divalent phenol compound used in the production of the aromatic polycarbonate of the component (A-2) include 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2- Bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy- Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) cyclohexane, (Hydroxyaryl) cycloalkanes such as norbornane and 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy Dihydroxyaryl ethers such as 3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide Dihydroxydialyl sulfide such as dihydroxydialyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; Dihydroxydiarylsulfone such as 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone and the like, 4,4'-dihydroxy Dihydroxydiphenyls such as cydiphenyl, 9,9-bis (4-hydroxyphenyl) Dihydroxydiaryl fluorenes such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) diphenyl methane, 1,3- Hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane. Bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenyl) -Bis (4-hydroxyphenylthio) -2,3-dioxapentaene, and the like. These divalent phenols may be used alone or in combination of two or more.

In the production of the aromatic polycarbonate as the component (A-2), a molecular weight modifier, an end terminator and the like may be used, if necessary. These can be used as long as they are usually used for polymerization of polycarbonate resin.

Specific examples of the molecular weight regulator include phenols such as phenol, on-butylphenol, m-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p- Butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, onhexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o -Cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, m- Phenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di- Phenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, A monoalkylphenol having an alkyl group in an ortho, meta or para position, a 9- (4-hi Methylphenyl) -9- (4-methoxyphenyl) fluorene, 9- (4-hydroxy- Adamantyl) phenol and the like.

Among these monohydric phenols, p-t-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferable. These compounds may be used alone or in combination of two or more compounds.

As the terminal terminating agent, a monovalent carboxylic acid and its derivative or a monovalent phenol may be used. For example, p-butylphenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluorohexylphenyl) phenol, pt - perfluorobutylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- 2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3 (Perfluorohexyloxycarbonyl) phenol, p-hydroxybenzoic acid perfluorododecyl, p- (1H, 1H-perfluorooctyloxy) phenol, , 2H, 2H, 9H-perfluorononanoic acid, and 1,1,1,3,3,3-tetrafluoro-2-propanol.

Further, with respect to the above-mentioned divalent phenol-based compound, it is also possible to use a branching agent to make a branched polycarbonate. The addition amount of the branching agent is preferably 0.01 to 3 mol%, more preferably 0.1 to 1.0 mol%, based on the divalent phenol compound.

Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, 4,4 '- [1- [4- [1- (4-hydroxyphenyl) Ethyl] phenyl] ethylidene] bisphenol, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [ (3-hydroxyphenyl) ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene, fluoroglycine, trimellitic acid and isotene bis Or more.

(A-1) in the polycarbonate resin (A) comprising the component (A-1) and the component (A-2) is 5 to 100% by mass, preferably 70 to 100% Preferably 50 to 100 mass%, and the content of (A-2) is 95 to 0 mass%, preferably 30 to 0 mass%, and more preferably 50 to 0 mass%.

When the content of the polyorganosiloxane block portion in the polycarbonate resin (A) is increased and the content of the polyorganosiloxane block portion in the polycarbonate resin (A) is less than 5% by mass or less than 95% It is not necessary to increase the content of the polyorganosiloxane block portion containing the structural unit represented by the general formula (II) in the production of the component (A-1) 1) component, the uniformity of the reaction is not lowered in the polymerization step, and the separability between the polymer and the cleansing water is not deteriorated in the cleansing step of the polymer. Therefore, the component (A-1) The productivity is improved.

The content of the polyorganosiloxane block moiety having the structural unit of the formula (II) in the polycarbonate resin (A) comprising the component (A-1) and the component (A-2) More preferably 0.5 to 25% by mass, still more preferably 0.5 to 15% by mass, still more preferably 0.5 to 10% by mass. When the amount is 0.1% by mass or more, the effect of improving the impact resistance is sufficient. On the other hand, if it is 40% by mass or less, sufficient flame retardancy and heat resistance are obtained.

[Graphene sheet (B)]

In the polycarbonate resin composition of the present invention, it is necessary to contain a graphene sheet as the component (B) in order to impart properties such as flame retardance, conductivity, rigidity, molded appearance, and thermal conductivity to the molded article.

The graphene sheet refers to a graphene sheet having one or a plurality of graphene planes and is usually made into a flaky form using ultrasonic energy and the level of flaking can be controlled by adjusting the sonification time .

