CN103608404A - Polycarbonate resin composition and molded article using same - Google Patents

Polycarbonate resin composition and molded article using same Download PDF

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CN103608404A
CN103608404A CN201280029564.7A CN201280029564A CN103608404A CN 103608404 A CN103608404 A CN 103608404A CN 201280029564 A CN201280029564 A CN 201280029564A CN 103608404 A CN103608404 A CN 103608404A
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resin composition
polycarbonate
poly carbonate
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carbonate resin
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CN103608404B (en
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野寺明夫
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Idemitsu Kosan Co Ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • 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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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • 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
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Abstract

The present invention provides a polycarbonate resin composition and a molded article obtained by molding the resin composition, wherein the polycarbonate resin composition is characterized in that: the polycarbonate resin composition comprises 70-99.5 mass% of a polycarbonate resin and 30-0.5 mass% of graphene sheets (B), wherein the polycarbonate resin is composed of a polycarbonate-polyorganosiloxane copolymer (A-1) and an aromatic polycarbonate (A-2) other than the polycarbonate-polyorganosiloxane copolymer (A-1) in a mass ratio of 5: 95-100: 0. The present invention provides a polycarbonate resin composition capable of forming a molded article having excellent flame retardancy, rigidity, impact resistance, electrical conductivity, molded appearance, thermal conductivity, and the like, and a molded article having the above properties obtained by molding the resin composition.

Description

Poly carbonate resin composition and use its molding
Technical field
The present invention relates to poly carbonate resin composition and use its molding.More specifically, relate to the poly carbonate resin composition of molding of excellences such as can forming flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance and thermal conductivity and the molding with above-mentioned proterties that this resin combination is shaped and is formed.
Background technology
In recent years, along with the development that electronic engineering learns a skill, signal conditioning package and teleworking equipment are promptly universal.And universal along with electronics, the electromagnetic interference that the noise being produced impacts to peripheral equipment, is increased by the faults such as mishandle due to static by electronic unit, day by day forms significant problem.In order to address these problems, to require the material that electroconductibility, system are electrically excellent, and along with the thin-walled property of goods, require all the more further high rigidization and flame retardant resistance.
All the time, be widely used in the conductive polymer material that is combined with electroconductive stuffing etc. in the macromolecular material that electroconductibility is low.As electroconductive stuffing, conventionally use steel fiber, metal-powder, carbon black and carbon fiber etc., when using steel fiber and metal-powder as electroconductive stuffing, although there is excellent electroconductibility, give effect, there is solidity to corrosion variation, be difficult to obtain the shortcoming of physical strength.When using carbon black as electroconductive stuffing, use the conductive carbon blacks such as Ketjen black, VULCAN XC72 and acetylene black that can obtain high conductivity to add on a small quantity, but these materials are not good to the dispersiveness of resin.Because the dispersiveness of carbon black has influence on the electroconductibility of resin combination, so in order to obtain stable electroconductibility, need unique cooperation and hybrid technology.
In addition, when using carbon fiber as electroconductive stuffing, can utilize general reinforcement to obtain required intensity, Young's modulus with carbon fiber, but in order to give electroconductibility, need high filling, the intrinsic physical property of resin reduces.
Patent documentation 1 discloses at polycarbonate-poly organo alkyl copolymer (sometimes referred to as PC-PDMS.) the middle technology that coordinates carbon nanotube and electroconductibility and flame retardant resistance are improved; Patent documentation 2 discloses the technology that coordinates graphite and give thermal conductivity in polycarbonate; Patent documentation 3 discloses the technology that coordinates functional graphene in resin.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-221508 communique
Patent documentation 2: TOHKEMY 2011-16937 communique
Patent documentation 3: Japanese Unexamined Patent Application Publication 2010-506013 communique
Summary of the invention
The problem that invention will solve
But, in the technology of recording at patent documentation 1, cannot give fully desired rigidity, but also cannot tackle the fire-retardant requirement of further thin-walled, may not necessarily make us being fully satisfied with.
In addition, although patent documentation 2 is to coordinate graphite and the technology of giving thermal conductivity in polycarbonate, if also do not use fire retardant, cannot show flame retardant resistance, and not about the record of electroconductibility, rigidity.The record of the Graphene of patent documentation 2 unmatchful nanometer grade thickness, being dispersed in the manufacture of using common forcing machine of the Graphene of nanometer grade thickness is difficult to carry out, and also do not reach and shows fully the excellent properties that Graphene has.And then, although patent documentation 3 is the technology that coordinate functional graphene, in polycarbonate material, there is no the record of the Graphene of relevant flame retardant resistance, electroconductibility the best.
The present invention completes in these cases, and its object is to provide the poly carbonate resin composition of the molding that can form the excellences such as flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance and thermal conductivity and the molding with above-mentioned proterties that this resin combination is shaped and is formed.
For solving the means of problem
The inventor furthers investigate repeatedly in order to reach above-mentioned purpose, the resin combination that found that the graphene film that contains specified amount with respect to polycarbonate-based resin can be applicable to this object, described polycarbonate-based resin contains polycarbonate-organosiloxane copolymer and aromatic copolycarbonate in addition thereof with specified proportion, and described polycarbonate-organosiloxane copolymer contains the organopolysiloxane block that comprises specific structure unit with regulation ratio.The present invention completes based on above-mentioned opinion.
That is, the invention provides following (1)～(8).
(1) a kind of poly carbonate resin composition, it is characterized in that, the polycarbonate-based resin (A) that comprises 70～99.5 quality % and the graphene film (B) of 30～0.5 quality %, described polycarbonate-based resin (A) consists of with mass ratio 5:95～100:0 polycarbonate-poly organo alkyl copolymer (A-1) and (A-1) aromatic copolycarbonate (A-2) in addition.
(2), according to the poly carbonate resin composition above-mentioned (1) Suo Shu, wherein, the thickness of graphene film (B) is that 5～10nm and size are more than 3 μ m.
(3) according to the poly carbonate resin composition above-mentioned (1) or (2) Suo Shu, wherein, the main chain of polycarbonate-poly organo alkyl copolymer (A-1) comprises the structural unit shown in the structural unit shown in general formula (I) and general formula (II), and polycarbonate-poly organo alkyl copolymer (A-1) organopolysiloxane block consisting of structural unit shown in this general formula (II) of containing 2～40 quality %.
