CN103608404B - Polycarbonate resin composition and molded article using same - Google Patents

Polycarbonate resin composition and molded article using same Download PDF

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CN103608404B
CN103608404B CN201280029564.7A CN201280029564A CN103608404B CN 103608404 B CN103608404 B CN 103608404B CN 201280029564 A CN201280029564 A CN 201280029564A CN 103608404 B CN103608404 B CN 103608404B
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poly carbonate
carbonate resin
polycarbonate
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CN103608404A (en
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野寺明夫
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Idemitsu Kosan Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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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    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; 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
    • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • 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
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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 (A) and 30-0.5 mass% of graphene sheets (B), wherein the polycarbonate resin (A) 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, the poly carbonate resin composition relating to 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.
Background technology
In recent years, the development learned a skill along with electronic engineering, signal conditioning package and electronic office equipment are promptly popularized.And universal along with electronics, the faults such as the electromagnetic interference that the noise produced by electronic unit impacts to peripheral equipment, mishandle caused by electrostatic increase, and day by day form significant problem.In order to address these problems, require electroconductibility, the material that system is 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, the conductive polymer material being combined with electroconductive stuffing etc. in the low macromolecular material of electroconductibility is widely used in.As electroconductive stuffing, usual 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, being difficult to obtain the shortcoming of physical strength.When using carbon black as electroconductive stuffing, use to add on a small quantity the conductive carbon blacks such as Ketjen black, VULCANXC72 and the acetylene black that can obtain high conductivity, but these materials are not good to the dispersiveness of resin.Dispersiveness due to carbon black has influence on the electroconductibility of resin combination, therefore needs unique cooperation and hybrid technology to obtain stable electroconductibility.
In addition, when using carbon fiber as electroconductive stuffing, general reinforcement carbon fiber can be utilized to obtain required intensity, Young's modulus, but need high filling to give electroconductibility, the physical property reduction that resin is intrinsic.
Patent documentation 1 discloses at polycarbonate-poly organo alkyl copolymer (sometimes referred to as PC-PDMS.) in coordinate carbon nanotube and make the technology that electroconductibility and flame retardant resistance improve; Patent documentation 2 discloses and in polycarbonate, coordinates graphite and the technology of giving thermal conductivity; Patent documentation 3 discloses the technology coordinating functional graphene in resin.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-221508 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-16937 publication
Patent documentation 3: Japanese Unexamined Patent Application Publication 2010-506013 publication
Summary of the invention
The problem that invention will solve
But, in the technology that patent documentation 1 is recorded, required rigidity cannot be given fully, but also further thin-walled flame-retardancy requirements cannot be tackled, may not necessarily make us fully being satisfied with.
In addition, although patent documentation 2 is the technology coordinating graphite and give thermal conductivity in polycarbonate, if also do not use fire retardant, then flame retardant resistance cannot be shown, and not about the record of electroconductibility, rigidity.Patent documentation 2 there is no the record of the Graphene to nanometer grade thickness, and being dispersed in use in the manufacture of common forcing machine of the Graphene of nanometer grade thickness is difficult to carry out, and does not also reach the excellent properties showing Graphene fully and have.And then, although patent documentation 3 is the technology coordinating functional graphene, in polycarbonate material, there is no the record of the Graphene about flame retardant resistance, electroconductibility the best.
The present invention completes in these cases, its object is to provide the poly carbonate resin composition that can form the excellent molding such as flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance and thermal conductivity and the molding with above-mentioned proterties be shaped by this resin combination.
For solving the means of problem
The present inventor furthers investigate repeatedly in order to reach above-mentioned purpose, found that the resin combination containing the graphene film of specified amount relative 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 comprising 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, comprise the polycarbonate-based resin (A) of 70 ~ 99.5 quality % and the graphene film (B) of 30 ~ 0.5 quality %, described polycarbonate-based resin (A) is made up of with mass ratio 5:95 ~ 100:0 polycarbonate-poly organo alkyl copolymer (A-1) and the aromatic copolycarbonate (A-2) beyond (A-1).
(2) poly carbonate resin composition according to above-mentioned (1), wherein, the thickness of graphene film (B) is 5 ~ 10nm and size is more than 3 μm.
(3) poly carbonate resin composition according to above-mentioned (1) or (2), wherein, the main chain of polycarbonate-poly organo alkyl copolymer (A-1) comprises the structural unit shown in general formula (I) and the structural unit shown in general formula (II), and the organopolysiloxane block that structural unit this general formula (II) shown in be made up of of polycarbonate-poly organo alkyl copolymer (A-1) containing 2 ~ 40 quality %.
[changing 1]
In formula, R 1and R 2separately represent the alkyl of carbon number 1 ~ 6 or alkoxyl group, X represents the alkylidene group of singly-bound, carbon number 1 ~ 8, the alkylidene of carbon number 2 ~ 8, the cycloalkylidene of carbon number 5 ~ 15, the ring alkylidene of carbon number 5 ~ 15 ,-S-,-SO-,-SO 2-,-O-or-CO-, R 3~ R 6separately represent the alkoxyl group of the alkyl of hydrogen atom, halogen atom or carbon number 1 ~ 6, carbon number 1 ~ 6 or the aryl of carbon number 6 ~ 12, Y represents and comprises aliphatics or aromatic organic residue, n is averaged repeating numbers and represents the integer of 1 ~ 600, a and b represents the integer of 0 ~ 4.］
(4) poly carbonate resin composition according to above-mentioned (3), wherein, Y is the organic residue being derived from chavicol or oxymethoxyallylbenzene.
(5) poly carbonate resin composition according to above-mentioned (3) or (4), wherein, the structural unit shown in general formula (I) is the structural unit derived by dihydroxyphenyl propane.
(6) poly carbonate resin composition according to any one of above-mentioned (3) ~ (5), wherein, the R in the structural unit shown in general formula (II) 3and R 4be methyl.