The graphene sheet used in the present invention preferably has a thickness of 5 to 10 nm and a size of 3 m or more. When the thickness of the graphene sheet used in the present invention is 5 to 10 nm and the size is 3 m or more, the dispersibility of the graphene sheet is improved, so that the graphene sheet is easy to be compounded with the resin and has excellent flame retardance, conductivity, rigidity, A molded article having excellent thermal conductivity can be obtained. In view of the above, the thickness of the graphene sheet is preferably 6 to 8 nm, and the size of the graphene sheet is preferably 3 to 30 μm, more preferably 5 to 25 μm, and still more preferably 5 to 20 μm . Among the constructions described above, the graphene sheet preferably has a size of 5 to 30 탆, more preferably 5 to 20 탆, from the viewpoint of imparting higher conductivity.

In the present invention, the graphene sheet has a plate-like shape. The thickness of the graphene sheet is the size of the graphene sheet in the thickness direction, and the size is the size of the graphene structure itself. Can be measured.

Examples of the product include "xGnP" (graphene / nanopletlet) manufactured by XG Sciences. In contrast to the carbon nanotubes, since they are open and flat, it is also possible to introduce a functional group to the peripheral edge portion and coat the surface with a surface treatment agent.

In the polycarbonate resin composition of the present invention, 70 to 99.5% by mass of the polycarbonate resin (A) and the graphene sheet (B) are mixed in order to impart properties such as conductivity, rigidity, flame retardance, By mass to 30% by mass to 0.5% by mass. When the content of the graphene sheet (B) is less than 0.5% by mass, the effect of imparting the above properties is not exhibited well. On the other hand, when the content of the graphene sheet (B) exceeds 30% by mass, the impact strength is remarkably decreased and the appearance of the molded article is deteriorated. From the above viewpoint, the preferable content of the graphene sheet (B) is 1 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the graphene sheet (B) and the polycarbonate resin (A).

[Polytetrafluoroethylene (C)]

In the polycarbonate resin composition of the present invention, it is preferable that polytetrafluoroethylene is contained as the component (C) in order to have a melt-dripping effect and impart high flame retardancy.

 The polytetrafluoroethylene (C) is polytetrafluoroethylene (hereinafter abbreviated as PTFE) having an average molecular weight of 500,000 or more and capable of forming a fibril, has a melt-dropping effect and can impart high flame retardancy. The average molecular weight thereof is required to be 500,000 or more, preferably 500,000 to 10,000,000, and more preferably 1,000,000 to 10,000,000.

Specific examples of the PTFE having fibril forming ability include "Teflon (registered trademark)" 6-J (manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.), Polyplon D-1, Polyplon F- (Manufactured by Daikin Industries, Ltd.), CD076 (manufactured by Asahi Glass Sulfuropolymers Co., Ltd.), and Argoplon F5 (manufactured by Monteflore).

The PTFE having the fibril forming ability as described above can be obtained, for example, by reacting tetrafluoroethylene in the presence of sodium, potassium or ammonium peroxydisulfide in an aqueous solvent at a temperature of from 0 to 200 DEG C , Preferably at 20 to 100 캜.

The content of the PTFE is usually 0.01 to 1 part by mass, preferably 0.05 to 0.9 part by mass, per 100 parts by mass of the total amount of the polycarbonate resin (A) and the graphene sheet (B) More preferably 0.1 to 0.8 parts by mass. When the content of the PTFE is in the above range, the desired flame retardancy has a sufficient effect of preventing the dropping of molten metal.

The polycarbonate resin composition of the present invention may contain, instead of the PTFE, a mixed powder comprising polytetrafluoroethylene particles and organic polymer particles.

The particle diameter of the polytetrafluoroethylene particles in the mixed powder is usually 10 μm or less, preferably 0.05 to 1.0 μm.

The polytetrafluoroethylene particles are prepared, for example, as an aqueous dispersion, which is dispersed in water containing an emulsifier or the like. The aqueous dispersion of the polytetrafluoroethylene particles is obtained by emulsion polymerization of a tetrafluoroethylene monomer using a fluorinated surfactant.

In the emulsion polymerization of the polytetrafluoroethylene particles, it is preferable that hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether as the copolymerization component are used in the range of not deteriorating the properties of the polytetrafluoroethylene And fluoroalkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used.

The content of the copolymerization component is preferably 10% by mass or less based on tetrafluoroethylene in the polytetrafluoroethylene particles.