[changing 1]
Figure BDA0000438736310000031
In formula, R 1and R 2the alkyl or the alkoxyl group that represent independently respectively carbon number 1～6, X represent the alkylidene group of singly-bound, carbon number 1～8, the cycloalkylidene of the alkylidene of carbon number 2～8, carbon number 5～15, the ring alkylidene of carbon number 5～15 ,-S-,-SO-,-SO 2-,-O-or-CO-, R 3～R 6the aryl that represents independently respectively the alkyl of hydrogen atom, halogen atom or carbon number 1～6, the alkoxyl group of carbon number 1～6 or carbon number 6～12, Y represents to comprise aliphatics or aromatic organic residue, n is average repeat number and represents 1～600 integer, and a and b represent 0～4 integer.］
(4), according to the poly carbonate resin composition above-mentioned (3) Suo Shu, wherein, Y is the organic residue that is derived from chavicol or oxymethoxyallylbenzene.
(5) according to the poly carbonate resin composition above-mentioned (3) or (4) Suo Shu, wherein, the structural unit of the structural unit shown in general formula (I) for being derived by dihydroxyphenyl propane.
(6) according to the poly carbonate resin composition described in any one in above-mentioned (3)～(5), wherein, the R in the structural unit shown in general formula (II) 3and R 4be methyl.
(7) according to the poly carbonate resin composition described in any one in above-mentioned (1)～(6), its also comprise with respect to (A) composition and (B) total amount 100 mass parts of composition be the tetrafluoroethylene (C) of 0.01～1 mass parts.
(8) molding, it forms the shaping of the poly carbonate resin composition described in any one in above-mentioned (1)～(7).
Invention effect
According to the present invention, can provide the poly carbonate resin composition of molding of excellences such as can forming flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance and thermal conductivity and the molding with above-mentioned proterties that this resin combination is shaped and is formed.
In addition, molding of the present invention has above-mentioned proterties, and can not cause the pollution of semi-conductor due to being come off by carbon etc., therefore expect that its Application Areas is extended to housing, parts, film and the trolley part etc. of the electric/electronic devices such as OA equipment, information equipment, electrification of domestic equipment.
Embodiment
First, poly carbonate resin composition of the present invention is described.
［ poly carbonate resin composition ］
Poly carbonate resin composition of the present invention is characterised in that, the polycarbonate-based resin (A) that comprises 70～99.5 quality % and the graphene film (B) of 30～0.5 quality %, described polycarbonate-based resin (A) consists of with mass ratio 5:95～100:0 polycarbonate-poly organo alkyl copolymer (A-1) and (A-1) aromatic copolycarbonate (A-2) in addition.
Below, each composition in poly carbonate resin composition of the present invention is described.
(polycarbonate-poly organo alkyl copolymer (A-1))
Polycarbonate-poly organo the alkyl copolymer (A-1) using in the present invention organopolysiloxane block being formed by the structural unit shown in this general formula (II) that preferably main chain comprises the structural unit shown in the structural unit shown in following general formula (I) and following general formula (II) and contains 2～40 quality %.It should be noted that, in this specification sheets, sometimes polycarbonate-poly organo alkyl copolymer is called to " PC-PDMS multipolymer ".
[changing 2]
Figure BDA0000438736310000051
Here, R 1and R 2the alkyl or the alkoxyl group that represent independently respectively carbon number 1～6, X represent the alkylidene group of singly-bound, carbon number 1～8, the cycloalkylidene of the alkylidene of carbon number 2～8, carbon number 5～15, the ring alkylidene of carbon number 5～15 ,-S-,-SO-,-SO 2-,-O-or-CO-, R 3～R 6the aryl that represents independently respectively the alkyl of hydrogen atom, halogen atom or carbon number 1～6, the alkoxyl group of carbon number 1～6 or carbon number 6～12, Y represents to comprise aliphatics or aromatic organic residue, n is average repeat number and represents 1～600 integer, and a and b represent 0～4 integer.As above-mentioned Y, preferred source is from organic residue of chavicol or oxymethoxyallylbenzene.In addition, as said n, the viewpoint from the performance of the poly carbonate resin composition of gained, is preferably 1～500 integer, and more preferably 5～200.
In this PC-PDMS multipolymer (A-1), from the viewpoint of flame retardant resistance and shock-resistance etc., the content of above-mentioned organopolysiloxane block is preferably 2～40 quality %, more preferably 3～25 quality %.
In addition,, from the viewpoint of the performance of the poly carbonate resin composition of gained, the structural unit shown in above-mentioned general formula (I) is preferably the structural unit being derived by dihydroxyphenyl propane, preferably makes the R in the structural unit shown in above-mentioned general formula (II) 3and R 4be methyl.
In addition, typically, in order to show shock-resistance, the large words of viscosity-average molecular weight of PC-PDMS multipolymer (A-1) are effectively, but when viscosity-average molecular weight becomes large, are difficult to the thin-wall member that is shaped.
By improving forming temperature, also can reduce the viscosity of resin combination, but now, the circulation that is shaped is elongated, less economical, in addition, when excessive temperature improves, can because of the thermal degradation when of resin combination, causes production stability to reduce.
Therefore, the viscosity-average molecular weight of PC-PDMS multipolymer (A-1) is preferably 15000～24000, more preferably 16000～22500, more preferably 17000～21000.
In viscosity-average molecular weight, be 15000 when above, the intensity of molding is abundant, in viscosity-average molecular weight, is 24000 when following, and the viscosity of multipolymer diminishes, and therefore, productivity during manufacture is good, and in addition, it is good that the shaping of thin-walled also becomes.
PC-PDMS multipolymer (A-1) is used the molecular weight regulator of the dihydric phenol shown in following general formula (1), organopolysiloxane, carbonyl chloride, carbonic ether or the chloro-formic ester shown in following general formula (2) and use as required to obtain.
[changing 3]
Figure BDA0000438736310000061
Here, in general formula (1), R 1and R 2, X, a and b and above-mentioned general formula (I) synonym, in general formula (2), R 3～R 6, Y, n and above-mentioned general formula (II) synonym, m represent 0 or 1, Z represent halogen ,-R 7oH ,-R 7cOOH ,-R 7nH 2,-COOH or-SH, R 7aryl substituted alkylene, the arylidene can on the alkylidene group of expression straight chain, side chain or ring-type, aryl substituted alkylene, ring with alkoxyl group.
In poly carbonate resin composition of the present invention, the dihydric phenol as shown in the general formula using in the raw material at PC-PDMS multipolymer (A-1) (1), is not particularly limited, and preferably 2, two (4-hydroxy phenyl) propane of 2-(is commonly called as: dihydroxyphenyl propane).When using dihydroxyphenyl propane as dihydric phenol, the X that becomes general formula (I) is the PC-PDMS multipolymer of isopropylidene and a=b=0.
