CN106280496A

CN106280496A - Polycarbonate resin composition

Info

Publication number: CN106280496A
Application number: CN201610703154.6A
Authority: CN
Inventors: 石川康弘; 田中隆义; 竹内敬直; 青木佑介
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2011-10-03
Filing date: 2012-10-02
Publication date: 2017-01-04
Anticipated expiration: 2032-10-02
Also published as: JP6106593B2; TWI586754B; TW201323517A; KR20140077164A; TW201634578A; CN103857745A; WO2013051557A1; CN103857745B; KR101971751B1; CN106280496B; JPWO2013051557A1; TWI604012B

Abstract

The present invention provides a polycarbonate resin composition having excellent color appearance while maintaining excellent characteristics of a polycarbonate-polyorganosiloxane copolymer. Specifically disclosed is a polycarbonate resin composition containing (A) 99.9-96 mass% of a polycarbonate resin0.1 to 4 parts by mass of titanium oxide (B), wherein the component (A) comprises: 5 to 100% by mass of a polycarbonate-polyorganosiloxane copolymer (A-1), 0 to 95% by mass of a polycarbonate-polyorganosiloxane copolymer (A-2), and 0 to 95% by mass of an aromatic polycarbonate (A-3) outside the polycarbonate-polyorganosiloxane copolymer, (A-1) has a repeating unit represented by formula (I) and a constituent unit represented by formula (II) in an amount of 2 to 20% by mass in the main chain, n is 25 to 65, (A-2) has a repeating unit represented by formula (I) and a constituent unit represented by formula (II) in an amount of 2 to 20% by mass in the main chain, and n is 70 to 350.

Description

Polycarbonate-based resin composition

The application is application number: 2012800487670, PCT Application No.: PCT/JP2012/075506, the applying date: 2012.10.2, denomination of invention: the divisional application of the application of " polycarbonate-based resin composition ".

Technical field

The present invention relates to polycarbonate-based resin composition.

Background technology

The excellences such as the mechanical strength of polycarbonate resin, electrical characteristics, the transparency, are widely used at electricity as engineering plastics In various field such as gas-electronic device field, automotive field etc..In mobile phone, Portable table type machine, digital camera, videocorder, electronic work The housing of tool etc. also utilizes polycarbonate resin, the probability fallen etc. when there is operation in these purposes, the most resistance to punching Hitting property is important, and appearance design (particularly color) is also important factor.

It addition, the coloring of resin material is to be relatively easy to, coloury resin material is effectively utilised at one's side ?.Use white, Lycoperdon polymorphum Vitt etc. the most in a large number.On the other hand, it is known to by the Merlon of polysiloxane copolymerization- Poly organo alkyl copolymer (hereinafter sometimes referred to PC-PDMS.).The excellent such as the resistance to impact of PC-PDMS, therefore by the phase It is ready to use in described purposes.It should be noted that resistance to impact is important in described purposes, on the other hand, appearance design is the most important, It is therefore desirable for use titanium oxide as pigment.

Past, it is known that the white outward appearance and there is good impact strength by the combination of PC-PDMS and titanium oxide Compositions.The excellences such as mechanical properties, optical characteristics such as the most known resistance to impact, rigidity and reflectivity Characteristics are the most excellent Polycarbonate-based resin composition (with reference to patent documentation 1).According to patent documentation 1, the content of titanium oxide is 5～10% contain The compositions having PC-PDMS demonstrates good reflectance and mechanical strength.It addition, it is the most known without phosphorus Demonstrate in the case of flame retardant, halogenated flame retardant excellence anti-flammability and in highly reflective, high light-proofness and thermally-stabilised Property excellent polycarbonate-based resin composition (with reference to patent documentation 2).According to patent documentation 2, the content of titanium oxide be 5～ The compositions containing PC-PDMS of 50% demonstrates good reflectance and Izod impact strength and anti-flammability.

Compositions described in these documents demonstrates high reflective character, but on the other hand containing due to titanium oxide Amount is many, and the intensity that the PC-PDMS that therefore its strength ratio is original is had is low, and in described purposes, its proportion is more than appropriate value, It is therefore contemplated that develop, there is good reflectance and mechanical strength etc. and the less combination containing PC-PDMS of titanium oxide content Thing.

On the other hand, it is also known that the titanium oxide containing small amount (such as 1～2.5 weight %) and the compositions of PC-PDMS (with reference to patent documentation 3).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 5-320519 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2004-91567 publication

Patent documentation 3: Japanese Unexamined Patent Application Publication 2007-509208 publication

Summary of the invention

The problem that invention is solved

In the compositions containing PC-PDMS described in patent documentation 3, as the means of raising anti-flammability, employ few Amount titanium oxide, but any record is not had for color appearance.

Therefore, the problem of the present invention is to provide a kind of polycarbonate-based resin composition, and it is maintaining Merlon-poly- The excellent characteristic of organosiloxane copolymer simultaneously, has the color appearance of excellence.

Solve the means of problem

The present inventor etc. have carried out research extensively and profoundly, if it was found that Merlon-poly organo alkyl copolymer In polysiloxane chain length, then be difficult to show intensity, therefore to show resistance to impact, need certain above poly-silicon The length of oxygen alkane chain length, and, if polysiloxanes chain length is long, although good intensity then can be shown, but the meeting of formed products surface The striped appearance producing black is bad, and it was found that, if under given conditions, then can have maintaining Merlon-poly- There is while the characteristic of organic siloxane copolymer the color appearance of excellence.

That is, the present invention relates to following [1]～[10].

[1] a kind of polycarbonate-based resin composition, its contain (A) polycarbonate-based resin 99.9～96 mass parts and (B) titanium oxide 0.1～4 mass parts, wherein, (A) composition adds up to 100 mass parts with (B) composition,

Described (A) polycarbonate-based resin comprises:

Merlon-poly organo alkyl copolymer (A-1) 5～100 mass %, Merlon-polysiloxane are common Aromatic copolycarbonate (A-3) 0～95 mass % beyond polymers (A-2) 0～95 mass % and described (A-1) and (A-2),

Described Merlon-poly organo alkyl copolymer (A-1) be main chain have the repetitive shown in logical formula (I) and Merlon-poly organo the alkyl copolymer of logical Component units shown in formula (II), wherein, the n in logical formula (II) be 25～ 65, and the content of the Component units shown in logical formula (II) is 2～20 mass %,

Described Merlon-poly organo alkyl copolymer (A-2) be main chain have the repetitive shown in logical formula (I) and Merlon-poly organo the alkyl copolymer of logical Component units shown in formula (II), wherein, the n in logical formula (II) be 70～ 350, and the content of the Component units shown in logical formula (II) is 2～20 mass %.

[changing 1]

[in formula, R¹And R²Separately represent halogen atom, the alkyl of carbon number 1～6 or the alkane of carbon number 1～6 Epoxide, X represents the ring Asia of singly-bound, the alkylidene of carbon number 1～8, the alkylidene radical of carbon number 2～8, carbon number 5～15 Alkyl, the ring alkylidene radical of carbon number 5～15 ,-S-,-SO-,-SO₂-,-O-or-CO-, a and b separately represent 0～4 Integer,

R³～R⁶Separately represent hydrogen atom, halogen atom or the alkyl of carbon number 1～6, the alkane of carbon number 1～6 Epoxide or the aryl of carbon number 6～12, Y represents singly-bound, containing aliphatic or aromatic organic residue, and n is average repetition Number.]