(7) poly carbonate resin composition according to any one of above-mentioned (1) ~ (6), it also comprises relative to total amount 100 mass parts of (A) composition and (B) composition is the tetrafluoroethylene (C) of 0.01 ~ 1 mass parts.
(8) molding, it makes the shaping of the poly carbonate resin composition according to any one of above-mentioned (1) ~ (7) form.
Invention effect
According to the present invention, the poly carbonate resin composition that can form the excellent molding such as flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance and thermal conductivity and the molding with above-mentioned proterties be shaped by this resin combination can be provided.
In addition, molding of the present invention has above-mentioned proterties, and the pollution of the caused semi-conductor etc. that to be come off by carbon can not be caused, therefore expect that its Application Areas is extended to the housing of the electric/electronic devices such as OA equipment, information equipment, electrification of domestic equipment, parts, film and trolley part etc.
Embodiment
First, poly carbonate resin composition of the present invention is described.
［ poly carbonate resin composition ］
The feature of poly carbonate resin composition of the present invention is, comprise the polycarbonate-based resin (A) of 70 ~ 99.5 quality % and the graphene film (B) of 30 ~ 0.5 quality %, described polycarbonate-based resin (A) is made up of with mass ratio 5:95 ~ 100:0 polycarbonate-poly organo alkyl copolymer (A-1) and the aromatic copolycarbonate (A-2) beyond (A-1).
Below, each composition in poly carbonate resin composition of the present invention is described.
(polycarbonate-poly organo alkyl copolymer (A-1))
The polycarbonate used in the present invention-poly organo alkyl copolymer (A-1) preferably main chain comprises the structural unit shown in following general formula (I) and the structural unit shown in following general formula (II) and the organopolysiloxane block be made up of the structural unit shown in this general formula (II) containing 2 ~ 40 quality %.It should be noted that, sometimes polycarbonate-poly organo alkyl copolymer is called " PC-PDMS multipolymer " in this specification sheets.
[changing 2]
Here, R 1and R 2separately represent the alkyl of carbon number 1 ~ 6 or alkoxyl group, X represents the alkylidene group of singly-bound, carbon number 1 ~ 8, the alkylidene of carbon number 2 ~ 8, the cycloalkylidene of carbon number 5 ~ 15, the ring alkylidene of carbon number 5 ~ 15 ,-S-,-SO-,-SO 2-,-O-or-CO-, R 3~ R 6separately represent the alkoxyl group of the alkyl of hydrogen atom, halogen atom or carbon number 1 ~ 6, carbon number 1 ~ 6 or the aryl of carbon number 6 ~ 12, Y represents and comprises aliphatics or aromatic organic residue, n is averaged repeating numbers and represents the integer of 1 ~ 600, a and b represents the integer of 0 ~ 4.As above-mentioned Y, preferred source is from the organic residue of chavicol or oxymethoxyallylbenzene.In addition, as said n, from the view point of the performance of the poly carbonate resin composition of gained, the integer of 1 ~ 500 is preferably, more preferably 5 ~ 200.
In this PC-PDMS multipolymer (A-1), from the view point of flame retardant resistance and shock-resistance etc., the content of above-mentioned organopolysiloxane block is preferably 2 ~ 40 quality %, is more preferably 3 ~ 25 quality %.
In addition, from the view point of the performance of the poly carbonate resin composition of gained, the structural unit that the structural unit shown in above-mentioned general formula (I) is preferably 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 words that the viscosity-average molecular weight of PC-PDMS multipolymer (A-1) is large are effective, but when viscosity-average molecular weight becomes large, are difficult to shaping thin-wall member.
Also can reduce the viscosity of resin combination by improving forming temperature, but now, forming cycle is elongated, less economical, in addition, when excessive temperature improves, production stability can be caused to reduce because of the thermal degradation when of resin combination.
Therefore, the viscosity-average molecular weight of PC-PDMS multipolymer (A-1) is preferably 15000 ~ 24000, is more preferably 16000 ~ 22500, more preferably 17000 ~ 21000.
When viscosity-average molecular weight is more than 15000, the intensity of molding is abundant, and when viscosity-average molecular weight is less than 24000, the viscosity of multipolymer diminishes, and therefore, productivity during manufacture is good, and in addition, the shaping of thin-walled also becomes good.
Dihydric phenol shown in PC-PDMS multipolymer (A-1) the following general formula of use (1), organopolysiloxane, carbonyl chloride, carbonic ether or the chloro-formic ester shown in following general formula (2) and the molecular weight regulator used as required obtain.
[changing 3]
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 7represent aryl substituted alkylene, the arylidene alkylidene group of straight chain, side chain or ring-type, aryl substituted alkylene, ring can with alkoxyl group.
In poly carbonate resin composition of the present invention, as the dihydric phenol shown in the general formula used in the raw material of PC-PDMS multipolymer (A-1) (1), be not particularly limited, preferably 2,2-two (4-hydroxy phenyl) propane (being commonly called as: dihydroxyphenyl propane).When using dihydroxyphenyl propane as dihydric phenol, the X becoming general formula (I) is isopropylidene and the PC-PDMS multipolymer of a=b=0.