As the dihydric phenol beyond dihydroxyphenyl propane, for example can list: two (4-hydroxy phenyl) methane, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) octanes of 2-, two (4-hydroxy phenyl) phenylmethane, two (4-hydroxy phenyl) ditan, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, two (4-hydroxy phenyl) naphthyl methane, 1, two (the 4-hydroxyl tert-butyl-phenyl) propane of 1-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (4-hydroxyl-3 of 2-, 5-tetramethylphenyl) propane, 2, two (4-hydroxyl-3-chloro-phenyl-) propane of 2-, 2, two (4-hydroxyl-3 of 2-, 5-dichlorophenyl) propane, 2, two (4-hydroxyl-3 of 2-, 5-dibromo phenyl) two (hydroxyaryl) alkanes such as propane, 1, two (4-hydroxy phenyl) pentamethylene, 1 of 1-, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 5,5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) norbornanes, 1 of 2-, two (hydroxyaryl) cycloalkanes such as two (4-hydroxy phenyl) cyclododecanes of 1-, 4,4 '-dihydroxy phenyl ether, 4,4 '-dihydroxyl-3, the dihydroxyl aryl ethers such as 3 '-3,5-dimethylphenyl ether, 4,4 '-dihydroxyl diphenylsulfide, 4,4 '-dihydroxyl-3, the dihydroxyl diaryl sulfide classes such as 3 '-dimethyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxyl-3, the dihydroxyl diaryl sulphoxide classes such as 3 '-dimethyl diphenyl sulfoxide, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxyl-3, the dihydroxyl diaryl sulfone classes such as 3 '-dimethyl diphenyl sulfone, 4, the dihydroxyl hexichol base class such as 4 '-dihydroxyl phenylbenzene, two (4-hydroxy phenyl) fluorenes, 9 of 9,9-, the dihydroxyl Diarylfluorenes such as two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-, two (4-hydroxy phenyl) ditan, 1, two (4-hydroxy phenyl) diamantane, 2 of 3-, two (4-hydroxy phenyl) diamantane, 1 of 2-, two (the 4-hydroxy phenyls)-5 of 3-, the dihydroxyl diaryl adamantanes such as 7-dimethyladamantane, 4,4 '-［ 1,3-phenylene two (1-methyl ethidine) ］ bis-phenol, 10, two (4-the hydroxy phenyl)-9-anthrones, 1 of 10-, two (the 4-hydroxybenzene sulfenyls)-2 of 5-, 3-dioxa amylene etc.
It is two or more that these dihydric phenols can be used separately or mix use.
Organopolysiloxane shown in general formula (2) can be by making to have the unsaturated C-C of olefinic phenol, preferred vinyl phenol, chavicol, oxymethoxyallylbenzene, isopropenyl phenol etc. carry out hydrosilylation reactions and easily manufacture with the end of organopolysiloxane chain with the polymerization degree n of regulation.Above-mentioned phenol is chavicol or oxymethoxyallylbenzene more preferably.Now, (A-1) Y in the general formula of composition (II) becomes the organic residue from chavicol or oxymethoxyallylbenzene.
As the organopolysiloxane shown in general formula (2), preferred R 3and R 4be the organopolysiloxane of methyl, for example, can list the compound of following general formula (3)～(11).
[changing 4]
In above-mentioned general formula (3)～(11), R 3～R 6same with general formula (II), represent independently respectively the aryl of the alkyl of hydrogen atom, halogen atom or carbon number 1～6, the alkoxyl group of carbon number 1～6 or carbon number 6～12, n is the average repeat number of organo-siloxane Component units and represents 1～600 integer.In addition R, 8represent alkyl, thiazolinyl, aryl or aralkyl, c represents positive integer, is generally 1～6 integer.
Wherein, from the viewpoint of the easy degree of polymerization, consider the phenol-modified organopolysiloxane shown in preferred formula (3).In addition, from the viewpoint of the easy degree of starting with, consider, preferably as a kind of α in the compound shown in general formula (4), ω-bis-[3-(o-hydroxy-phenyl) propyl group] polydimethylsiloxane, as a kind of α in the compound shown in general formula (5), ω-bis-[3-(4-hydroxyl-2-p-methoxy-phenyl) propyl group] polydimethylsiloxane.
Above-mentioned phenol-modified organopolysiloxane can utilize known method to manufacture.As manufacture method, for example, can list method shown below.
First, make the reaction under an acidic catalyst exists of cyclotrisiloxane and sily oxide, synthetic α, ω-dihydro organopolysiloxane.Now, by changing the charge ratio of cyclotrisiloxane and sily oxide, can synthesize the α with desirable average repeating unit, ω-dihydro organopolysiloxane.Then, at hydrosilylation reactions, use under the existence of catalyzer, make this α, the oxybenzene compound that ω-dihydro organopolysiloxane and chavicol, oxymethoxyallylbenzene etc. have unsaturated fatty hydrocarbons base carries out addition reaction, thereby can manufacture the phenol-modified organopolysiloxane with desirable average repeating unit.
In addition, in this stage, because low-molecular-weight cyclic polyorganosiloxane, excessive above-mentioned oxybenzene compound left behind as impurity, therefore, preferably under reduced pressure heat and the distillation of these low molecular compounds is removed.
((A-1) aromatic copolycarbonate (A-2)) in addition
In poly carbonate resin composition of the present invention, (A-2) composition as above-mentioned (A-1) aromatic copolycarbonate in addition can be used by the material that the manufacture method of known aromatic copolycarbonate obtains in the past,, reaction is being to the organic solvent of inertia, under the existence of alkali aqueous solution, dihydric phenol based compound and carbonyl chloride are reacted, then add the polymerizing catalysts such as tertiary amine or quaternary ammonium salt and make the interfacial polymerization of its polymerization; Dihydric phenol based compound is dissolved in the mixing solutions of pyridine or pyridine and inert solvent, imports carbonyl chloride and the pyridine method directly manufactured etc.