[2] according to the polycarbonate-based resin composition described in above-mentioned [1], wherein, at the composition list shown in logical formula (II) In unit, Y is the organic residue from chavicol or acetaminol.

[3] according to the polycarbonate-based resin composition described in above-mentioned [1] or [2], wherein, at the weight shown in logical formula (I) In multiple unit, X is isopropylidene, and a=b=0.

[4] according to the polycarbonate-based resin composition according to any one of above-mentioned [1]～[3], wherein, in logical formula (II) In shown Component units, R³～R⁶It is methyl.

[5] according to the polycarbonate-based resin composition according to any one of above-mentioned [1]～[4], wherein, at (A) composition Polycarbonate-based resin in, from the content of the Component units shown in the logical formula (II) of (A-2) composition relative to (A-1)～ (A-3) total amount of composition is below 2.5 mass %.

[6] according to the polycarbonate-based resin composition according to any one of above-mentioned [1]～[5], wherein, relative to (A) Total 100 mass parts of composition and (B) composition contains mixed powder 0.1～1 mass parts of politef possibly together with (C).

[7] according to the polycarbonate-based resin composition according to any one of above-mentioned [1]～[6], wherein, relative to (A) Total 100 mass parts of composition and (B) composition possibly together with 0.01～0.15 mass parts (D) selected from the alkali metal salt of organic sulfonic acid and At least one in the alkali salt of organic sulfonic acid.

[8] a kind of formed products, it comprises the polycarbonate-based resin composition according to any one of above-mentioned [1]～[7].

[9] a kind of elec-tric-electronic sets spare unit, and it is polycarbonate-based that it comprises according to any one of above-mentioned [1]～[7] Resin combination.

[10] a kind of automotive part, it comprises the polycarbonate-based resin combination according to any one of above-mentioned [1]～[7] Thing.

Invention effect

According to the present invention it is possible to provide a kind of polycarbonate-based resin composition, it is maintaining Merlon-poly-organosilicon The excellent characteristic of siloxane copolymers simultaneously, has the color appearance of excellence.The polycarbonate-based resin composition of the present invention is also There is the anti-flammability of excellence.

Detailed description of the invention

[polycarbonate-based resin composition]

The present invention relates to a kind of polycarbonate-based resin composition, it contains (A) polycarbonate-based resin 99.9～96 matter Amount part and (B) titanium oxide 0.1～4 mass parts (wherein, (A) composition and (B) composition add up to 100 mass parts.)

Described (A) polycarbonate-based resin comprises:

[changing 2]

In logical formula (I), as R¹And R²The halogen atom separately represented, can enumerate: fluorine atom, chlorine atom, bromine are former Son, atomic iodine.

As R¹And R²The alkyl separately represented, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, various butyl (" various " expression includes straight-chain and the group of all of branched, below has same implication.), various amyl group, various Hexyl.As R¹And R²The alkoxyl separately represented, can enumerate the situation that alkyl portion is described alkyl.

The alkylidene represented as X, can enumerate such as: methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene Deng, the preferably alkylidene of carbon number 1～5.The alkylidene radical represented as X, can enumerate: ethidine, isopropylidene etc..As The ring alkylidene that X represents, can enumerate: the ring of ring penta diyl, hexamethylene diyl, the pungent diyl of ring etc., preferably carbon number 5～10 is sub- Alkyl.The ring alkylidene radical represented as X, can enumerate such as: cyclohexylidene base, 3,5,5-3-methyl cyclohexanol fork base, 2-adamantylidene The ring alkylidene radical of the ring alkylidene radical of base etc., preferably carbon number 5～10, more preferably carbon number 5～8.

A and b separately represents the integer of 0～4, preferably 0～2, more preferably 0 or 1.

In logical formula (II), as R³～R⁶The halogen atom separately represented, can enumerate: fluorine atom, chlorine atom, bromine are former Son, atomic iodine.As R³～R⁶The alkyl that separately represents, alkoxyl, can enumerate and R¹And R²The identical base of situation Group.As R³～R⁶The aryl separately represented, can enumerate: phenyl, naphthyl etc..

Comprise aliphatic organic residue as what Y represented, can enumerate such as: carbon number 1～10 (preferably carbon atom Several 1～6, be more preferably carbon number 1～3) alkylidene etc..It addition, comprise aromatic organic residue as what Y represented, Can enumerate such as: the arlydene etc. of the ring carbons numbers 6～12 such as phenylene, naphthylene, biphenyl diyl.

((A) polycarbonate-based resin)

-(A-1)-

First " Merlon-poly organo alkyl copolymer (A-1) " to one of (A) composition and for neccessary composition is carried out Explanation.

In Merlon-poly organo alkyl copolymer (A-1), the content of the Component units shown in above-mentioned logical formula (II) is 2～20 mass %, it is preferably 2～15 mass %, more preferably 2～10 mass %, more preferably 3～8 mass %, the most excellent Elect 4～7 mass %, particularly preferably 4～6 mass % as.If less than 2 mass %, then the effect that impact strength improves is not filled Point, if additionally more than 20 mass %, then the reduction of thermostability increases.

It addition, in (A-1), the averaged repeating numbers n in the Component units shown in above-mentioned logical formula (II) is 25～65, is preferably 30～60, more preferably 30～50, more preferably 30～45.(A-1), in, if n is less than 25, then impact strength improves Effect is insufficient, if more than 65, is then difficult to obtain the color appearance of excellence.

(A-1) viscosity-average molecular weight (Mv) is preferably 16,000～30,000, more preferably 16,000～25,000, enter one Step is preferably 17,000～23,000.If viscosity-average molecular weight (A-1) is within the range, then the intensity of formed products is abundant, copolymerization It is excessive that the viscosity of thing will not become, and productivity ratio during manufacture is stable, the most easily carries out thin molded.

Merlon-poly organo alkyl copolymer (A-1) can by make the divalent phenol shown in following formula (1), Polysiloxane shown in following formula (2) manufactures with phosgene, carbonic ester or chloro-formate copolymerization.It addition, by making The polycarbonate oligomer polycarbonate oligomer of chloro-carbonic acid ester group (the such as end have) reacts with polysiloxane, Merlon-poly organo alkyl copolymer (A-1) can also be produced.

In the manufacture of Merlon-poly organo alkyl copolymer (A-1), preferably make shown in following formula (2) poly-has The response rate of organic siloxane is more than 95%, is more preferably more than 97%, is further preferably more than 99%.

[changing 3]

[in formula (1), X, R¹～R², a with b identical with the situation in described logical formula (I).In formula (2), R³～R⁶, Y and N is identical with the situation in described logical formula (II), and when manufacturing (A-1), n is 25～65.Z represents halogen atom ,-R⁷OH、-R⁷-Z′- R⁸-OH、-R⁷COOH、-R⁷NH₂,-COOH or-SH, described R⁷Represent substituted or unsubstituted alkylidene, substituted or unsubstituted ring Alkylidene or substituted or unsubstituted arlydene.Described R⁸It is expressed as the arlydene of ring carbon atom number 6～12, described Z ' expression The alkylidene of carbon number 1～8, the alkylidene radical of carbon number 2～8, the ring alkylidene of carbon number 5～10, carbon number 5～ The ring alkylidene radical of 10.M represents 0 or 1.]

The halogen atom represented as Z, can enumerate such as: fluorine atom, chlorine atom, bromine atoms, atomic iodine.Among them preferably For chlorine atom.