The organic polymer particles in the mixed powder are not particularly limited, but from the viewpoint of dispersibility of the polytetrafluoroethylene particles when blended with the polycarbonate resin (A), the organic polymer particles having affinity for the polycarbonate resin .

The content of the mixed powder composed of the polytetrafluoroethylene particles and the organic polymer particles is usually 0.1 to 1 part by mass, preferably 0.1 to 1 part by mass, per 100 parts by mass of the total amount of the polycarbonate resin (A) and the graphene sheet (B) 0.1 to 0.9 part by mass, more preferably 0.2 to 0.8 part by mass.

When the content of the mixed powder is 0.1 parts by mass or more, dripping performance is good and flame retardancy can be achieved. On the other hand, if it is 1 part by mass or less, the proportion of the organic polymer in the composition is not excessively increased, and flame retardancy can be achieved.

[Optional ingredients]

In the polycarbonate resin composition of the present invention, in addition to the components (A), (B) and (C) or the powder mixture described above, And may contain various known additives to be added to the carbonate resin composition. Examples of such additives include phosphorus antioxidants, alkali (earth) metal salts of organic sulfonic acids as flame retardant, fillers, hindered amine light stabilizers, antioxidants other than phosphorus, ultraviolet absorbers, antistatic agents, , A release agent, a dye, a pigment, and an elastomer for improving impact resistance.

(Phosphorus antioxidant)

The phosphorus-based antioxidant used in the present invention is not particularly limited. Typical examples thereof include, in addition to tris (nonylphenyl) phosphite and 2-ethylhexyldiphenylphosphite, trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, trinonylphosphite, tridecylphosphite , Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2-chloroethyl) phosphite, and tris (2,3-dichloropropyl) phosphite, tricyclohexyl phosphite Tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (hydroxyphenyl) phosphite, tris (2,4- Di-tert-butylphenyl) phosphite, and triaryl phosphites such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, Trialkylphosphate such as tris (2-chloroethyl) phosphate and tris (2,3-dichloropropyl) phosphate, tricyclohexyl-1-phosphate And triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate and 2-ethylphenyl diphenyl phosphate, and the like. Of these, triaryl phosphite and triaryl phosphate are preferably used.

In the present invention, these phosphorus-based antioxidants may be used singly or in combination of two or more. The content of the phosphorus-based antioxidant in the polycarbonate resin composition is preferably 0.1 to 1 part by mass based on 100 parts by mass of the polycarbonate resin (A). When the phosphorus antioxidant is contained in the above range, a sufficient antioxidation effect can be obtained.

(Alkali (earth) metal salt of organic sulfonic acid)

In the polycarbonate resin composition of the present invention, an alkali metal salt and / or an alkaline earth metal salt of an organic sulfonic acid (hereinafter also referred to as an organic sulfonic acid alkali (earth) metal salt) may be contained in order to improve flame retardancy.

Examples of the organic sulfonic acid include perfluoroalkanesulfonic acid and polystyrene sulfonic acid.

Examples of the organic (alkaline) sulfonic acid (earth) metal salt include organic alkali metal salts and alkaline earth metal salts of organic sulfonic acids having at least one carbon atom.

Examples of the alkali metal include sodium, potassium, lithium and cesium, and examples of the alkaline earth metal include magnesium, calcium, strontium and barium. Of these, salts of sodium, potassium and cesium are preferred.

As the component (C), an alkali metal salt and / or an alkaline earth metal salt of perfluoroalkanesulfonic acid or polystyrenesulfonic acid is preferable.

Examples of the alkali (earth) metal salt of perfluoroalkanesulfonic acid include those represented by the following general formula (12).

In the formula (12), d represents an integer of 1 to 10, M represents an alkali metal such as lithium, sodium, potassium and cesium, or an alkaline earth metal such as magnesium, calcium, strontium and barium, .

Examples of such metal salts include those described in Japanese Patent Publication No. 47-40445.

Examples of the perfluoroalkanesulfonic acid in the general formula (12) include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, , Perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid. In particular, potassium salts thereof are preferably used.

In addition, examples of the alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, diphenylsulfonic acid, naphthalenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone- -3,3'-disulfonic acid, naphthalenetrisulfonic acid, fluorine substituents thereof, and alkali metal salts and alkaline earth metal salts of organic sulfonic acids such as polystyrenesulfonic acid. Of these, perfluoroalkanesulfonic acid and diphenylsulfonic acid are particularly preferable as the organic sulfonic acid.