As the dihydric phenol beyond dihydroxyphenyl propane, include, for example out: 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) octane 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-hydroxytertiarybutylphenyl) propane of 1-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (the 4-hydroxyl-3 of 2-, 5-tetramethylphenyl) propane, 2, two (4-hydroxyl-3-chloro-phenyl-) propane of 2-, 2, two (the 4-hydroxyl-3 of 2-, 5-dichlorophenyl) propane, 2, two (the 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 phenyl)-3 of 1-, 5, two (hydroxyaryl) cycloalkanes such as 5-trimethyl-cyclohexane, 2,2-two (4-hydroxy phenyl) norbornanes, 1,1-two (4-hydroxy phenyl) cyclododecanes, 4,4 '-dihydroxy phenyl ether, 4, the dihydroxyl aryl ethers such as 4 '-dihydroxyl-3,3 '-3,5-dimethylphenyl ether, 4,4 '-dihydroxydiphenyl thioether, 4, the dihydroxyl diaryl sulfide classes such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfide, 4,4 '-dihydroxydiphenyl sulfoxide, 4, the dihydroxyl diaryl sulphoxide classes such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfoxide, 4,4 '-dihydroxy-diphenyl sulfone, 4, the dihydroxyl diaryl sulfone classes such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfone, 4, the dihydroxydiphenyl classes such as 4 '-dihydroxydiphenyl, the dihydroxyl Diarylfluorenes such as two (4-hydroxy phenyl) fluorenes of 9,9-, 9,9-two (4-hydroxy-3-methyl phenyl) fluorenes, the dihydroxyl diaryl adamantanes such as two (4-hydroxy phenyl) ditan, 1,3-two (4-hydroxy phenyl) diamantane, 2,2-two (4-hydroxy phenyl) diamantane, 1,3-two (4-hydroxy phenyl)-5,7-dimethyladamantanes, 4,4 '-［ 1,3-phenylene two (1-methyl ethidine) ］ bis-phenol, 10,10-two (4-hydroxy phenyl)-9-anthrones, 1,5-two (4-hydroxybenzene sulfenyl)-2,3-dioxa amylenes etc.
These dihydric phenols can be used alone or used in combination two or more.
Organopolysiloxane shown in general formula (2) can be carried out hydrosilylation reactions by the end of organopolysiloxane chain with the polymerization degree n with regulation such as the phenol, preferred vinyl phenol, chavicol, oxymethoxyallylbenzene, isopropenyl phenol etc. that make to have the unsaturated C-C of olefinic and easily be manufactured.Above-mentioned phenol is more preferably chavicol or oxymethoxyallylbenzene.Now, the Y in the general formula (II) of (A-1) composition 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, such as, 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), separately represent the alkoxyl group of the alkyl of hydrogen atom, halogen atom or carbon number 1 ~ 6, carbon number 1 ~ 6 or the aryl of carbon number 6 ~ 12, n is the averaged repeating numbers of organo-siloxane Component units and the integer of expression 1 ~ 600.In addition, R 8represent alkyl, thiazolinyl, aryl or aralkyl, c represents positive integer, is generally the integer of 1 ~ 6.
Wherein, from the viewpoint of the easy degree of polymerization, the phenol-modified organopolysiloxane shown in preferred formula (3).In addition, from the viewpoint of easy degree of starting with, preferably as α a kind of 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, such as, can list method shown below.
First, cyclotrisiloxane and sily oxide are reacted in the presence of acidic, synthesis α, ω-dihydro organopolysiloxane.Now, by changing the charge ratio of cyclotrisiloxane and sily oxide, the α with desired average repeat unit can be synthesized, ω-dihydro organopolysiloxane.Then, under the existence of hydrosilylation reactions catalyzer, make this α, the oxybenzene compound that ω-dihydro organopolysiloxane and chavicol, oxymethoxyallylbenzene etc. have unsaturated fatty hydrocarbons base carries out addition reaction, thus can manufacture the phenol-modified organopolysiloxane with desired average repeat unit.
In addition, in this stage, because low-molecular-weight cyclic polyorganosiloxane, excessive above-mentioned oxybenzene compound get off as impurities left, therefore, preferably under reduced pressure carry out heating and the distillation of these low molecular compounds is removed.
(aromatic copolycarbonate (A-2) beyond (A-1))
In poly carbonate resin composition of the present invention, (A-2) composition as the aromatic copolycarbonate beyond above-mentioned (A-1) can use the material obtained by the manufacture method of known aromatic copolycarbonate, namely, under the existence to the organic solvent of reaction in inertia, alkali aqueous solution, dihydric phenol based compound and carbonyl chloride are reacted, then adds the polymerizing catalyst such as tertiary amine or quaternary ammonium salt and the interfacial polymerization that makes it be polymerized; Dihydric phenol based compound is dissolved in the mixing solutions of pyridine or pyridine and inert solvent, imports the pyridine method etc. that carbonyl chloride and directly carrying out manufactures.
As the dihydric phenol based compound used in the manufacture of the aromatic copolycarbonate of (A-2) composition, can list: 2, two (4-hydroxy phenyl) propane (being commonly called as: dihydroxyphenyl propane) of 2-, 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) octane 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 (the 4-hydroxyl-3 of 2-, 5-3,5-dimethylphenyl) propane, 2, two (4-hydroxyl-3-chloro-phenyl-) propane of 2-, 2, two (the 4-hydroxyl-3 of 2-, 5-dichlorophenyl) propane, 2, two (the 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 phenyl)-3 of 1-, 5, two (hydroxyaryl) cycloalkanes such as 5-trimethyl-cyclohexane, 2,2-two (4-hydroxy phenyl) norbornanes, 1,1-two (4-hydroxy phenyl) cyclododecanes, 4,4 '-dihydroxy phenyl ether, 4, the dihydroxyl aryl ethers such as 4 '-dihydroxyl-3,3 '-3,5-dimethylphenyl ether, 4,4 '-dihydroxydiphenyl thioether, 4, the dihydroxyl diaryl sulfide classes such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfide, 4,4 '-dihydroxydiphenyl sulfoxide, 4, the dihydroxyl diaryl sulphoxide classes such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfoxide, 4,4 '-dihydroxy-diphenyl sulfone, 4, the dihydroxyl diaryl sulfone classes such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfone, 4, the dihydroxybiphenyl classes such as 4 '-dihydroxybiphenyl, the dihydroxyl Diarylfluorenes such as two (4-hydroxy phenyl) fluorenes of 9,9-, 9,9-two (4-hydroxy-3-methyl phenyl) fluorenes, the dihydroxyl diaryl adamantanes such as two (4-hydroxy phenyl) ditan, 1,3-two (4-hydroxy phenyl) diamantane, 2,2-two (4-hydroxy phenyl) diamantane, 1,3-two (4-hydroxy phenyl)-5,7-dimethyladamantanes, 4,4 '-［ 1,3-phenylene two (1-methyl ethidine) ］ bis-phenol, 10,10-two (4-hydroxy phenyl)-9-anthrones, 1,5-two (4-hydroxybenzene sulfenyl)-2,3-dioxa amylenes etc.These dihydric phenols can be used alone or used in combination two or more.