-the R represented as Z⁷OH、-R⁷-Z′-R⁸-OH、-R⁷COOH、-R⁷NH₂In R⁷The alkylidene represented, can enumerate example As: the alkylidene of the carbon numbers 1～10 (preferably 1～5) such as methylene, ethylidene, propylidene, trimethylene, pentamethylene. It addition, as R⁷The ring alkylidene represented, can enumerate such as: the ring carbons number such as cyclopentylene, cyclohexylidene 3～10 is (excellent Elect 4～8 as) ring alkylidene.As R⁷The arlydene represented, can enumerate such as: phenylene, naphthylene, biphenyl diyl etc. become The arlydene of ring carbon atom number 6～12.

R⁷Can be by the alkyl of carbon number 1～5, the alkoxyl of carbon number 1～5, the virtue of ring carbons number 6～12 Bases etc. replace.As this alkyl, can enumerate: methyl, ethyl, propyl group, various butyl etc..As this alkoxyl, can enumerate: alkyl Position is the group of described alkyl.As this aryl, phenyl etc. can be enumerated.

As Z ' represent alkylidene, alkylidene radical, ring alkylidene, ring alkylidene radical, the base identical with the situation of X can be enumerated Group.As the alkylidene radical of Z ', preferably carbon number 2～8, more preferably isopropylidene.

-(A-2)-

Then " Merlon-poly organo alkyl copolymer (A-2) " to one of (A) composition and for optional member is carried out Explanation.

In Merlon-poly organo alkyl copolymer (A-2), the content of the Component units shown in described logical formula (II) is 2～20 mass %, it is preferably 2～15 mass %, more preferably 2～10 mass %, more preferably 3～8 mass %, especially It is preferably 3～7 mass %.If less than 2 mass %, then the effect that impact strength improves is insufficient, if additionally more than 20 matter Amount %, then the reduction of thermostability increases.

It addition, in (A-2), the averaged repeating numbers n in the Component units shown in above-mentioned logical formula (II) is 70～350, preferably It is 80～200, more preferably 80～110, more preferably 80～100.If n is less than 70, then the effect that impact strength improves The most insufficient, if more than 350, then viscosity increases, and operability is deteriorated.

(A-2) viscosity-average molecular weight (Mv) is preferably 16,000～30,000, more preferably 16,000～25,000, enter one Step is preferably 17,000～23,000.If viscosity-average molecular weight (A-2) is within the range, then the intensity of formed products is abundant, copolymerization It is excessive that the viscosity of thing will not become, and productivity ratio during manufacture is stable, the most easily carries out thin molded.

Further, from the generation of the bad order of suppression blackstreak, it is easy to acquisition improves the effect of impact strength Viewpoint is set out, and the Component units shown in described logical formula (II) in (A-2) is preferably 2.5 mass % relative to (A) composition total amount Below, it is more preferably below 2.0 mass %.

Merlon-poly organo alkyl copolymer (A-2) can by make the divalent phenol shown in described formula (1), Polysiloxane (wherein, n is 70～350) shown in described formula (2) and phosgene, carbonic ester or chloro-formate copolymerization Manufacture.It addition, by making the polycarbonate oligomer polycarbonate oligomer of chloro-carbonic acid ester group (the such as end have) with poly- Organosiloxane reacts, it is also possible to produce Merlon-poly organo alkyl copolymer (A-2).

In the manufacture of Merlon-poly organo alkyl copolymer (A-2), preferably make shown in described formula (2) poly-has The response rate of organic siloxane is more than 90%, is more preferably more than 95%, is further preferably more than 97%, especially Preferably it is more than 99%.

In the polycarbonate-based resin composition of the present invention, as the formula (1) used in the raw material of (A-1) or (A-2) Shown divalent phenol, has a various material, but particularly preferred 2, double (4-hydroxy phenyl) propane of 2-(common name: bisphenol-A).If using Bisphenol-A is as divalent phenol, then (A-1) or (A-2) becomes: in logical formula (I), and X is isopropylidene and is a=b=0.

As the bis-phenol beyond bisphenol-A, can enumerate such as: double (4-hydroxy phenyl) methane, 1,1-is double (4-hydroxy phenyl) Ethane, 2, double (4-hydroxy phenyl) butane of 2-, 2, double (4-hydroxy phenyl) octane of 2-, double (4-hydroxy phenyl) phenylmethane, double (4-hydroxy phenyl) diphenyl methane, 2, double (the 4-hydroxy-3-methyl phenyl) propane of 2-, double (4-hydroxy phenyl) naphthyl methane, 1,1-double (4-hydroxytertiarybutylphenyl) propane, 2, double (4-hydroxyl-3-bromophenyl) propane of 2-, 2,2-double (4-hydroxyl-3,5-tetra- Aminomethyl phenyl) propane, 2, double (4-hydroxyl-3-chlorphenyl) propane of 2-, 2, double (4-hydroxyl-3,5-Dichlorobenzene base) propane of 2-, 2, Double (hydroxyaryl) alkanes such as double (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2-；1,1-double (4-hydroxy phenyl) Pentamethylene., 1, 1-bis(4-hydroxyphenyl)cyclohexane, 1, double (the 4-hydroxy phenyl)-3 of 1-, 5,5-trimethyl-cyclohexanes, 2, double (the 4-hydroxy benzenes of 2- Base) norbornane, 1, double (hydroxyaryl) cycloalkanes such as double (4-hydroxy phenyl) cyclododecanes of 1-；4,4 '-dihydroxy phenyl Ether, 4,4 '-dihydroxy-3, the dihydroxy aryl ethers such as 3 '-3,5-dimethylphenyl ether；4,4 '-dihydroxydiphenyl thioether, 4,4 '- Dihydroxy-3, the dihydroxy diaryl thioether class such as 3 '-dimethyl diphenyl sulfide；4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '- Dihydroxy-3, the dihydroxy diaryl sulfoxide type such as 3 '-dimethyl diphenyl sulfoxide；4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-two Hydroxyl-3, the dihydroxy diaryl sulfone class such as 3 '-dimethyl diphenyl sulfone；4, the dihydroxybiphenyl class such as 4 '-dihydroxybiphenyl；9,9- Double (4-hydroxy phenyl) fluorenes, 9, the dihydroxy diaryl fluorenes class such as double (4-hydroxy-3-methyl phenyl) fluorenes of 9-；Double (4-hydroxy phenyls) Diphenyl methane, 1, double (4-hydroxy phenyl) diamantane (obsolete) of 3-, 2, double (4-hydroxy phenyl) diamantane (obsolete) of 2-, 1, double (the 4-hydroxy benzenes of 3- Base)-5, the dihydroxy diaryl adamantane such as 7-dimethyladamantane；4,4 '-[1,3-phenylene is double (1-methyl ethidine)] Bis-phenol, 10, double (4-hydroxy phenyl)-9-anthrone of 10-, 1, double (the 4-hydroxy benzenes sulfenyl)-2 of 5-, 3-dioxole etc..

These divalent phenols can be used alone a kind, it is also possible to is mixed with two or more.

Polysiloxane shown in formula (2) can be by making the preferred second of phenols with olefinic unsaturation carbon-carbon bond Thiazolinyl phenol, chavicol, acetaminol, isopropenyl phenol etc. have the polysiloxane chain of regulation polymerization degree n End generation hydrosilylation (hydrosilanation) reaction and be easily manufactured.Above-mentioned phenol is more preferably allyl Base phenol or acetaminol.Now, the Y in the logical formula (II) of (A-1), (A-2) is from chavicol or acetaminol Organic residue.