The dihydric phenol based compound using in manufacture as the aromatic copolycarbonate at (A-2) composition, can list: 2, two (4-hydroxy phenyl) propane of 2-(is commonly called as: dihydroxyphenyl propane), two (4-hydroxy phenyl) methane, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) octanes of 2-, two (4-hydroxy phenyl) phenylmethane, two (4-hydroxy phenyl) ditan, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, two (4-hydroxy phenyl) naphthyl methane, 1, two (4-hydroxyl-3-tert-butyl-phenyl) propane of 1-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (4-hydroxyl-3 of 2-, 5-3,5-dimethylphenyl) propane, 2, two (4-hydroxyl-3-chloro-phenyl-) propane of 2-, 2, two (4-hydroxyl-3 of 2-, 5-dichlorophenyl) propane, 2, two (4-hydroxyl-3 of 2-, 5-dibromo phenyl) two (hydroxyaryl) alkanes such as propane, 1, two (4-hydroxy phenyl) pentamethylene, 1 of 1-, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 5,5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) norbornanes, 1 of 2-, two (hydroxyaryl) cycloalkanes such as two (4-hydroxy phenyl) cyclododecanes of 1-, 4,4 '-dihydroxy phenyl ether, 4,4 '-dihydroxyl-3, the dihydroxyl aryl ethers such as 3 '-3,5-dimethylphenyl ether, 4,4 '-dihydroxyl diphenylsulfide, 4,4 '-dihydroxyl-3, the dihydroxyl diaryl sulfide classes such as 3 '-dimethyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxyl-3, the dihydroxyl diaryl sulphoxide classes such as 3 '-dimethyl diphenyl sulfoxide, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxyl-3, the dihydroxyl diaryl sulfone classes such as 3 '-dimethyl diphenyl sulfone, 4, the dihydroxybiphenyl classes such as 4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) fluorenes, 9 of 9,9-, the dihydroxyl Diarylfluorenes such as two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-, two (4-hydroxy phenyl) ditan, 1, two (4-hydroxy phenyl) diamantane, 2 of 3-, two (4-hydroxy phenyl) diamantane, 1 of 2-, two (the 4-hydroxy phenyls)-5 of 3-, the dihydroxyl diaryl adamantanes such as 7-dimethyladamantane, 4,4 '-［ 1,3-phenylene two (1-methyl ethidine) ］ bis-phenol, 10, two (4-the hydroxy phenyl)-9-anthrones, 1 of 10-, two (the 4-hydroxybenzene sulfenyls)-2 of 5-, 3-dioxa amylene etc.It is two or more that these dihydric phenols can be used separately or mix use.
When manufacturing the aromatic copolycarbonate of (A-2) composition, also can use as required molecular weight regulator, end terminator etc.They are so long as normally used material in the polymerization of polycarbonate resin just can be used various materials.
With regard to concrete molecular weight regulator, as monobasic phenol, for example, can list: phenol, adjacent normal-butyl phenol, between normal-butyl phenol, align butylphenol, adjacent isobutyl-phenol, between isobutyl-phenol, to isobutyl-phenol, o-tert-butylphenol, between tert.-butyl phenol, p-tert-butylphenol, adjacent n-pentyl phenol, between n-pentyl phenol, align amyl phenol, adjacent n-hexyl phenol, between n-hexyl phenol, align hexylphenol, to tert-octyl phenol, o cyclohexyl phenol, between cyclohexylphenol, p-cyclohexylphenol, orthoxenol, between phenylphenol, p-phenyl phenol, adjacent n-nonyl phenol, between nonylphenol, align nonylphenol, adjacent cumyl phenol, between cumyl phenol, to cumyl phenol, adjacent naphthyl phenol, between naphthyl phenol, to naphthyl phenol, 2,5-DI-tert-butylphenol compounds, 2,4-DTBP, 3,5-DI-tert-butylphenol compounds, 2,5-dicumyl phenol, 3,5-dicumyl phenol, p-cresol, bromophenol, tribromophenol, at ortho position, between position or contraposition there is the monoalkyl phenol of the straight chain shape of average carbon number 12～35 or the alkyl of chain, 9-(4-hydroxy phenyl)-9-(4-p-methoxy-phenyl) fluorenes, 9-(4-hydroxy-3-methyl phenyl)-9-(4-methoxyl group-3-aminomethyl phenyl) fluorenes, 4-(1-adamantyl) phenol etc.
In these monobasic phenol, preferably p-tert-butylphenol, to cumyl phenol, p-phenyl phenol etc.In addition, these compounds can be used singly or in combination two or more compounds.
As end terminator, can use monocarboxylic acid and its derivative, monobasic phenol.For example can list: p-tert-butylphenol, p-phenyl phenol, to cumyl phenol, to perfluor nonylphenol, to (perfluor nonyl phenyl) phenol, to (perfluoro hexyl phenyl) phenol, to perfluor tert.-butyl phenol, 1-(is to hydroxybenzyl) perfluoro decane, to (2-(1H, 1H-perfluor three (dodecyloxy))-1, 1, 1, 3, 3, 3-hexafluoro propyl group) phenol, 3, two (perfluor hexyloxy carbonyl) phenol of 5-, P-hydroxybenzoic acid perfluor dodecyl ester, p-(1H, 1H-perfluor octyloxy) phenol, 2H, 2H, 9H-perfluoro-pelargonic acid, 1, 1, 1, 3, 3, 3-hexafluoro-2-propyl alcohol etc.
And then, for above-mentioned dihydric phenol based compound, also can use branching agent and form branching polycarbonate.The addition of this branching agent is preferably 0.01～3 % by mole, more preferably 0.1～1.0 % by mole with respect to above-mentioned dihydric phenol based compound.
As branching agent, for example can list: 1,1,1-tri-(4-hydroxy phenyl) ethane, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-methylethyl] phenyl] ethidine] bis-phenol, α, α ', α "-tri-(4-hydroxy phenyls)-1; 3; 5-triisopropylbenzene, 1-[Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl]-4-[α ', α '-bis-(4 "-hydroxy phenyl) ethyl] benzene, chloro glycine, trimellitic acid, isatin two (ortho-cresol) etc. has the compounds of 3 above functional groups.
Comprising (A-1) composition and (A-2) in (A) polycarbonate-based resin of composition, content (A-1) is 5～100 quality %, be preferably 70～100 quality %, 50～100 quality % more preferably; (A-2) content is 95～0 quality %, be preferably 30～0 quality %, 50～0 quality % more preferably.
Content at (A-1) is more than 5 quality %, or content (A-2) is that 95 quality % are when following, due to the quantitative change low temperature impact strengths that make that contain of the organopolysiloxane block part in (A) polycarbonate-based resin are improved more, therefore without the content that increases the organopolysiloxane block part that contains the structural unit shown in general formula (II) when manufacturing (A-1) composition, thereby when manufacturing (A-1) composition, the homogeneity of the reaction in polymerization process can not reduce, and in the matting of polymkeric substance, the separation property of polymkeric substance and rinse water can variation, therefore the productivity of (A-1) composition becomes good.
Comprising (A-1) composition and (A-2) in the polycarbonate-based resin (A) of composition, the content of organopolysiloxane block part with the structural unit of general formula (II) be preferably 0.1～40 quality %, more preferably 0.5～25 quality %, more preferably 0.5～15 quality %, be further preferably 0.5～10 quality %.At its content, be 0.1 quality % when above, the effect that improves impact strength is abundant, on the other hand, at its content, is 40 quality % when following, has sufficient flame retardant resistance, thermotolerance.