When manufacturing the aromatic copolycarbonate of (A-2) composition, also molecular weight regulator, end terminator etc. can be used as required.As long as normally used material in the polymerization of their polycarbonate resins, just can use various material.
With regard to concrete molecular weight regulator, as unitary phenol, such as, 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, p-cumylphenol, 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 of average carbon number 12 ~ 35 or the alkyl of branched, 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 unitary phenol, preferred p-tert-butylphenol, p-cumylphenol, p-phenyl phenol etc.In addition, these compounds can be used alone or combinationally use two or more compound.
As end terminator, monocarboxylic acid and its derivative, unitary phenol can be used.Such as can list: p-tert-butylphenol, p-phenyl phenol, p-cumylphenol, to perfluor nonylphenol, to (perfluor nonyl phenyl) phenol, to (perfluoro hexyl phenyl) phenol, to perfluoro-t-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 perfluorododecyl 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 relative to above-mentioned dihydric phenol based compound, is more preferably 0.1 ~ 1.0 % by mole.
As branching agent, such as 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 "-three (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. have the compound of more than 3 functional groups.
In (A) the polycarbonate-based resin comprising (A-1) composition and (A-2) composition, the content of (A-1) is 5 ~ 100 quality %, is preferably 70 ~ 100 quality %, is more preferably 50 ~ 100 quality %; (A-2) content is 95 ~ 0 quality %, is preferably 30 ~ 0 quality %, is more preferably 50 ~ 0 quality %.
Be more than 5 quality % at the content of (A-1), or when content (A-2) is below 95 quality %, owing to making the many and make low temperature impact strength improve containing quantitative change of the organopolysiloxane block section in (A) polycarbonate-based resin, therefore without the need to increasing the content of the organopolysiloxane block section containing the structural unit shown in general formula (II) when manufacturing (A-1) composition, thus when manufacturing (A-1) composition, the homogeneity of the reaction in polymerization process can not reduce, and the separation property of polymkeric substance and rinse water can not be deteriorated in the matting of polymkeric substance, therefore the productivity of (A-1) composition becomes good.
In the polycarbonate-based resin (A) comprising (A-1) composition and (A-2) composition, the content with the organopolysiloxane block section of the structural unit of general formula (II) is preferably 0.1 ~ 40 quality %, is more preferably 0.5 ~ 25 quality %, more preferably 0.5 ~ 15 quality %, be further preferably 0.5 ~ 10 quality %.When its content is more than 0.1 quality %, the effect improving impact strength is abundant, on the other hand, when its content is below 40 quality %, has sufficient flame retardant resistance, thermotolerance.
(graphene film (B))
In poly carbonate resin composition of the present invention, in order to give the proterties such as flame retardant resistance, electroconductibility, rigidity, shaping outward appearance and thermal conductivity to molding, and need containing graphene film as (B) composition.
Graphene film refers to the graphene board with one or more layers Graphene face, usually uses ultrasonic energy and becomes flake, and the level of sheet can be controlled by adjustment ultrasonic (sonification) time.
The thickness of the graphene film used in the present invention is preferably 5 ~ 10nm, and its size is preferably more than 3 μm.The thickness of the graphene film used in the present invention be 5 ~ 10nm and size is more than 3 μm time, the dispersiveness of graphene film improves, and easily and resin compounded, obtains the molding of flame retardant resistance, electroconductibility, rigidity, shaping outward appearance and excellent thermal conductivity.From the view point of above-mentioned, the thickness of graphene film is preferably 6 ~ 8nm, and the size of graphene film is preferably 3 ~ 30 μm, is more preferably 5 ~ 25 μm, more preferably 5 ~ 20 μm.In proterties as above, from the view point of giving higher electroconductibility, the size of graphene film is preferably 5 ~ 30 μm, is more preferably 5 ~ 20 μm.
In the present invention, graphene film is the shape of tabular, and its thickness refers to the size of the thickness direction that graphene film is overlapping, and its size refers to the size of graphene-structured itself, and the method that embodiment can be utilized to record measures.
As goods, " xGnP " (GRAPHENENANOPLATELETS) etc. having XGSciences company to manufacture.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 contain above-mentioned polycarbonate-based resin (A) with the ratio of 70 ~ 99.5 quality % and contain this graphene film (B) with the ratio of 30 ~ 0.5 quality %.When the content of graphene film (B) is lower than 0.5 quality %, be difficult to the imparting effect playing above-mentioned proterties, on the other hand, when the content of graphene film (B) is more than 30 quality %, shock strength significantly reduces, and the outward appearance that is shaped also reduces.From the view point of above, the preferred content of this graphene film (B) is 1 ~ 30 quality % relative to the total amount of itself and polycarbonate-based resin (A), is more preferably 1 ~ 20 quality %.
(tetrafluoroethylene (C))
In order to there is anti-dropping (anti-dripping) effect, giving high flame retardant, in poly carbonate resin composition of the present invention, preferably contain tetrafluoroethylene as (C) composition.
This tetrafluoroethylene (C) is for having the tetrafluoroethylene of the molecular-weight average more than 500000 of protofibril (fibril) Forming ability (hreinafter referred to as PTFE.), it has anti-dropping effect, and can give high flame retardant.Its molecular-weight average needs to be more than 500000, is preferably 500000 ~ 10000000, more preferably 1000000 ~ 10000000.