As the polysiloxane shown in formula (2), such as following polysiloxane can be enumerated.

[changing 4]

In described formula (3)～(11), R³～R⁶With the R in formula (1)³～R⁶Equally.N is that organosiloxane constitutes list The averaged repeating numbers of unit, represents 25～65 in the case of (A-1), represent 70～350 in the case of (A-2).It addition, c just represents Integer, the integer of preferably 1～6, the integer of more preferably 1～3, more preferably 3.

Wherein, from the viewpoint of polymerization easiness, phenol modified polyorganosiloxanes (the preferably c shown in preferred formula (3) =3).From the viewpoint of obtaining easiness, further preferably as a kind of α in the compound shown in formula (4), ω- Double [3-(o-hydroxy-phenyl) propyl group] polydimethylsiloxane or as a kind of α in the compound shown in formula (5), ω-bis-[3-(4-hydroxy 3-methoxybenzene base) propyl group] polydimethylsiloxane.

Above-mentioned phenol modified polyorganosiloxanes can utilize known method to manufacture.As known autofrettage, there is example Such as following autofrettage.

Make cyclotrisiloxane and disiloxane react in the presence of acidic, synthesize α, the organic poly-silica of ω-dihydro Alkane.Now, by changing the rate of charge of cyclotrisiloxane and disiloxane, the α with desired repetitive can be synthesized, ω-dihydro organopolysiloxane.Then, in the presence of hydrosilylation reactions catalyst, this chavicol, Ding Zi are made Fragrant phenol etc. has phenolic compounds and a α of unsaturated fatty hydrocarbons base, ω-dihydro organopolysiloxane generation additive reaction, thus The phenol modified polyorganosiloxanes with desired repetitive can be manufactured.

It addition, in this stage, the cyclic polyorganosiloxane of low-molecular-weight, excessive above-mentioned phenolic compounds are with impurity Form remains, and the most under reduced pressure heats, is distilled off by these low molecular compounds.

-(A-3)-

Then " aromatic copolycarbonate (A-3) " of one of (A) composition is illustrated.

(A-3) the whole aromatic copolycarbonates beyond (A-1) and (A-2) are equivalent to.Wherein, as (A-3), it is preferably Only comprise the aromatic copolycarbonate of the Component units shown in described logical formula (I).

In the polycarbonate-based resin composition of the present invention, (A-3) can use and utilize conventional aromatic copolycarbonate The aromatic copolycarbonate that obtains of autofrettage, i.e. in the presence of the organic solvent, aqueous alkali of reactionlessness, make bivalence benzene After phenol system compound and phosgene reaction, add the polymerization catalyst such as tertiary amine or quaternary ammonium salt and make its interfacial polymerization being polymerized； Make divalent phenol based compound be dissolved in the mixed solution of pyridine or pyridine and atent solvent, import phosgene and directly manufacture Pyridine method etc..

When above-mentioned reaction, end terminator, molecular weight regulator, branching agent etc. can be used as required.

As the divalent phenol based compound used in the manufacture of (A-3), 2 can be enumerated, double (4-hydroxy phenyl) propane of 2-(= Bisphenol-A), double (4-hydroxy phenyl) methane, 1, double (4-hydroxy phenyl) ethane of 1-, 2, double (4-hydroxy phenyl) butane of 2-, 2,2- Double (4-hydroxy phenyl) octane, double (4-hydroxy phenyl) phenylmethane, double (4-hydroxy phenyl) diphenyl methane, 2, the double (4-of 2- Hydroxy-3-methyl phenyl) propane, double (4-hydroxy phenyl) naphthyl methane, 1, double (4-hydroxyl-3-tert-butyl-phenyl) propane of 1-, 2,2-double (4-hydroxyl-3-bromophenyl) propane, 2, double (4-hydroxyl-3,5-3,5-dimethylphenyl) propane of 2-, 2,2-double (4-hydroxyl- 3-chlorphenyl) propane, 2, double (4-hydroxyl-3,5-Dichlorobenzene base) propane of 2-, 2, double (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2- Deng double (hydroxyaryl) alkanes；1,1-double (4-hydroxy phenyl) Pentamethylene., 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-is double (4-hydroxy phenyl)-3,5,5-trimethyl-cyclohexanes, 2, double (4-hydroxy phenyl) norbornane of 2-, 1,1-is double (4-hydroxy phenyl) Double (hydroxyaryl) cycloalkane such as cyclododecane；4,4 '-dihydroxy phenyl ether, 4,4 '-dihydroxy-3,3 '-3,5-dimethylphenyl The dihydroxy aryl ethers such as ether；4,4 '-dihydroxydiphenyl thioether, 4,4 '-dihydroxy-3,3 '-dimethyl diphenyl sulfide etc. Dihydroxy diaryl thioether class；4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxy-3,3 '-dimethyl diphenyl sulfoxide etc. Dihydroxy diaryl sulfoxide type；4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxy-3, the dihydroxy such as 3 '-dimethyl diphenyl sulfone Base diaryl sulfone class；4, the dihydroxybiphenyl class such as 4 '-dihydroxybiphenyl；9,9-double (4-hydroxy phenyl) fluorenes, 9, double (the 4-hydroxyl of 9- Base-3-aminomethyl phenyl) the dihydroxy diaryl fluorenes class such as fluorenes；Double (4-hydroxy phenyl) diphenyl methane, 1, double (the 4-hydroxy benzenes of 3- Base) diamantane (obsolete), 2, double (4-hydroxy phenyl) diamantane (obsolete) of 2-, 1, double (the 4-hydroxy phenyl)-5 of 3-, the dihydroxy such as 7-dimethyladamantane Base diaryl adamantane；4,4 '-[1,3-phenylene double (1-methyl ethidine)] bis-phenols, 10,10-double (4-hydroxy phenyl)- 9-anthrone, 1, double (the 4-hydroxy benzenes sulfenyl)-2 of 5-, 3-dioxa amylene etc..These divalent phenols can individually use, also Can be used in mixed way two or more.

When the manufacture of (A-3), generally use end terminator or molecular weight regulator.

As molecular weight regulator, as long as being that typically in the polymerization of polycarbonate resin the molecular weight regulator used, Then can use various material.

Specifically, as a bivalent phenol, can enumerate such as: phenol, adjacent normal-butyl phenol, a normal-butyl phenol, align Butylphenol, adjacent isobutyl group phenol, an isobutyl group phenol, to isobutyl group phenol, o-tert-butylphenol, a tert-butyl phenol, right Tert-butyl phenol, adjacent n-pentyl phenol, a n-pentyl phenol, align amyl phenol, adjacent n-hexyl phenol, a n-hexyl phenol, Align hexylphenol, to tert-octyl phenol, o cyclohexyl phenol, a cyclohexylphenol, p-cyclohexylphenol, o-phenyl phenol, Between phenylphenol, 4-hydroxydiphenyl, adjacent n-nonyl phenol, a nonyl phenol, align nonyl phenol, adjacent cumyl phenol, a cumyl Phenol, p-cumylphenol, adjacent naphthyl phenol, a naphthyl phenol, to naphthyl phenol, 2,5-DI-tert-butylphenol compounds, 2, the tertiary fourth of 4-bis- Base phenol, 3,5-DI-tert-butylphenol compounds, 2,5-dicumyl phenol, 3,5-dicumyl phenol, paracresol, bromophenol, tribromphenol, At ortho position, meta or para position have straight-chain that average carbon atom number is 12～35 or branched alkyl monoalkyl phenol, 9-(4-hydroxy phenyl)-9-(4-methoxyphenyl) fluorenes, 9-(4-hydroxy-3-methyl phenyl)-9-(4-methoxyl group-3-methylbenzene Base) fluorenes, 4-(1-adamantyl) phenol etc..