(graphene film (B))
In poly carbonate resin composition of the present invention, for molding being given to the proterties such as flame retardant resistance, electroconductibility, rigidity, shaping outward appearance and thermal conductivity, and need to contain graphene film as (B) composition.
Graphene film refers to the Graphene plate with one or more layers Graphene face, conventionally uses ultrasonic energy and becomes laminarly, and the level of sheet can be controlled by adjusting ultrasonic (sonification) time.
The thickness of the graphene film using in the present invention is preferably 5～10nm, more than its size is preferably 3 μ m.The thickness of the graphene film using is in the present invention that 5～10nm and size are 3 μ m when above, and the dispersiveness of graphene film improves, and easy and resin compounded obtains the molding of flame retardant resistance, electroconductibility, rigidity, shaping outward appearance and excellent thermal conductivity.From above-mentioned viewpoint, the thickness of graphene film is preferably 6～8nm, and the size of graphene film is preferably 3～30 μ m, more preferably 5～25 μ m, 5～20 μ m more preferably.In proterties as above, from giving the viewpoint of higher electroconductibility, the size of graphene film is preferably 5～30 μ m, 5～20 μ m more preferably.
In the present invention, graphene film is tabular shape, and its thickness refers to the size of the overlapping thickness direction forming of graphene film, and its size refers to the size of graphene-structured itself, and the method that can utilize embodiment to record is measured.
As goods, " xGnP " (GRAPHENE NANOPLATELETS) that YouXG Sciences company manufactures etc.Owing to being open wide and smooth shape contrary with carbon nanotube, therefore can also introduce functional group or apply interface treating agent on surface by edge part around.
In poly carbonate resin composition of the present invention, in order to give the proterties such as electroconductibility, rigidity, flame retardant resistance, thermal conductivity, need to contain with the ratio of 70～99.5 quality % above-mentioned polycarbonate-based resin (A) and contain this graphene film (B) with the ratio of 30～0.5 quality %.At the content of graphene film (B), during lower than 0.5 quality %, be difficult to bring into play the effect of giving of above-mentioned proterties, on the other hand, when the content of graphene film (B) surpasses 30 quality %, shock strength significantly reduces, and shaping outward appearance also reduces.From above viewpoint, the preferred content of this graphene film (B) is 1～30 quality %, 1～20 quality % more preferably with respect to the total amount of itself and polycarbonate-based resin (A).
(tetrafluoroethylene (C))
In order to there is anti-molten drop (anti-dripping) effect, to give high flame retardant, in poly carbonate resin composition of the present invention, preferably contain tetrafluoroethylene as (C) composition.
This tetrafluoroethylene (C) for more than 500000 tetrafluoroethylene of the molecular-weight average that there is protofibril (fibril) and form ability (following, referred to as PTFE.), it has anti-molten drop effect, and can give high flame retardant.Its molecular-weight average need to be preferably 500000～10000000 for more than 500000, and more preferably 1000000～10000000.
PTFE as having protofibril formation ability, is not particularly limited, and particularly, can list: " Teflon(registered trademark) " manufacture of fluorine chemistry company of 6-J(Mitsui Du Pont); Tetrafluoroethylene (Polyflon) D-1, tetrafluoroethylene F-103, tetrafluoroethylene F201, tetrafluoroethylene MPA FA-100(Daikin Industries company manufacture); CD076(Asahi Glass Fluoropolymers company manufactures) and the manufacture of Algoflon F5(Montefluos company) etc.
As above there is the PTFE that protofibril forms ability can be by for example making under the pressure of tetrafluoroethylene at 7～700kPa under the existence of sodium, potassium or ammonium peroxo disulfate compound in aqueous solvent, 0～200 ℃ of temperature, preferably polymerization obtains at 20～100 ℃.
The content of this PTFE is generally 0.01～1 mass parts with respect to total amount 100 mass parts of above-mentioned polycarbonate-based resin (A) and graphene film (B), is preferably 0.05～0.9 mass parts, more preferably 0.1～0.8 mass parts.When the content of this PTFE is above-mentioned scope, the anti-molten drop in target flame retardant resistance becomes abundant.
In poly carbonate resin composition of the present invention, can replace above-mentioned PTFE and contain the mixed powder that comprises polytetrafluoroethylparticle particle and organic system polymer particle.
The particle diameter of the polytetrafluoroethylparticle particle in this mixed powder be generally 10 μ m following, be preferably 0.05～1.0 μ m.
Polytetrafluoroethylparticle particle is made into the aqueous liquid dispersion forming in the water that contains emulsifying agent etc. such as being dispersed in.The aqueous liquid dispersion of this polytetrafluoroethylparticle particle obtains by using fluorochemical surfactant and making tetrafluoroethylene monomer carry out letex polymerization.
When the letex polymerization of polytetrafluoroethylparticle particle, can in the scope of characteristic that does not diminish tetrafluoroethylene, use the fluorine-containing alkyl esters of (methyl) vinylformic acid such as the Fluorine containing olefines such as R 1216, chlorotrifluoroethylene, fluoroalkyl ethene and perfluoroalkyl vinyl ether, (methyl) perfluoroalkyl acrylate as copolymer composition.
The content of copolymer composition is preferably below 10 quality % with respect to the tetrafluoroethylene in polytetrafluoroethylparticle particle.
As the organic system polymer particle in this mixed powder, be not particularly limited, the dispersed viewpoint of the polytetrafluoroethylparticle particle when being matched with polycarbonate-based resin (A) considers preferably polycarbonate resin is had the organic system polymer particle of affinity.
The content of the mixed powder that comprises polytetrafluoroethylparticle particle and organic system polymer particle with respect to total amount 100 mass parts of polycarbonate-based resin (A) and graphene film (B) be generally 0.1～1 mass parts, be preferably 0.1～0.9 mass parts, 0.2～0.8 mass parts more preferably.
At the content of above-mentioned mixed powder, be 0.1 mass parts when above, melt-dropping property is good, can realize flame retardant resistance.On the other hand, at the content of above-mentioned mixed powder, be 1 mass parts when following, the ratio of the organic system polymkeric substance in composition can excessively not increase, and can realize flame retardant resistance.