As the PTFE with protofibril Forming ability, be not particularly limited, specifically, 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 MPAFA-100(Daikin Industries company manufacture); CD076(AsahiGlassFluoropolymers company manufactures) and the manufacture of AlgoflonF5(Montefluos company) etc.
Under the PTFE as above with protofibril Forming ability can pass through such as to make the pressure of tetrafluoroethylene at 7 ~ 700kPa under the existence of sodium, potassium or ammonium peroxo disulfate compound in aqueous solvent, be polymerized at temperature 0 ~ 200 DEG C, preferably 20 ~ 100 DEG C and obtain.
The content of this PTFE is generally 0.01 ~ 1 mass parts relative 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, is more preferably 0.1 ~ 0.8 mass parts.When the content of this PTFE is above-mentioned scope, the anti-dropping in target flame retardant resistance becomes abundant.
In poly carbonate resin composition of the present invention, above-mentioned PTFE can be replaced and containing the mixed powder comprising polytetrafluoroethylparticle particle and organic based polymer particle.
The particle diameter of the polytetrafluoroethylparticle particle in this mixed powder is generally less than 10 μm, is preferably 0.05 ~ 1.0 μm.
Polytetrafluoroethylparticle particle is made into such as to be dispersed in the aqueous liquid dispersion containing in the water of emulsifying agent etc.The aqueous liquid dispersion of this polytetrafluoroethylparticle particle is by using fluorochemical surfactant and making tetrafluoroethylene monomer carry out letex polymerization and obtain.
When the letex polymerization of polytetrafluoroethylparticle particle, the fluorine-containing alkyl ester of (methyl) vinylformic acid such as the Fluorine containing olefines such as R 1216, chlorotrifluoroethylene, fluoroalkyl and perfluoroalkyl vinyl ether, (methyl) perfluoroalkyl acrylate can be used in the scope of characteristic not damaging tetrafluoroethylene as copolymer composition.
The content of copolymer composition is preferably below 10 quality % relative to the tetrafluoroethylene in polytetrafluoroethylparticle particle.
As the organic based polymer particle in this mixed powder, be not particularly limited, from the viewpoint of the dispersiveness of polytetrafluoroethylparticle particle when being matched with polycarbonate-based resin (A), preferably polycarbonate resin is had to the organic based polymer particle of affinity.
The content comprising the mixed powder of polytetrafluoroethylparticle particle and organic based polymer particle is generally 0.1 ~ 1 mass parts relative to total amount 100 mass parts of polycarbonate-based resin (A) and graphene film (B), is preferably 0.1 ~ 0.9 mass parts, is more preferably 0.2 ~ 0.8 mass parts.
When the content of above-mentioned mixed powder is more than 0.1 mass parts, melt-dropping property is good, can realize flame retardant resistance.On the other hand, when the content of above-mentioned mixed powder is below 1 mass parts, the ratio of the organic based polymer in composition can not excessively increase, and can realize flame retardant resistance.
(any added ingredients)
In poly carbonate resin composition of the present invention, except above-mentioned (A) composition, (B) composition and (C) composition or mixed powder, the known various added ingredients in the past added in poly carbonate resin composition can also be contained as required in the scope not damaging effect of the present invention.As such added ingredients, such as, can list: antioxidant, UV light absorber, static inhibitor, lubricant, releasing agent, dyestuff, pigment, shock-resistance improvement elastomerics etc. beyond phosphorous antioxidant, alkali (soil) metal-salt as the organic sulfonic acid of fire-retardant rising agent, supporting material, weighting agent, hindered amine system photostabilizer, phosphorus system.
(phosphorous antioxidant)
As phosphorous antioxidant used in the present invention, be not particularly limited.As representative examples, 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-chloropropyl) 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-chloropropyl) ester; The tricresyl phosphate cycloalkyl esters such as thricyclohexyl-1-phosphoric acid ester; The triaryl phosphates etc. such as triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (nonyl phenyl) ester, phosphoric acid 2-ethylphenyl diphenyl ester.Wherein, preferably triaryl phosphites and triaryl phosphate is used.
In the present invention, these phosphorous antioxidants can be used alone one, also can combinationally use two or more.In addition, the content of this phosphorous antioxidant in poly carbonate resin composition is preferably 0.1 ~ 1 mass parts relative to polycarbonate-based resin (A) 100 mass parts.By comprising this phosphorous antioxidant of above-mentioned scope, sufficient antioxidant effect can be obtained.
(alkali (soil) metal-salt of organic sulfonic acid)
In poly carbonate resin composition of the present invention, in order to improve flame retardant resistance, an alkali metal salt and/or the alkaline earth salt (hereinafter also referred to organic sulfonic acid alkali (soil) metal-salt) of organic sulfonic acid can be contained.
As organic sulfonic acid, perfluoroalkane sulfonate, polystyrolsulfon acid etc. can be listed.
As organic sulfonic acid alkali (soil) metal-salt, though various salt can be listed, for having organic sulfonic acid an alkali metal salt, the alkaline earth salt of at least one carbon atom.
As basic metal, sodium, potassium, lithium and caesium etc. can be listed, as alkaline-earth metal, magnesium, calcium, strontium and barium etc. can be listed.Wherein, the salt of preferred sodium, potassium and caesium.
As (C) composition, an alkali metal salt of preferred perfluoroalkane sulfonate or polystyrolsulfon acid and/or alkaline earth salt.
As alkali (soil) metal-salt of perfluoroalkane sulfonate, the salt shown in following general formula (12) can be listed.
（C dF 2d+1SO 3） eＭ…（12）
In formula (12), d represents the integer of 1 ~ 10, 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 such as, recorded in Japanese Patent Publication 47-40445 publication is suitable.