In these bivalent phenols, p-t-butyl phenol, p-cumylphenol, 4-hydroxydiphenyl etc. are preferably used.The most also Two or more compound be can be used together.

Further, relative to above-mentioned divalent phenol based compound, can by 0.01～3 mole of %, particularly 0.1～1 The scope of mole % with branching agent, forms branching polycarbonate, as branching agent, it is possible to use 1,1,1-tri-(4-hydroxy benzenes Base) ethane, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethidine] bis-phenols, α, α ', α "-three (4- Hydroxy phenyl)-1,3,5-triisopropylbenzenes, 1-[Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl]-4-[α ', α '-bis-(4 "-hydroxyl Phenyl) ethyl] benzene, phloroglucinol (Off ロログリシ Application), trimellitic acid, isatin double (orthoresol) etc. have more than 3 senses The compound of group.

(compounding ratio of each (A) composition)

(A) content of (A-1)～(A-3) in polycarbonate-based resin is (A-1) 5～100 mass %, (A-2) 0～95 Quality % and (A-3) 0～95 mass %.

If the content of (A-1) (A) in composition is less than 5 mass %, then need when manufacturing (A-1) to make containing logical formula (II) The content of the polysiloxane block section of shown construction unit is more than 20 mass %, in this case, is manufacturing (A- 1) in polymerization process time, the uniformity of reaction reduces sometimes, and polymer and rinse water in the matting of polymer Separation property be deteriorated sometimes, therefore the productivity ratio of (A-1) is substantially reduced.On the other hand, if the content of (A-2), (A-3) exceedes 95 mass %, then owing to the ratio of (A-1) is less than 5 mass %, so that increase when manufacturing (A-1) containing logical formula (II) institute The content of the polysiloxane block section of the construction unit shown, the most preferred for reason similar to the above.

The content of (A-1) from viewpoint similar to the above, (A) composition is preferably 20～100 mass %, more excellent Electing 30～100 mass %, more preferably 40～100 mass % as, the content of (A-2) is preferably 0～80 mass %, more excellent Electing 0～70 mass %, more preferably 0～60 mass %, particularly preferably 0～40 mass % as, the content of (A-3) is preferred It is 0～80 mass %, more preferably 0～70 mass %, more preferably 0～60 mass %, particularly preferably 0～40 matter Amount %.

It should be noted that as (A) composition, be preferably be made up of (A-1) and (A-2) material, by (A-1) and (A- 3) material constituted, the material being all made up of (A-1)～(A-3).(A) in the case of composition contains only (A-1) and (A-2), Both are preferably (A-1) 20～95 mass % and (A-2) 80～5 mass %, more preferably (A-1) 20～90 matter containing ratio Amount % and (A-2) 80～10 mass %, more preferably (A-1) 40～80 mass % and (A-2) 60～20 mass %, special It is preferably (A-1) 50～70 mass % and (A-2) 50～30 mass %.

(A), in the case of composition contains only (A-1) and (A-3), both are preferably (A-1) 20～95 matter containing ratio Amount % and (A-3) 80～5 mass %, more preferably (A-1) 20～90 mass % and (A-3) 80～10 mass %, the most excellent Elect (A-1) 50～90 mass % and (A-3) 50～10 mass % as.

It addition, (A) composition contain (A-1)～(A-3) whole in the case of, they be preferably (A-1) containing ratio 20～80 mass %, (A-2) 10～60 mass % and (A-3) 10～50 mass %, more preferably (A-1) 25～60 mass %, (A-2) 10～50 mass % and (A-3) 25～60 mass %.

((B) titanium oxide)

In the polycarbonate-based resin composition of the present invention, from the viewpoint of impact strength, (B) titanium oxide (dioxy Change titanium: TiO₂) content be 0.1～4 mass parts relative to (A) 99.9～96 mass parts, preferably with respect to (A) 99.5～97 matter Amount part be 0.5～3 mass parts, further preferably relative to (A) 99.5～98 mass parts be 0.5～2 mass parts (wherein, (A) become Point and (B) composition add up to 100 mass parts.).

Mean diameter of titanium oxide is preferably 0.05～0.5 μm, more preferably 0.1～0.4 μm, more preferably 0.15～0.3 μm.

Titanium oxide can be the titanium oxide that its surface is wrapped by.The surface of titanium oxide can be by including aluminum, silicon, magnesium, oxidation The hydrous oxide of at least one element of the elements such as zirconium, titanium, stannum and/or oxide cladding.Titanium oxide can be further by not The polyhydric alcohol of nitrogen atom, organo-silicon compound, alkanol amine, higher aliphatic acids etc. carry out surface process.As titanium oxide, Preferably it is coated with by aluminum, the hydrous oxide of silicon and/or oxide.It addition, it is also preferred that carried out table by the polyhydric alcohol of not nitrogen atom Titanium oxide after the process of face.

As the polyhydric alcohol of the not nitrogen atom for being coated with titanium oxide, can enumerate: trimethylolpropane, trihydroxy methyl second Alkane, double trimethylolpropane, trimethylolpropane ethoxylate, tetramethylolmethane etc., wherein, drop from being possible to prevent impact strength From the viewpoint of low, preferably trimethylolpropane and trimethylolethane.These polyhydric alcohol can be used alone a kind, it is also possible to It is applied in combination two or more.

By the method for the polyhydric alcohol clad surface of not nitrogen atom, can be any one in damp process and dry process. Damp process can be carried out by the following method: adds oxidation in the polyhydric alcohol of not nitrogen atom and the mixed liquor of low boiling point solvent Low boiling point solvent is removed after titanium, stirring.Dry process can be carried out by the following method: by polyhydric alcohol and the oxidation of not nitrogen atom Titanium mixes in enjoying the mixers such as She Er mixer, rotary drum, or the polyhydric alcohol of not nitrogen atom is dissolved in a solvent, Or the method that titanium oxide is sprayed by the mixed solution that obtains in a solvent of dispersion.

The manufacture method of titanium oxide can be to utilize any one method carrying out manufacturing in chlorine method, sulfuric acid process.It addition, The crystal structure of titanium oxide can use any one in rutile-type, Detitanium-ore-type, but from polycarbonate-based resin combination The viewpoints such as the heat stability of thing and light resistance are set out, preferably rutile-type.

((C) mixed powder containing politef)

The polycarbonate-based resin composition of the present invention can also coordinate the mixed powder containing politef further As (C) composition.Mixed powder containing politef comprise below mean diameter 10 μm politef system particle and Organic based polymer particle.

The form of the mixed powder containing politef is with politef system particle and organic based polymer particle Mixing ratio, particle diameter and different, be not particularly limited.Such as exist: organic based polymer particle surrounds politef system particle The form of surrounding, opposite to that ground politef system particle surround the form, multiple of surrounding of organic based polymer particle Particle is relative to the form etc. of 1 particle coacervation.