Examples of the alkali (earth) metal salt of polystyrene sulfonic acid include an alkali (earth) metal salt of an aromatic vinyl resin containing a sulfonic acid group represented by the following general formula (13).

[Chemical Formula 5]

In the formula (13), Q represents a sulfonic acid group, and R ⁹ represents a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms. s represents an integer of 1 to 5, t represents a mole fraction, and 0 <t? 1.

Examples of the metal include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium. Examples of the metal include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium.

R ⁹ is a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.

s is an integer of 1 to 5, and t is 0 <t? 1. Therefore, the sulfonic acid group (Q) may contain a partially or fully substituted group in the aromatic ring.

The content of the alkali (earth) metal salt of the organic sulfonic acid (C) is preferably from 0.01 to 0.15 parts by mass, more preferably from 0.02 to 0.13 parts by mass, more preferably from 0.02 to 0.13 parts by mass, Is 0.03 to 0.12 parts by mass. If it is 0.01 parts by mass or more and 0.15 parts by mass or less, the flame retardancy can be sufficiently improved.

The polycarbonate resin composition of the present invention contains substantially none of the organic halogen-based flame retardant and the organic phosphoric acid ester-based flame retardant. Therefore, there is no fear of generation of noxious gas, contamination of the molding machine, soot of the resin, and deterioration of heat resistance.

[Method of preparing polycarbonate resin composition]

The polycarbonate resin composition of the present invention can be produced by mixing the component (A) [(A-1) and (A-2)] described above, the component (B) It can be prepared by blending optional components in a predetermined ratio and kneading.

The mixing and kneading at this time is preliminarily mixed with a conventionally used apparatus such as a ribbon blender or a drum tumbler, and the mixture is kneaded by a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, As shown in FIG.

The heating temperature at the time of kneading is appropriately selected in the range of usually 240 to 300 占 폚.

The components other than the polycarbonate resin may be added in advance as a master batch by melt-kneading with a polycarbonate resin.

The polycarbonate resin composition of the present invention can be produced by various methods such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding and foam molding by using the above melt molding machine or by using the obtained pellets as raw materials. A molded body can be produced.

Particularly, the pellet-shaped molding material can be produced by the above-mentioned melt-kneading method, and then this pellet can be suitably used for the production of an injection molded product by injection molding or injection compression molding.

In addition, as the injection molding method, a gas injection molding method for lightening the appearance or preventing the appearance of the appearance can be adopted.

Since the molded article of the present invention produced in this way has excellent flame retardance, rigidity, impact resistance, conductivity, molded appearance, thermal conductivity, and does not cause contamination of semiconductors or the like due to dropping of carbon, And is suitably used for housings, parts, films, and automobile parts of electric / electronic devices such as information devices and home telephone devices.

Example

EXAMPLES Next, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited at all by these examples.

The characteristic values in the respective examples were obtained in accordance with the following manner.

<Viscosity-average molecular weight of PC-PDMS copolymer (A-1) and aromatic polycarbonate (A-2)>

The viscosity average molecular weight (Mv) of these is obtained by measuring the viscosity of a methylene chloride solution at 20 占 폚 by using a Uberothe type viscometer, and calculating the intrinsic viscosity [?] From the viscosity and calculating the viscosity as follows.

&Lt; Evaluation of performance of polycarbonate resin composition (hereinafter abbreviated as PC composition)

(Production method of test piece)

Each component was blended at the ratios shown in Tables 1 to 3 and fed to an extruder (model name: VS40, manufactured by Tanabe Plastic Machinery Co., Ltd.), melted and kneaded at 240 캜 and pelletized. In all Examples and Comparative Examples, 0.2 parts by mass of Irganox 1076 (manufactured by BASF Japan Ltd.) was added as an antioxidant. The obtained pellets were dried at 120 占 폚 for 12 hours and then injection molded by injection molding machine (manufactured by Toshiba Machine Co., Ltd., model: IS100N) at a cylinder temperature of 260 占 폚 and a mold temperature of 80 占 폚 to obtain test pieces. Using the obtained test pieces, the following measurements were carried out and the performance was evaluated.