In general formula (12), as perfluoroalkane sulfonate, such as, can list: perfluoromethane sulfonic acid, R 116 sulfonic acid, perfluoropropane sulfonic acid, perfluorobutane, perfluoro-methyl butane sulfonic acid, perfluorohexanesulfonic 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, the fluorine of 5-trichlorobenzene sulfonic acid, sulfobenzide-3-sulfonic acid, sulfobenzide-3,3 '-disulfonic acid, naphthalene trisulfonic acid and these sulfonic acid replaces an alkali metal salt, alkaline earth salt etc. of the organic sulfonic acid such as body and polystyrolsulfon acid.Wherein, as organic sulfonic acid, particularly preferably perfluoroalkane sulfonate and phenylbenzene sulfonic acid.
As alkali (soil) metal-salt of polystyrolsulfon acid, alkali (soil) metal-salt of the aromatic vinyl base system resin containing sulphonate-base shown in following general formula (13) can be listed.
[changing 5]
In formula (13), Q represents sulphonate-base, R 9represent the alkyl of hydrogen atom or carbon number 1 ~ 10.S represents the integer of 1 ~ 5, and t represents molar fraction, 0 < t≤1.
Here, the sulphonate-base of Q is an alkali metal salt and/or the alkaline earth salt of sulfonic acid, as metal, can list sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium etc.
In addition, R 9for the alkyl of hydrogen atom or carbon number 1 ~ 10, be preferably hydrogen atom or methyl.
S is the integer of 1 ~ 5, and t is the relation of 0 < t≤1.Therefore, sulphonate-base (Q) can comprise aromatic nucleus is all replaced and obtain sulphonate-base, aromatic moiety is replaced and the sulphonate-base that obtains.
(C) content of alkali (soil) metal-salt of organic sulfonic acid be preferably 0.01 ~ 0.15 mass parts relative to polycarbonate-based resin (A) 100 mass parts, be more preferably 0.02 ~ 0.13 mass parts, more preferably 0.03 ~ 0.12 mass parts.This content be more than 0.01 mass parts and below 0.15 mass parts time, fully can improve flame retardant resistance.
Polycarbonate-based resin composition of the present invention is not in fact containing any one in organic halogenated flame retardant and organophosphate flame retardant.Therefore, the risk of reduction of the generation of obnoxious flavour, the pollution of forming mill, the burning of resin, thermotolerance can not be there is.
(preparation method of poly carbonate resin composition)
Poly carbonate resin composition of the present invention can be prepared as follows: above-mentioned (A) composition ［ (A-1) and (A-2) ］, (B) composition and (C) composition used as required or mixed powder and various any composition are coordinated to scale, carry out mixing, thus prepare this poly carbonate resin composition.
Cooperation now and mixing can 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 time mixing is suitably selected usually in the scope of 240 ~ 300 DEG C.
It should be noted that, except polycarbonate-based resin containing composition also can in advance mixing with polycarbonate-based resin melting, namely add with the form of masterbatch (masterbatch).
Poly carbonate resin composition of the present invention can use above-mentioned melting mixing forming mill to manufacture various molding; Or can, with the particle obtained for raw material, utilize injection molding method, ejection compress moulding method, extrusion molding method, blow-moulding process, press forming method, vacuum forming process 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, that is, manufacture granular shaping raw material by above-mentioned melting mixing method, 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, also can in order to prevent the indenture of outward appearance (Japanese original text: ヒ ケ) or adopt gas inject manufacturing process in order to lightweight.
For for the molding of the present invention produced with upper type, the excellence such as its flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance, thermal conductivity, and the pollution of the caused semi-conductor etc. that to be come off by carbon can not be caused, be therefore suitable for the housing of the electric/electronic devices such as OA equipment, information equipment, electrification of domestic equipment, parts, film and trolley part etc.
Embodiment
Below, the present invention will be described in more detail to utilize embodiment and comparative example, but the present invention is not by 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 determination of ubbelohde viscometer 20 DEG C, obtain limiting viscosity [η] by this viscosity, 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)
Coordinate each composition according to the ratio shown in table 1 ~ table 3, be supplied to forcing machine (model: VS40, limit, field plastics machinery (strain) manufacture), at 240 DEG C, carry out melting mixing, carry out granulating.It should be noted that, in all embodiments and comparative example, coordinated the Irganox1076(BASFJAPAN(strain as antioxidant) manufacture) 0.2 mass parts.The particle of gained after 12 hours 120 DEG C of dryings, is carried out injection forming, thus obtains test film under injection machine (toshiba machine (strain) manufacture, model: IS100N) expects the condition of cylinder temperature 260 DEG C, die temperature 80 DEG C.Use the test film obtained, carry out following mensuration, performance is evaluated.
(1) IZOD(cantilever-type impact strength): according to ASTMD256, at 23 DEG C (wall thickness 1/8 inch), unit: kJ/m 2
(2) bending elastic modulus: according to ASTMD-790(test conditions etc.: 23 DEG C, 4mm), unit: MPa
(3) volume intrinsic resistance value: according to JISK6911(test panel: 80 × 80 × 3mm), unit: 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; Evaluate according to following benchmark.
Zero: good, ×: there is on surface the bad outward appearances such as pit.
The thickness of < graphene film and size >
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, the aqueous sodium hydroxide solution and methylene dichloride that are held in this dihydroxyphenyl propane of room temperature are passed through from orifice plate with the flow of the flow of 138 ls/h and 69 ls/h and import to the tube-type reactor of internal diameter 10mm, pipe range 10m respectively, wherein and flow carbonyl chloride and be blown into the flow of 10.7kg/ hour, it is made to react 3 hours continuously.Tube-type reactor used herein is double wall tube, passes into water coolant at sleeve portion, and the outflow temperature of reaction solution is remained on 25 DEG C.In addition, the pH value of liquid effluent is adjusted to 10 ~ 11.
Leave standstill according to the reaction solution obtained with upper type, be separated thus and remove aqueous phase, gather methylene dichloride phase (220 liters), obtain PC oligopolymer (concentration 317g/ liter).The polymerization degree of PC oligopolymer obtained here is 2 ~ 4, and the concentration of chloroformic acid ester group is 0.7 mole/L.