The mixed powder containing politef used in the present invention needs: comprise the polytetrafluoroethyl-ne of below particle diameter 10 μm In alkene particle and organic based polymer, and powder body, politef does not become the agglomerate of more than 10 μm.Contain as such There is the mixed powder of politef, preferably: the polytetrafluoroethylparticle particle aqueous liquid dispersion of particle diameter 0.05～1.0 μm and organic system After the mixing of polymer particle aqueous liquid dispersion by solidification or spray drying powder body from obtained by mixed powder or at grain Lead to after the monomer constituting organic based polymer being polymerized in the presence of the polytetrafluoroethylparticle particle aqueous liquid dispersion of footpath 0.05～1.0 μm Supersolidification or spray drying and powder body from obtained by mixed powder or in the polytetrafluoro being mixed with particle diameter 0.05～1.0 μm The dispersion liquid of beta particles aqueous liquid dispersion and organic based polymer particle aqueous liquid dispersion will have ethylenic unsaturated bond After monomer emulsion polymerization by solidification or be spray-dried and powder body from obtained by mixed powder.

It addition, the polytetrafluoroethylparticle particle aqueous liquid dispersion of particle diameter 0.05～1.0 μm can be by using fluorine-containing surfactants The emulsion polymerization of agent makes tetrafluoroethylene monomer polymerization obtain.During emulsion polymerization, as copolymer composition in politef, can To use: Fluorine containing olefine, (methyl) propylene such as hexafluoropropene, chlorotrifluoroethylene, fluoroalkylvinyl, perfluoroalkyl vinyl ethers The fluorine-containing Arrcostabs of (methyl) acrylic acid such as acid perfluoroalkyl ester.These copolymer compositions are preferably 10 mass % relative to tetrafluoroethene Below.

As the marketable material of politef system particle aqueous liquid dispersion, Asashi ICI can be enumerated The Fluon AD-1 of Fluoropolymer company, AD-936, Polyflon D-1, D-2 of Daikin Industries company, three wells Teflon (registered trade mark) 30J of fluorine chemistry company of Du Pont etc. are as representative examples.

Described organic based polymer particle is not particularly limited, and can enumerate such as: Merlon (PC), poly terephthalic acid Glycol ester, polybutylene terephthalate (PBT), PEN, PBN, 6-nylon, 66-nylon, polyarylate, polyphenylene oxide, Noryl, polyphenylene sulfide, polyether-ketone, polyether-ether-ketone, polysulfones, polyether sulfone, polyamide Acid imide, Polyetherimide, polypropylene, polyethylene, polystyrene, high impact polystyrene, poly-(methyl) alkyl acrylate, Polyacetals, comprise aromatic series alkenyl compound and the copolymer of vinyl cyanide based compound, phenolic resin, Lauxite, trimerization Melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicones, polyurethane, ethylene-propylene copolymer, benzene second Alkene-butadiene block copolymer, polybutadiene, polyisoprene, the random copolymer of styrene-butadiene and block copolymerization The diene series rubbers such as thing, the hydride of this block copolymer, acrylonitrile-butadiene copolymer, butadiene isoprene copolymer Glue, the random copolymer of ethylene-propylene and block copolymer, the random copolymer of Ethylene/Butylene and block copolymer, ethylene with The copolymer of the ethylene-esters of unsaturated carboxylic acids such as the copolymer of alpha-olefin, ethylene-methyl acrylate, Ethylene-butyl acrylate, Acrylic flexible polymer, the ethane-acetic acid ethyenyls such as acrylate-butadiene copolymer, such as butyl acrylate-butadiene The ethylene-propylenes such as the copolymer of ester, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer are non- Conjugated diene terpolymer, butylene-isoprene copolymer, chlorinated polyethylene, polysiloxane, poly-(methyl) acrylic acid The rubber polymers such as Arrcostab, comprise polysiloxane and the compounded rubber of poly-(methyl) alkyl acrylate, rubber mass Polymer and aromatic vinyl monomer and the graft copolymer of cyanided vinyl monomer glycerol polymerization, comprise poly-organosilicon The compounded rubber of oxygen alkane and poly-(methyl) alkyl acrylate and the compounded rubber graft copolymerization of vinyl monomer-grafted Thing and relative to whole polymer contain can with composition 50 mass % of they copolymerization below polymer etc..These polymerizations Thing can be used singly or in combination of two or more.

From the viewpoint of the dispersibility of politef, it is preferably, with polycarbonate-based resin, there is being polymerized of affinity Thing, particularly preferably with poly-(methyl) alkyl acrylate polymer as main constituent, rubber polymer, further preferably contains More than 30 mass % there is the polymer of poly-(methyl) alkyl acrylate of the alkyl of carbon number more than 4.

As described rubber polymer, can illustrate: polybutadiene, polyisoprene, styrene-butadiene random Copolymer and block copolymer, the hydride of this block copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene are common The diene series rubbers such as polymers, the random copolymer of ethylene-propylene and block copolymer, the random copolymer of Ethylene/Butylene and embedding Ethylene-the unsaturations such as section copolymer, ethylene and the copolymer of alpha-olefin, ethylene-methyl acrylate, Ethylene-butyl acrylate The acrylic acid series flexible polymers such as the copolymer of carboxylate, acrylate-butadiene copolymer, such as butyl acrylate-butadiene Thing, the copolymer of ethane-acetic acid ethyenyl ester, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene are common Ethylene-propylene non-conjugated diene terpolymer, the butylene-isoprene copolymers etc. such as polymers, these polymer can be independent Use, it is also possible to be applied in combination two or more.

Wherein, preferably illustrate ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymer diene series rubber, third Olefin(e) acid system elastomeric polymer, can illustrate polybutadiene, SB, preferably polybutadiene, benzene second especially Alkene-butadiene copolymer, polysiloxane, poly-(methyl) alkyl acrylate, comprise polysiloxane and poly-(methyl) The compounded rubber etc. of alkyl acrylate.Autofrettage as these organic based polymer, it is possible to use polymerisation in bulk, solution gather The generally well-known methods such as conjunction, suspension polymerisation, emulsion polymerization.

Politef system particle in mixed powder containing politef and the mixing of organic polymer thing particle Ratio is not particularly limited, but preferably polytetrafluoroethylene system particle is 0.1～90 mass %.About mixing containing politef Close powder body, can be obtained by mixing by politef system particle dispersion and organic polymer thing particle dispersion stirred Aqueous liquid dispersion is put in the hot water being dissolved with the slaine such as calcium chloride, magnesium sulfate and carries out the method etc. saltoutd, solidify, by This reclaims with the isolated in form of particle.

In the case of coordinating (C) composition in the polycarbonate-based resin composition of the present invention, its use level is relative to (A) Total 100 mass parts of composition and (B) composition is preferably 0.1～1 mass parts, more preferably 0.1～0.6 mass parts.

(alkali metal salt of (D) organic sulfonic acid and/or the alkali salt of organic sulfonic acid)

From the viewpoint of anti-flammability, the polycarbonate-based resin composition of the present invention can also coordinate selected from organic sulphur At least one in the alkali metal salt of acid and the alkali salt of organic sulfonic acid is as (D) composition.

As organic sulfonic acid, organic sulfonic acid, polystyrolsulfon acid etc. can be listed.

As alkali metal, sodium, potassium, lithium and caesium etc. can be listed.

It addition, as alkaline-earth metal, magnesium, calcium, strontium and barium etc. can be enumerated.Wherein, as organic sulfonate, preferably use The alkali metal salt of sodium, potassium and caesium.