(added ingredients arbitrarily)
In poly carbonate resin composition of the present invention, except above-mentioned (A) composition, (B) composition and (C) composition or mixed powder, can also in the scope of not damaging effect of the present invention, contain the known various added ingredientss that in the past added in poly carbonate resin composition as required.As such added ingredients, such as listing: phosphorous antioxidant, be antioxidant beyond photostabilizer, phosphorus system, UV light absorber, static inhibitor, lubricant, releasing agent, dyestuff, pigment, shock-resistance improvement with elastomerics as alkali (soil) metal-salt, supporting material, weighting agent, the hindered amine of the organic sulfonic acid of fire-retardant rising agent etc.
(phosphorous antioxidant)
As phosphorous antioxidant used in the present invention, be not particularly limited.As typical example, except tricresyl phosphite (nonyl phenyl) ester, phosphorous acid 2-ethylhexyl diphenyl ester, can also list: the trialkyl phosphites such as trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite monooctyl ester, tris(nonyl phenyl) phosphate, tridecyl phosphite, tricresyl phosphite (octadecyl) ester, distearyl pentaerythrityl diphosphite, tricresyl phosphite (2-chloroethyl) ester, tricresyl phosphite (2,3-, bis-chloropropyls) ester; The tricresyl phosphite cycloalkyl esters such as tricresyl phosphite cyclohexyl ester; The triaryl phosphites such as triphenyl phosphite, tricresyl phosphite, tricresyl phosphite (ethylphenyl) ester, tricresyl phosphite (butyl phenyl) ester, tricresyl phosphite (hydroxy phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; The trialkylphosphates such as trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tricresyl phosphate (octadecyl) ester, distearyl pentaerythritol diphosphate, tricresyl phosphate (2-chloroethyl) ester, tricresyl phosphate (2,3-, bis-chloropropyls) ester; The tricresyl phosphate cycloalkyl esters such as thricyclohexyl-1-phosphoric acid ester; The triaryl phosphates such as triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (nonyl phenyl) ester, phosphoric acid 2-ethylphenyl diphenyl ester etc.Wherein, preferably use triaryl phosphites and triaryl phosphate.
In the present invention, these phosphorous antioxidants can be used separately a kind of, also can be used in combination two or more.In addition, the content of this phosphorous antioxidant in poly carbonate resin composition is preferably 0.1～1 mass parts with respect to polycarbonate-based resin (A) 100 mass parts.By comprising this phosphorous antioxidant of above-mentioned scope, can access sufficient antioxidant effect.
(alkali of organic sulfonic acid (soil) metal-salt)
In poly carbonate resin composition of the present invention, in order to improve flame retardant resistance, can contain an alkali metal salt and/or the alkaline earth salt (below also referred to as organic sulfonic acid alkali (soil) metal-salt) of organic sulfonic acid.
As organic sulfonic acid, can list perfluoroalkane sulfonate, polystyrolsulfon acid etc.
As organic sulfonic acid alkali (soil) metal-salt, though can list various salt, for thering is organic sulfonic acid an alkali metal salt, the alkaline earth salt of at least one carbon atom.
As basic metal, can list sodium, potassium, lithium and caesium etc., as alkaline-earth metal, can list magnesium, calcium, strontium and barium etc.Wherein, the salt of preferred sodium, potassium and caesium.
As (C) composition, an alkali metal salt and/or the alkaline earth salt of preferred perfluoroalkane sulfonate or polystyrolsulfon acid.
Alkali (soil) metal-salt as perfluoroalkane sulfonate, can list the salt shown in following general formula (12).
（C dF 2d+1SO 3） eＭ…（12）
In formula (12), d represents 1～10 integer, and M represents the alkaline-earth metal such as the basic metal such as lithium, sodium, potassium and caesium or magnesium, calcium, strontium and barium, and e represents the valence of M.
As these metal-salts, the metal-salt of for example recording in Japanese Patent Publication 47-40445 communique is suitable.
In general formula (12), as perfluoroalkane sulfonate, such as listing: perfluoromethane sulfonic acid, R 116 sulfonic acid, perfluoropropane sulfonic acid, perfluorinated butane sulfonic acid, perfluoro-methyl butane sulfonic acid, perflexane sulfonic acid, PF 5070 sulfonic acid and Perfluorooctane sulfonates etc.Particularly preferably use the sylvite of these sulfonic acid.
In addition, can also list: alkylsulphonic acid, Phenylsulfonic acid, alkyl benzene sulphonate (ABS), phenylbenzene sulfonic acid, naphthene sulfonic acid, 2,5-dichloro benzosulfonic acid, 2,4,5-trichlorobenzene sulfonic acid, sulfobenzide-3-sulfonic acid, sulfobenzide-3, an alkali metal salt of the organic sulfonic acids such as the fluorine replacement body of 3 '-disulfonic acid, naphthalene trisulfonic acid and these sulfonic acid and polystyrolsulfon acid, alkaline earth salt etc.Wherein, as organic sulfonic acid, particularly preferably perfluoroalkane sulfonate and phenylbenzene sulfonic acid.
As alkali (soil) metal-salt of polystyrolsulfon acid, can list alkali (soil) metal-salt of the aromatic vinyl base system resin that contains sulphonate-base shown in following general formula (13).
[changing 5]
Figure BDA0000438736310000161
In formula (13), Q represents sulphonate-base, R 9the alkyl that represents hydrogen atom or carbon number 1～10.S represents 1～5 integer, and t represents molar fraction, 0 < t≤1.
Here, an alkali metal salt that the sulphonate-base of Q is sulfonic acid and/or alkaline earth salt, as metal, can list sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium etc.
In addition R, 9alkyl for hydrogen atom or carbon number 1～10, is preferably hydrogen atom or methyl.
S is 1～5 integer, and t is the relation of 0 < t≤1.Therefore, sulphonate-base (Q) can comprise aromatic nucleus is all replaced and the sulphonate-base that obtains, aromatic nucleus partly replaced and the sulphonate-base that obtains.
(C) content of the alkali of organic sulfonic acid (soil) metal-salt is preferably 0.01～0.15 mass parts, more preferably 0.02～0.13 mass parts, 0.03～0.12 mass parts more preferably with respect to polycarbonate-based resin (A) 100 mass parts.More than this content is 0.01 mass parts and when 0.15 mass parts is following, can fully improve flame retardant resistance.
Polycarbonate-based resin composition of the present invention does not contain in fact any in organic halogenated flame retardant and organophosphate flame retardant.Therefore, can there is not the generation of obnoxious flavour, the risk of the burning of the pollution of forming mill, resin, stable on heating reduction.
(preparation method of poly carbonate resin composition)
Poly carbonate resin composition of the present invention can be as the preparation of getting off: above-mentioned (A) composition ［ (A-1) and (A-2) ］, (B) composition and (C) composition using as required or mixed powder and various any composition are coordinated to scale, carry out mixing, thereby prepare this poly carbonate resin composition.