Production Example 2 ［ manufacture of reactive PDMS ］
The 86 quality % sulfuric acid of 1,1,3, the 3-tetramethyl disiloxane of the octamethylcyclotetrasiloxane of 1483g, 96g and 35g are mixed, at room temperature stirs 17 hours.Afterwards, be separated oil phase, add the sodium bicarbonate of 25g, stir 1 hour.After filtration, 150 DEG C, 3torr(4 × 10 2pa) carry out vacuum distilling under, removing low boilers, obtains oil.
In the mixture of the platinum as platinum chloride-ol salt complex of the 2-chavicol of 60g and 0.0014g, oily 294g obtained above is added at the temperature of 90 DEG C.The temperature limit that this mixture limit remains on 90 ~ 115 DEG C is stirred 3 hours.With methylene dichloride, product is extracted, wash 3 times with the methanol aqueous solution of 80 quality %, remove excessive 2-chavicol.By this product anhydrous sodium sulfate drying, be heated to 115 DEG C in a vacuum, distillation is except desolventizing.For obtained terminal 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 obtained in Production Example 2 is dissolved in methylene dichloride 2 liters, the PC oligopolymer obtained in remix Production Example 1 10 liters.Add the solution and triethylamine 5.7cm that sodium hydroxide 26g are dissolved in 1 liter, water wherein 3, at room temperature stir 1 hour with 500rpm, make it react.
After reaction terminates, in above-mentioned reaction system, add solution, methylene dichloride 8 liters and the p-tert-butylphenol 96g after the aqueous sodium hydroxide solution 5 liters dihydroxyphenyl propane 600g being dissolved in 5.2 quality %, at room temperature stir 2 hours with 500rpm, make it react.
After reaction, add methylene dichloride 5 liters, then carry out the washing with 5 premium on currency successively, with the neutralizing treatment of 0.03 mole/L aqueous sodium hydroxide solution 5 liters, acid elution with 0.2 mole/L hydrochloric acid 5 liters and the washing with 5 liters, water 2 times, finally remove methylene dichloride, obtain laminar PC-PDMS multipolymer.By the vacuum-drying 24 hours at 120 DEG C of the PC-PDMS multipolymer of gained.Viscosity-average molecular weight is 17000, PDMS containing ratio is 4.0 quality %.
It should be noted that, PDMS containing ratio based on 1the peak of the methyl of the sec.-propyl of the dihydroxyphenyl propane observed at 1.7ppm in H-NMR is tried to achieve with the strength ratio at the peak of the methyl of the dimethyl siloxane observed at 0.2ppm.
Embodiment 1 ~ 10 and comparative example 1 ~ 13
According to above-mentioned " making method of test film ", make the test film in each example respectively, use this test film to utilize various test evaluation performance.Its result as shown in Table 1 to Table 3.
[table 1]
Table 1
[table 2]
Table 2
[table 3]
Table 3
［ note ］
(A) composition:
(A-1) PC-PDMS: the PC-PDMS multipolymer that the viscosity-average molecular weight obtained in Production Example 3 is 17000, PDMS containing ratio is 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: " GRAPHENENANOPLATELETSxGnP " (manufacture of XGSciences company), thickness 6 ~ 8nm, size (chip size) 5 μm
Graphene film 2: " GRAPHENENANOPLATELETSxGnP " (manufacture of XGSciences company), thickness 6 ~ 8nm, size (chip size) 15 μm
Graphene film 3: " GRAPHENENANOPLATELETSxGnP " (manufacture of XGSciences company), thickness 2 ~ 4nm, size (chip size) 2 μm
(C) composition:
PTFE:PTFE " CD076 " (AsahiGlassFluoropolymers(strain) manufactures)
Other compositions:
Carbon nanotube 1: many walls diameter 50 ~ 100nm, length 1 ~ 10 μm, both ends open, amorphous carbon amounts 15 quality %(サ Application Na ノ テ ッ Network company manufacture)
Carbon nanotube 2: many walls diameter 10 ~ 30nm, length 1 ~ 10 μm, both ends open, amorphous carbon amounts 15 quality %(サ Application Na ノ テ ッ Network company manufacture)
Graphite: " PC99-300M " (she manufactures eastern blacklead industry (strain)), median size 56 μm, thickness 1.7 μm
From table 1 ~ table 3, belong to poly carbonate resin composition of the present invention by containing graphene film with specified proportion, thus can obtain high flame retardant and the reduction of shock strength is tailed off, rigidity, electroconductibility and shaping outward appearance are also excellent.Contain PC-PDMS multipolymer particularly by with specific ratio, thus make shock strength and excellent in flame retardance.By containing PTFE further, thus the flame retardant resistance of thin-walled can be realized further.In addition, by using thickness to be 5 ~ 10nm and size is the graphene film of more than 3 μm, thus higher flame retardant resistance, rigidity, electroconductibility is obtained.
On the other hand, in the carbon nanotube that comparative example uses, compared with graphene film, rigidity and flame retardant resistance are deteriorated, 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 excellent molding such as flame retardant resistance, rigidity, shock-resistance, electroconductibility, shaping outward appearance and thermal conductivity.This molding is expected to its Application Areas and is extended in the housing of the electric/electronic devices such as OA equipment, information equipment, electrification of domestic equipment, parts, film and trolley part etc.

Claims (29)

1. a poly carbonate resin composition, it is characterized in that, comprise the polycarbonate-based resin (A) of 70 ~ 99.5 quality % and the graphene film (B) of 30 ~ 0.5 quality %, described polycarbonate-based resin (A) is made up of with the mass ratio of 5:95 ~ 100:0 polycarbonate-poly organo alkyl copolymer (A-1) and the aromatic copolycarbonate (A-2) beyond (A-1), and the thickness of described graphene film (B) is 5 ~ 10nm.