In various organic sulfonic acid alkali metal salts and organic sulfonic acid alkali salt, preferably use following as organic sulfonic acid The alkali metal salt of perfluoroalkane sulfonate shown in formula (12), alkali salt.

(C_cF_2c+1SO₃)_dM···(12)

[in formula, c represents the integer of 1～10, and M represents the alkali such as the alkali metal such as lithium, sodium, potassium and caesium or magnesium, calcium, strontium and barium Earth metal, d represents the atomicity of M.]

The such as slaine described in Japanese Patent Publication 47-40445 publication belongs to these slaines.

In described formula (12), as perfluoroalkane sulfonate, include, for example out perfluor methanesulfonic acid, perfluor ethyl sulfonic acid, complete Fluorine propane sulfonic acid, perfluor fourth sulfonic acid, perfluoro-methyl fourth sulfonic acid, the own sulfonic acid of perfluor, perfluor sulfonic acid in heptan and perfluorooctane sulfonate etc..The most excellent Choosing uses their potassium salt.

It addition, can enumerate alkyl sulfonic acid, benzenesulfonic acid, alkyl benzene sulphonate, diphenyl sulfonic acid, LOMAR PWA EINECS 246-676-2,2,5-dichloro-benzenes sulphur Acid, 2,4,5-trichloro-benzenes sulfonic acid, sulfobenzide .-3-sulfonic acid, sulfobenzide .-3,3 '-disulfonic acid, naphthalene trisulfonic acid and their fluorine take For the alkali metal salt of the organic sulfonic acid such as thing and polystyrolsulfon acid, alkali salt etc..

As organic sulfonic acid, particularly preferred perfluoroalkane sulfonate and diphenyl sulfonic acid.

As alkali metal salt and/or the alkali salt of polystyrolsulfon acid, can list shown in following formula (13) Aromatic vinyl base system resin containing sulphonate-base.

[changing 5]

[in formula (13), X represents that sulphonate-base, m represent the integer of 1～5.Y represents hydrogen atom or carbon number 1～10 Alkyl.N represents mole fraction, is 0 < n 1.]

Here, the alkali metal salt that sulphonate-base is sulfonic acid and/or alkali salt, as metal, can list sodium, potassium, Lithium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium etc..

It should be noted that Y is hydrogen atom or the alkyl of carbon number 1～10, preferably hydrogen atom or methyl.

M is the integer of 1～5, and n is the relation of 0 ＜ n 1.

That is, sulphonate-base (X) can be replacement complete to aromatic rings, it is also possible to include replacing aromatic moiety or not taking Generation.

In the case of the polycarbonate-based resin composition of the present invention coordinates (D) composition, relative to (A) composition and (B) Total 100 its use level of mass parts of composition is preferably 0.01～0.15 mass parts, is preferably 0.02～0.13 mass parts, more excellent Elect 0.03～0.1 mass parts as.

(other compositions)

In the polycarbonate-based resin composition of the present invention, as other compositions, interpolation in the past can be coordinated as required Various additive kinds known in polycarbonate-based resin composition.As these other compositions, can enumerate such as: strengthen Material, filler, stabilizer, antioxidant, UV absorbent, antistatic agent, lubricant, releasing agent, dyestuff, pigment, its His fire retardant, resistance to impact improvement elastomer etc..

In the case of the polycarbonate-based resin composition of the present invention coordinates other compositions, relative to (A) composition and (B) Total 100 its use level of mass parts of composition is respectively preferably below below 20 mass parts, more preferably 10 mass parts, further It is preferably below 5 mass parts.

The polycarbonate-based resin composition of the present invention preferably coordinates phosphorus system stabilizer.

The polycarbonate-based resin composition of the present invention contains titanium oxide, but adds titanium oxide in polycarbonate-based resin Time, it is sometimes found that make polycarbonate-based resin decomposition so that it is the undesirable effect that molecular weight reduces.Phosphorus system stabilizer can be use up Suppress this undesirable effect possibly.

As the phosphorus system stabilizer used in the present invention, aromatic series phosphine compound and/or phosphoric acid based compound can be enumerated.

As aromatic series phosphine compound, can enumerate such as: triphenylphosphine, diphenyl butylphosphine, diphenyl octadecyl phosphine, Three (p-methylphenyl) phosphine, three (to nonyl phenyl) phosphine, three naphthyl phosphines, diphenyl-(hydroxymethyl)-phosphine, diphenyl-(acetyl oxygen Ylmethyl)-phosphine, diphenyl-(β-alkylcarboxy ethyl)-phosphine, three-(rubigan) phosphines, three-(to difluorophenyl) phosphines, hexichol Base benzyl phosphine, diphenyl-beta-cyano ethyl phosphine, diphenyl-(p-hydroxybenzene)-phosphine, diphenyl-Isosorbide-5-Nitrae-dihydroxy phenyl-2- Phosphine, phenyl napthyl benzyl phosphine etc..Wherein it is possible to particularly preferably use triphenylphosphine.

It addition, as phosphoric acid based compound, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester etc. can be enumerated.Specifically For, can enumerate: triphenyl phosphite, three (nonyl phenyl) phosphite ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, Tridecyl phosphite, trioctylphosphite, three (octadecyl) phosphite ester, didecyl list phenyl phosphites, two Octyl group list phenyl phosphites, diisopropyl list phenyl phosphites, diphenyl iso-octyl phosphite ester, diphenyl n-octyl are sub- Phosphate ester, monobutyl diphenylphosphite, single decyl diphenyl phosphite ester, single octyl diphenyl phosphite ester, double (2,6- Di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, 2,2-di-2-ethylhexylphosphine oxide (4,6-di-tert-butyl-phenyl) octyl group is sub- Phosphate ester, double (nonyl phenyl) pentaerythritol diphosphites, double (2,4-di-t-butyl phenyl) tetramethylolmethane diphosphorous acid Ester, distearyl pentaerythrityl diphosphite, Tributyl phosphate ester, triethyl phosphate, trimethyl phosphate, triphenyl phosphorus Acid esters, diphenyl list neighbour's biphenyl phosphate, dibutylphosphoric acid ester, dioctyl phosphate ester, diisopropyl phosphate ester, 4,4 '-connection Penylene di 2 ethylhexyl phosphonic acid four (2,4-di-tert-butyl-phenyl) ester, phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester, phenyl-phosphonic acid dipropyl Deng.

Be preferably diphenyl iso-octyl phosphite ester, diphenyl n-octyl phosphite ester, trisnonylphenyl phosphite, three Methyl phosphorodithioate, three (2,4-di-tert-butyl-phenyl) phosphite ester and phenyl-phosphonic acid dimethyl esters.

In the case of coordinating above-mentioned phosphorus system stabilizer, preferred relative to total 100 mass parts of (A) composition He (B) composition It it is 0.1～1 mass parts.

The polycarbonate-based resin composition of the present invention can be by by described (A) composition and (B) composition and according to need The described additive kind wanted coordinates, mixing and obtain.

This cooperation and mixing can pass through commonly used approach, such as, use ribbon blender (ribbon Blender), Henschel blender (henschel mixer), Banbury mixer (Banbury mixer), rotary drum (drum Tumbler), the method for single screw extrusion machine, double screw extruder, co-kneader, multi-screw extruder etc. is carried out.

It should be noted that mixing time heating-up temperature can usual 250～320 DEG C scope enter select.