(1) IZOD (Izod Impact Strength): 23 占 폚 (1/8 inch thickness) according to ASTM D256, unit: kJ / m2

(2) Flexural modulus: According to ASTM D-790 (Test conditions: 23 캜, 4 mm), unit: MPa

(3) Volume resistivity: According to JIS K 6911 (test plate: 80 × 80 × 3 mm), unit: Ω · cm

(4) Flammability According to UL94 combustion test (specimen thickness: 1.5 mm, 1.0 mm, or 3.0 mm)

(5) molding appearance; And evaluated according to the following criteria.

○: Good, ×: Poor appearance such as particles on the surface

&Lt; Thickness and size of graphene sheet &gt;

The thickness and size of the graphene sheet were measured by observation of the electron microscope.

Production Example 1 [Production of PC oligomer]

60 kg of bisphenol A was dissolved in 400 liters of a 5 mass% aqueous sodium hydroxide solution to prepare an aqueous solution of sodium hydroxide of bisphenol A.

Subsequently, an orifice plate was placed in a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m at a flow rate of 138 liters / hour and an aqueous solution of sodium hydroxide of bisphenol A kept at room temperature at a flow rate of 69 liters / Phosgene was blown into the flask at a flow rate of 10.7 kg / hour, and the flask was continuously reacted for 3 hours. The tubular reactor used herein was a double tube, and the outlet temperature of the reaction liquid was maintained at 25 ° C through cooling water in the jacket portion. The pH of the effluent was adjusted to 10 to 11.

The reaction solution thus obtained was allowed to stand still so that the water phase was separated and removed, and a methylene chloride phase (220 liters) was sampled to obtain a PC oligomer (concentration: 317 g / liter). The degree of polymerization of the PC oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 mol / l.

Production Example 2 [Production of reactive PDMS]

1,483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86 mass% sulfuric acid were mixed and stirred at room temperature for 17 hours. Thereafter, the oil phase was separated, and 25 g of sodium hydrogencarbonate was added and stirred for 1 hour. After filtration, the mixture was subjected to vacuum distillation at 150 DEG C and 3 torr (4 x 10 &lt; ² &gt; Pa) to remove low-boiling point water to obtain an oil.

To a mixture of 60 g of 2-allylphenol and 0.0014 g of platine chloride as platinum chloride-alcoholate complex, 294 g of the oil obtained above was added at a temperature of 90 占 폚. The mixture was stirred for 3 hours while maintaining the temperature at 90 to 115 ° C. The product was extracted with methylene chloride and washed three times with 80% by mass aqueous methanol to remove excess 2-allylphenol. The product was dried with anhydrous sodium sulfate and heated at 115 ° C in vacuo to distill off the solvent. The terminal phenol PDMS obtained had a repeating number of dimethylsilanoloxy units of 30 by NMR measurement.

Production Example 3 [Production of PC-PDMS copolymer]

182 g of the reactive PDMS obtained in Production Example 2 was dissolved in 2 liters of methylene chloride, and 10 liters of the PC oligomer obtained in Production Example 1 were mixed. Thereto, 26 g of sodium hydroxide was dissolved in 1 liter of water, 5.7 cm 3 of triethylamine was added, and the mixture was reacted at 500 rpm at room temperature for 1 hour with stirring.

After completion of the reaction, 600 g of bisphenol A dissolved in 5 liters of a 5.2% by mass aqueous sodium hydroxide solution, 8 liters of methylene chloride and 96 g of pt-butylphenol were added to the reaction system and stirred at 500 rpm for 2 hours at room temperature , &Lt; / RTI &gt;

After the reaction, 5 liters of methylene chloride was added, and further washed with 5 liters of water, alkaline washing with 5 liters of a 0.03 mol / liter aqueous sodium hydroxide solution, acid washing with 5 liters of 0.2 mol / liter hydrochloric acid, And then methylene chloride was finally removed to obtain a PC-PDMS copolymer on flakes. The obtained PC-PDMS copolymer was vacuum-dried at 120 DEG C for 24 hours. The viscosity average molecular weight was 17,000 and the PDMS content was 4.0% by mass.

In addition, PDMS content of the methyl group of the isopropyl of bisphenol A observed at 1.7 ppm in ¹ H-NMR peaks was determined based on the intensity ratio of the peak of methyl group of dimethylsiloxane observed in 0.2 ppm.

Examples 1 to 10 and Comparative Examples 1 to 13

Each of the test pieces in each example was produced in accordance with the above-described &quot; method for producing a test piece &quot;, and the performance thereof was evaluated by various tests. The results are shown in Tables 1 to 3.