2. poly carbonate resin composition according to claim 1, wherein, the main chain of polycarbonate-poly organo alkyl copolymer (A-1) comprises the structural unit shown in general formula (I) and the structural unit shown in general formula (II), and the organopolysiloxane block that structural unit this general formula (II) shown in be made up of of polycarbonate-poly organo alkyl copolymer (A-1) containing 2 ~ 40 quality %
In formula, R 1and R 2separately represent the alkyl of carbon number 1 ~ 6 or alkoxyl group, X represents the alkylidene group of singly-bound, carbon number 1 ~ 8, the alkylidene of carbon number 2 ~ 8, the cycloalkylidene of carbon number 5 ~ 15, the ring alkylidene of carbon number 5 ~ 15 ,-S-,-SO-,-SO 2-,-O-or-CO-, R 3~ R 6separately represent the alkoxyl group of the alkyl of hydrogen atom, halogen atom or carbon number 1 ~ 6, carbon number 1 ~ 6 or the aryl of carbon number 6 ~ 12, Y represents and comprises aliphatics or aromatic organic residue, n is averaged repeating numbers and represents the integer of 1 ~ 600, a and b represents the integer of 0 ~ 4.
3. poly carbonate resin composition according to claim 2, wherein, Y is the organic residue being derived from chavicol or oxymethoxyallylbenzene.
4. the poly carbonate resin composition according to Claims 2 or 3, wherein, the structural unit shown in general formula (I) is the structural unit derived by dihydroxyphenyl propane.
5. the poly carbonate resin composition according to Claims 2 or 3, wherein, the R in the structural unit shown in general formula (II) 3and R 4be methyl.
6. the poly carbonate resin composition according to any one of claims 1 to 3, it also comprises relative to total amount 100 mass parts of (A) composition and (B) composition is the tetrafluoroethylene (C) of 0.01 ~ 1 mass parts.
7. a molding, it makes the shaping of the poly carbonate resin composition according to any one of claim 1 ~ 6 form.
8. poly carbonate resin composition according to claim 1, wherein,
In the polycarbonate-based resin (A) be made up of (A-1) composition and (A-2) composition, the content of (A-1) composition is 70 ~ 100 quality %.
9. poly carbonate resin composition according to claim 1, wherein,
In the polycarbonate-based resin (A) be made up of (A-1) composition and (A-2) composition, the content of (A-1) composition is 50 ~ 100 quality %.
10. poly carbonate resin composition according to claim 2, wherein,
In described polycarbonate-poly organo alkyl copolymer (A-1), the content with the organopolysiloxane block section of the structural unit shown in described general formula (II) is 3 ~ 25 quality %.
11. poly carbonate resin compositions according to claim 2, wherein,
In described polycarbonate-based resin (A), the content with the organopolysiloxane block section of the structural unit shown in described general formula (II) is 0.1 ~ 40 quality %.
12. poly carbonate resin compositions according to claim 2, wherein,
In described polycarbonate-based resin (A), the content with the organopolysiloxane block section of the structural unit shown in described general formula (II) is 0.5 ~ 25 quality %.
13. poly carbonate resin compositions according to claim 2, wherein,
In described polycarbonate-based resin (A), the content with the organopolysiloxane block section of the structural unit shown in described general formula (II) is 0.5 ~ 15 quality %.
14. poly carbonate resin compositions according to claim 2, wherein,
In described polycarbonate-based resin (A), the content with the organopolysiloxane block section of the structural unit shown in described general formula (II) is 0.5 ~ 10 quality %.
15. poly carbonate resin compositions according to claim 1, wherein,
The content of graphene film (B) is 1 ~ 30 quality % relative to the total amount of itself and polycarbonate-based resin (A).
16. poly carbonate resin compositions according to claim 1, wherein,
The content of graphene film (B) is 1 ~ 20 quality % relative to the total amount of itself and polycarbonate-based resin (A).
17. poly carbonate resin compositions according to claim 2, wherein,
N in described general formula (II) is 1 ~ 500.
18. poly carbonate resin compositions according to claim 2, wherein,
N in described general formula (II) is 5 ~ 200.
19. poly carbonate resin compositions according to claim 1, wherein,
The thickness of described graphene film (B) is 6 ~ 8nm.
20. poly carbonate resin compositions according to claim 1, wherein,
The size of described graphene film (B) is 3 ~ 30 μm.
21. poly carbonate resin compositions according to claim 1, wherein,
The size of described graphene film (B) is 5 ~ 25 μm.
22. poly carbonate resin compositions according to claim 1, wherein,
The size of described graphene film (B) is 5 ~ 30 μm.
23. poly carbonate resin compositions according to claim 1, wherein,
The size of described graphene film (B) is 5 ~ 20 μm.
24. poly carbonate resin compositions according to claim 1,
It also comprises relative to polycarbonate-based resin (A) 100 mass parts content is the phosphorous antioxidant of 0.1 ~ 1 mass parts.
25. poly carbonate resin compositions according to claim 1,
It also comprises relative to polycarbonate-based resin (A) 100 mass parts content is an alkali metal salt and/or the alkaline earth salt of the organic sulfonic acid of 0.01 ~ 0.15 mass parts.
26. poly carbonate resin compositions according to claim 25, wherein,
An alkali metal salt of described organic sulfonic acid and/or alkaline earth salt are perfluoroalkane sulfonate or polystyrolsulfon acid an alkali metal salt and/or alkaline earth salt.
27. poly carbonate resin compositions according to claim 1, wherein,
The viscosity-average molecular weight of described polycarbonate-poly organo alkyl copolymer (A-1) is 15000 ~ 24000.
28. poly carbonate resin compositions according to claim 1, wherein,
The viscosity-average molecular weight of described polycarbonate-poly organo alkyl copolymer (A-1) is 16000 ~ 22500.
29. poly carbonate resin compositions according to claim 1, wherein,
The viscosity-average molecular weight of described polycarbonate-poly organo alkyl copolymer (A-1) is 17000 ~ 21000.
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