Cooperation now and mixing can be by utilizing normally used machine, such as ribbon mixer, rotary drum etc., carry out pre-mixing, and use the method for Henschel mixer, banbury mixers, single screw extrusion machine, twin screw extruder, multiple screw extruder, compound motion kneading machine (ko-kneader) etc. to carry out.
Heating temperature when mixing is suitably selected conventionally in the scope of 240～300 ℃.
It should be noted that, except polycarbonate-based resin contain composition also can be in advance mixing with polycarbonate-based resin melting, with the form of masterbatch (master batch), add.
Poly carbonate resin composition of the present invention can be used above-mentioned melting mixing forming mill to manufacture various molding; Or the particle obtaining of can take is raw material, utilize injection molding method, ejection compress moulding method, extrusion molding method, blow-moulding process, press forming method, vacuum forming method and foaming and molding method etc. to manufacture various molding.
Poly carbonate resin composition of the present invention can be particularly preferred for following situation,, by above-mentioned melting mixing method, manufactures granular shaping raw material that is, then uses this particle and utilizes injection forming, ejection compress moulding to manufacture injection-molded article.
It should be noted that, as ejection forming method, ヒ ケ) or adopt gas inject manufacturing process for lightweight also can be in order to prevent indenture (the Japanese original text: of outward appearance.
For the molding of the present invention according to producing with upper type, the excellences such as its flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance, thermal conductivity, and can not cause the pollution of semi-conductor due to being come off by carbon etc., therefore be suitable for housing, parts, film and the trolley part etc. of the electric/electronic devices such as OA equipment, information equipment, electrification of domestic equipment.
Embodiment
Below, the present invention will be described in more detail to utilize embodiment and comparative example, but the present invention is not subject to any restriction of these examples.
It should be noted that, the characteristic value in each example is obtained according to main points shown below.
The viscosity-average molecular weight > of < PC-PDMS multipolymer (A-1) and aromatic copolycarbonate (A-2)
About their viscosity-average molecular weight (Mv), use the viscosity of the dichloromethane solution at 20 ℃ of determination of ubbelohde viscometer, by this viscosity, obtain limiting viscosity [η], then utilize following formula to calculate this viscosity-average molecular weight.
［η］＝1.23×10 -5Ｍｖ 0.83
< poly carbonate resin composition is (below sometimes referred to as PC composition.) performance evaluation >
(making method of test film)
According to the ratio shown in table 1～table 3, coordinate each composition, be supplied to forcing machine (model: VS40, limit, field plastics machinery (strain) are manufactured), at 240 ℃, carry out melting mixing, carry out granulating.It should be noted that, in all embodiment and comparative example, coordinated the Irganox1076(BASF JAPAN(strain as antioxidant) manufacture) 0.2 mass parts.By the particle of gained, at 120 ℃ after dry 12 hours, at injection machine, (toshiba machine (strain) is manufactured, model: IS100N) under the condition of 260 ℃ of material cylinder temperature, 80 ℃ of die temperatures, carry out injection forming, thereby obtain test film.Use resulting test film, carry out following mensuration, performance is evaluated.
(1) IZOD(cantilever-type impact strength): according to ASTM D256, at 23 ℃ (1/8 inch of wall thickness), unit: kJ/m 2
(2) bending elastic modulus: according to ASTM D-790(test conditions etc.: 23 ℃, 4mm), unit: MPa
80 * 80 * 3mm), unit (3) volume intrinsic resistance value: according to JIS K6911(test panel:: Ω cm
(4) according to flame retardant resistance UL94 combustion test (test film thickness: 1.5mm, 1.0mm or 3.0mm)
(5) shaping outward appearance; According to following benchmark, evaluate.
Zero: good, *: the bad outward appearances such as pit on surface, there is.
The thickness of < graphene film and big or small >
The thickness of graphene film and size utilize the observation of electron microscope to measure.
Production Example 1 ［ manufacture of PC oligopolymer ］
Make the dihydroxyphenyl propane of 60kg be dissolved in the 5 quality % aqueous sodium hydroxide solutions of 400 liters, be prepared into the aqueous sodium hydroxide solution of dihydroxyphenyl propane.
Then, by be held in the aqueous sodium hydroxide solution of this dihydroxyphenyl propane of room temperature and methylene dichloride respectively with the flow of the flow of 138 ls/h and 69 ls/h from orifice plate by importing to the tube-type reactor of internal diameter 10mm, pipe range 10m, wherein and flow carbonyl chloride and be blown into the flow of 10.7kg/ hour, it is reacted 3 hours continuously.Tube-type reactor used herein is double wall tube, at sleeve portion, passes into water coolant, and the outflow temperature of reaction solution is remained on to 25 ℃.In addition, the pH value of liquid effluent is adjusted to 10～11.
By standing according to the reaction solution obtaining with upper type, separated and remove water thus, gather methylene dichloride phase (220 liters), obtain PC oligopolymer (concentration 317g/ liter).Here the polymerization degree of resulting PC oligopolymer is 2～4, and the concentration of chloroformic acid ester group is 0.7 mole/L.
Production Example 2 ［ manufacture of reactive PDMS ］
By 1,1,3 of the octamethylcyclotetrasiloxane of 1483g, 96g, the 86 quality % sulfuric acid of 3-tetramethyl disiloxane and 35g mix, and at room temperature stir 17 hours.Afterwards, separated oil phase, adds the sodium bicarbonate of 25g, stirs 1 hour.After filtration, 150 ℃, 3torr(4 * 10 2pa) under, carry out vacuum distilling, remove low boilers, obtain oil.
At the temperature of 90 ℃, in the mixture of the 2-chavicol of 60g and the platinum as platinum chloride-ol salt complex of 0.0014g, add oily 294g obtained above.Stir 3 hours on the temperature limit that this mixture limit is remained on to 90～115 ℃.With methylene dichloride, product is extracted, with the methanol aqueous solution of 80 quality %, wash 3 times, remove excessive 2-chavicol.By this product anhydrous sodium sulfate drying, be heated in a vacuum 115 ℃, distillation is except desolventizing.For resulting end phenol PDMS, according to the mensuration of NMR, the repeat number of dimethyl-silicon alcoxyl base unit is 30.
Production Example 3 ［ manufacture of PC-PDMS multipolymer ］
The reactive PDMS182g that makes to obtain in Production Example 2 is dissolved in 2 liters of methylene dichloride, 10 liters of the PC oligopolymer obtaining in remix Production Example 1.Add wherein sodium hydroxide 26g is dissolved in to 1 liter of solution forming of water and triethylamine 5.7cm 3, with 500rpm, at room temperature stir 1 hour, make its reaction.