[week]

(A) Component:

(A-1) PC-PDMS: PC-PDMS copolymer having a viscosity average molecular weight of 17,000 and a PDMS content of 4.0% by mass obtained in Preparation Example 3

(A-2) PC: "FN1900A" (manufactured by Idemitsu Kosan Co., Ltd.), viscosity average molecular weight 19,500

Component (B):

Graphene sheet 1: "graphene nanoplatelet xGnP" (manufactured by XG Sciences), thickness 6 to 8 nm, size (sheet size) 5 μm

Graphene sheet 2: "graphene nanoplatelet xGnP" (manufactured by XG Sciences), thickness 6 to 8 nm, size (sheet size) 15 μm

Graft sheet 3: "graphene nanoplatelet xGnP" (manufactured by XG Sciences), thickness 2 to 4 nm, size (sheet size) 2 μm

(C) Component:

PTFE: PTFE "CD076" (manufactured by Asahi Garasulfur Polymers Co., Ltd.)

Other ingredients:

Carbon nanotubes 1 Multi-wall diameter 50 to 100 nm, length 1 to 10 占 퐉, openings at both ends, Amorphous carbon content 15 mass% (manufactured by Sunnano Tek)

Carbon nanotubes 2: Multiwall diameter 10 to 30 nm, length 1 to 10 占 퐉, openings at both ends, Amorphous carbon content 15 mass% (manufactured by Sunnano Tek)

Graphite: &quot; PC99-300M &quot; (manufactured by Ito Graphite Industry Co., Ltd.), average particle diameter 56 탆, thickness 1.7 탆

As can be seen from Tables 1 to 3, the polycarbonate resin composition according to the present invention contains a graphene sheet in a specific proportion, thereby achieving high flame retardancy and reducing the decrease in impact strength , Rigidity, conductivity, and molded appearance. In particular, when the PC-PDMS copolymer is contained in a specific ratio, the impact strength and flame retardancy are excellent. Further, by containing PTFE, flame retardancy of a thinner film can be further improved. Further, by using a graphene sheet having a thickness of 5 to 10 nm and a size of 3 m or more, higher flame retardancy, rigidity and conductivity can be obtained.

On the other hand, in the carbon nanotubes used in the comparative examples, the rigidity and the flame retardancy are inferior to those of the graphene sheet, and the micro-order graphite not only significantly deteriorates the impact strength but also the flame retardancy.

Industrial availability

The polycarbonate resin composition of the present invention can provide a molded article excellent in flame retardancy, rigidity, impact resistance, conductivity, molded appearance, and further, thermal conductivity. The molded article is expected to expand the application fields of housings, parts, films, automobile parts, and the like of electrical and electronic devices such as office automation equipment, information equipment, and home telephone equipment.

Claims (8)

A polycarbonate resin (A) having a mass ratio of the polycarbonate-polyorganosiloxane copolymer (A-1) and the aromatic polycarbonate (A-2) other than (A- (B) having a thickness of 5 to 10 nm and a size of 3 占 퐉 or more in an amount of 30 to 0.5% by mass, based on the entirety of the polycarbonate resin composition. The method according to claim 1,
The main chain of the polycarbonate-polyorganosiloxane copolymer (A-1) contains a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and the structural unit represented by the general formula (II) And 2 to 40 mass% of a polyorganosiloxane block composed of a structural unit is contained in the polycarbonate resin composition.
[Chemical Formula 1]

Wherein R ¹ and R ² are each independently an alkyl or alkoxy group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, an alkylidene group having 5 to 15 carbon atoms A cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO-, R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom or 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, Y represents an aliphatic or aromatic organic residue, n is an average number of repeating units, And a and b represent an integer of 0 to 4, 3. The method of claim 2,
And Y is an allyl phenol or an organic residue from an organol. 3. The method of claim 2,
Wherein the structural unit represented by the general formula (I) is a structural unit derived from bisphenol A. 3. The method of claim 2,
Wherein R ³ and R ⁴ in the structural unit represented by the general formula (II) are all methyl groups. 3. The method according to claim 1 or 2,
The polycarbonate resin composition further comprises 0.01 to 1 part by mass of polytetrafluoroethylene (C) per 100 parts by mass of the total amount of the component (A) and the component (B). A molded article obtained by molding the polycarbonate resin composition according to claim 1 or 2. delete