After reaction finishes, to adding in above-mentioned reaction system, dihydroxyphenyl propane 600g is dissolved in to 8 liters of solution, methylene dichloride and the p-tert-butylphenol 96g after 5 liters of the aqueous sodium hydroxide solutions of 5.2 quality %, with 500rpm, at room temperature stirs 2 hours, make its reaction.
After reaction, add 5 liters of methylene dichloride, then use successively the washing of 5 premium on currency, neutralizing treatment with 5 liters of 0.03 mole/L aqueous sodium hydroxide solutions, with the washing of 5 liters of the acid elution of 5 liters of 0.2 mole/L hydrochloric acid and waters 2 times, finally remove methylene dichloride, obtain laminar PC-PDMS multipolymer.By the vacuum-drying 24 hours at 120 ℃ of the PC-PDMS multipolymer of gained.Viscosity-average molecular weight is that 17000, PDMS containing ratio is 4.0 quality %.
It should be noted that, PDMS containing ratio based on 1recently try to achieve with the intensity at the peak of the methyl of the dimethyl siloxane of observing at 0.2ppm at the peak of the methyl of the sec.-propyl of the dihydroxyphenyl propane of observing at 1.7ppm in H-NMR.
Embodiment 1～10 and comparative example 1～13
According to above-mentioned " making method of test film ", make respectively the test film in each example, use this test film performance of having utilized various test evaluations.Its result as shown in Table 1 to Table 3.
[table 1]
Table 1
[table 2]
Table 2
Figure BDA0000438736310000211
[table 3]
Table 3
Figure BDA0000438736310000212
［ notes ］
(A) composition:
(A-1) PC-PDMS: the viscosity-average molecular weight obtaining in Production Example 3 is 17000, PDMS containing ratio is the PC-PDMS multipolymer of 4.0 quality %
(A-2) PC: " FN1900A " (the emerging product of bright dipping (strain) manufacture), viscosity-average molecular weight 19500
(B) composition:
Graphene film 1: " GRAPHENE NANOPLATELETS xGnP " (manufacture of XG Sciences company), thickness 6～8nm, size (chip size) 5 μ m
Graphene film 2: " GRAPHENE NANOPLATELETS xGnP " (manufacture of XG Sciences company), thickness 6～8nm, size (chip size) 15 μ m
Graphene film 3: " GRAPHENE NANOPLATELETS xGnP " (manufacture of XG Sciences company), thickness 2～4nm, size (chip size) 2 μ m
(C) composition:
PTFE:PTFE " CD076 " (Asahi Glass Fluoropolymers(strain) manufactures)
Other compositions:
Carbon nanotube 1: many walls diameter 50～100nm, length 1～10 μ m, both ends open, decolorizing carbon amount 15 quality %(サ ンナ ノテック companies manufacture)
Carbon nanotube 2: many walls diameter 10～30nm, length 1～10 μ m, both ends open, decolorizing carbon amount 15 quality %(サ ンナ ノテック companies manufacture)
Graphite: " PC99-300M " (she manufactures in eastern blacklead industry (strain)), median size 56 μ m, thickness 1.7 μ m
From table 1～table 3, belong to poly carbonate resin composition of the present invention by containing graphene film with specified proportion, thereby can obtain high flame retardant and the reduction of shock strength is tailed off, rigidity, electroconductibility and shaping outward appearance are also excellent.Especially by containing PC-PDMS multipolymer with specific ratio, thereby make shock strength and excellent in flame retardance.By further containing PTFE, thereby can further realize the flame retardant resistance of thin-walled.In addition, by used thickness, be that 5～10nm and size are graphene films more than 3 μ m, thereby obtain higher flame retardant resistance, rigidity, electroconductibility.
On the other hand, in the carbon nanotube using at comparative example, compare with graphene film, rigidity and flame retardant resistance variation, and in micron-sized graphite, not only shock strength significantly reduces, and cause flame retardant resistance to reduce.
Utilizability in industry
Poly carbonate resin composition of the present invention can form the molding that flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance and thermal conductivity etc. are excellent.This molding is expected in housing, parts, film and trolley part etc. that its Application Areas is extended to the electric/electronic devices such as OA equipment, information equipment, electrification of domestic equipment.

Claims (8)

1. a poly carbonate resin composition, it is characterized in that, the graphene film B of the polycarbonate-based Resin A that comprises 70～99.5 quality % and 30～0.5 quality %, described polycarbonate-based Resin A consists of with the mass ratio of 5:95～100:0 with A-1 aromatic copolycarbonate A-2 in addition polycarbonate-organopolysiloxane copolymer A-1.
2. poly carbonate resin composition according to claim 1, wherein, the thickness of graphene film B is that 5～10nm and size are more than 3 μ m.
3. poly carbonate resin composition according to claim 1 and 2, wherein, the main chain of polycarbonate-organopolysiloxane copolymer A-1 comprises the structural unit shown in the structural unit shown in general formula (I) and general formula (II), and the organopolysiloxane block being formed by the structural unit shown in this general formula (II) that 2～40 quality % are contained in polycarbonate-organopolysiloxane copolymer A-1
Figure FDA0000438736300000011
In formula, R 1and R 2the alkyl or the alkoxyl group that represent independently respectively carbon number 1～6, X represent the alkylidene group of singly-bound, carbon number 1～8, the cycloalkylidene of the alkylidene of carbon number 2～8, carbon number 5～15, the ring alkylidene of carbon number 5～15 ,-S-,-SO-,-SO 2-,-O-or-CO-, R 3～R 6the aryl that represents independently respectively the alkyl of hydrogen atom, halogen atom or carbon number 1～6, the alkoxyl group of carbon number 1～6 or carbon number 6～12, Y represents to comprise aliphatics or aromatic organic residue, n is average repeat number and represents 1～600 integer, and a and b represent 0～4 integer.
4. poly carbonate resin composition according to claim 3, wherein, Y is the organic residue that is derived from chavicol or oxymethoxyallylbenzene.
5. according to the poly carbonate resin composition described in claim 3 or 4, wherein, the structural unit shown in general formula (I) is the structural unit being derived by dihydroxyphenyl propane.
6. according to the poly carbonate resin composition described in any one in claim 3～5, wherein, the R in the structural unit shown in general formula (II) 3and R 4be methyl.
7. according to the poly carbonate resin composition described in any one in claim 1～6, its total amount 100 mass parts that also comprise with respect to A composition and B composition are the tetrafluoroethylene C of 0.01～1 mass parts.
8. a molding, it makes in claim 1～7 poly carbonate resin composition described in any one be shaped to form.
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