The shaping of the polycarbonate-based resin composition of the present invention obtained as mentioned above can use known Various manufacturing process, such as: injection molding method, ejection compress moulding method, extrusion molding method, flow forming method, compressing method, Vacuum forming process and foaming and molding method etc..

It should be noted that in this specification, preferably (include preferred scope.) combination between technical scheme is certain Preferably, in all of regulation, arbitrarily preferably technical scheme (can be included preferred scope.) combination.

Embodiment

Embodiments of the invention are further illustrated.It should be noted that the present invention not any by these examples Limit.It should be noted that in each example, viscosity-average molecular weight (Mv), unreacted PDMS amount, the response rate of PDMS pass through following side Method is obtained.

(the 1. assay method of viscosity-average molecular weight (Mv))

The limiting viscosity (η) of the dichloromethane solution at using Ubbelohde viscosity pipet to measure 20 DEG C, and by following relation Formula (Schnell formula) calculates.

(η)=1.23 × 10^-5×Mv^0.83

(the 2. computational methods of unreacted PDMS amount)

I Merlon-polydimethylsiloxanecopolymer copolymer 6g that () obtains in each case is dissolved in dichloromethane 50ml institute After the solution obtained adding acetone 50ml and normal hexane 150ml and mixing, stand 30 minutes.

(ii) use filter paper (No.5A) to reclaim filtrate by sucking filtration, the filtrate reclaimed is concentrated solid, measure the dry of gained Gu the weight of thing.Obtained dry substance is dissolved in deuterochloroform, carries out¹H-NMR measures.From unreacted phenol modified poly-two Integrated value x of the proton (δ 6.7ppm) at the hydroxyl ortho position of methylsiloxane, belong to the proton (δ 0.6ppm) of methene chain Integrated value y, calculates ratio z (%) of unreacted PDMS by following formula.

Z=2 × x ÷ y × 100

(iii) on the other hand, additionally prepare in Merlon-polydimethylsiloxanecopolymer copolymer, be added with phenol modification to gather The standard specimen of dimethyl siloxane 150～2000ppm, carries out operation similar to the above, thus obtains z and unreacted PDMS and measures The relational expression of (ppm ,=phenol modified dimethyl polysiloxane addition).

By the z obtained in (ii) and the relational expression obtained by (iii), calculate unreacted PDMS and measure (ppm).

(computational methods of the response rate of 3.PDMS)

The response rate of PDMS is calculated according to following calculating formula.

PDMS response rate (quality %)=(1-unreacted PDMS measures (quality %) ÷ polydimethylsiloxaneresidue residue amount (matter Amount %)) × 100

The synthesis example of<synthesis example 1>polycarbonate oligomer

2000 mass ppm are added relative to bisphenol-A to be dissolved in the sodium hydrate aqueous solution of 5.6 mass % Sodium dithionite, dissolving bisphenol-A makes the concentration of bisphenol-A be 13.5 mass % wherein, prepares the sodium hydroxide water of bisphenol-A Solution.

Under the sodium hydrate aqueous solution 40L/hr of this bisphenol-A, the flow of dichloromethane 15L/hr, with the stream of 4.0kg/hr Measure the tube-type reactor to internal diameter 6mm, pipe range 30m and be passed through phosgene continuously.Tube-type reactor is with jacket portion, to chuck In be passed through cooling water, the temperature of reactant liquor is maintained at less than 40 DEG C.

The reactant liquor flowing out tube-type reactor is imported to have continuously the band baffle plate that internal volume is 40L of swept-back wing In tank reactor, then add the sodium hydrate aqueous solution of bisphenol-A with 2.8L/hr, add 25 matter with 0.07L/hr wherein Measure % sodium hydrate aqueous solution, add water with 17L/hr, add 1 mass % aqueous triethylamine with 0.64L/hr, carry out anti- Should.The reactant liquor overflowed from tank reactor is extracted out continuously, by standing, is separated off aqueous phase, collects dichloromethane phase.

The concentration of the polycarbonate oligomer so obtained is 318g/L, and chloro-carbonic acid ester group concentration is 0.75mol/L.Separately Outward, its weight average molecular weight (Mw) is 1190.

It should be noted that use THF (oxolane) is as developing solvent, by GPC (post: TOSOH TSK-GEL MULTIPORE HXL-M (2)+Shodex KF801 (1), temperature 40 DEG C, flow velocity 1.0ml/ minute, detector: RI), with The form of polystyrene standard conversion molecular weight (weight average molecular weight: Mw) measures weight average molecular weight (Mw).

<manufacturing example 1>Merlon-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-1]

The 50L tank reactor possessing baffle plate, slurry type stirring flabellum and cooling chuck adds in synthesis example 1 and manufactures Polycarbonate oligomer solution 15L, dichloromethane 8.9L, the 2-allyl that averaged repeating numbers is 40 of dimethylsiloxy units Base phenol end modified dimethyl polysiloxane (PDMS-1) 307g and triethylamine 8.8mL, adds 6.4 the most wherein Quality % sodium hydrate aqueous solution 1389g, carries out 10 minutes polycarbonate oligomers and 2-chavicol terminal-modified poly-two The reaction of methylsiloxane.

PTBP129g [is dissolved in dichloro by the dichloromethane solution adding p-t-butyl phenol (PTBP) in this polymer fluid Methane 2.0L and the solution that obtains], the sodium hydrate aqueous solution of bisphenol-A [make bisphenol-A 1147g be dissolved in sodium hydroxide 581g with The solution obtained in the aqueous solution that sodium dithionite 2.3g is dissolved in water 8.5L and obtains], implement 50 minutes polyreactions. Add after the dichloromethane 10L of dilution, stir 10 minutes, be then peeled off as the organic facies containing Merlon and contained The bisphenol-A of amount and the aqueous phase of sodium hydroxide, and isolate organic facies.

The dichloromethane solution of the Merlon-polydimethylsiloxanecopolymer copolymer for so obtaining, holds with 15 successively The long-pending 0.03mol/L sodium hydrate aqueous solution of %, 0.2mol/L hydrochloric acid are carried out, then by pure water repeated washing until cleaning After aqueous phase in electric conductivity be 0.01 below μ S/m.Merlon-the Dimethicone Copolyol that will be obtained by cleaning The dichloromethane solution of thing concentrates, pulverizes, and is under reduced pressure dried at 120 DEG C by obtained thin slice.

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-1) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 4.8 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 49.5, viscous Average molecular weight (Mv) is 18,600.It addition, the response rate that the amount of unreacted PDMS-1 is below 150ppm, PDMS-1 is More than 99.5%.

<manufacturing example 2>Merlon-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-2]

In manufacturing example 1, by the 2-terminal-modified PDMS of chavicol that the repeat number of dimethylsiloxy units is 40 (PDMS-1) usage amount is set to 256g, and the solution that use PTBP 107g is dissolved in dichloromethane 2.0L and obtains is as to uncle The dichloromethane solution of butylphenol (PTBP), operates the most equally, manufactures Merlon-polydimethylsiloxane Copolymer.

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-2) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 4.0 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 55.9, viscous Average molecular weight (Mv) is 21,400.It addition, the amount of unreacted PDMS-1 be below 150ppm, the response rate of PDMS-1 be More than 99.5%.

<manufacturing example 3>Merlon-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-3]

Manufacture in example 1, by the 2-terminal-modified PDMS of chavicol that the repeat number of dimethylsiloxy units is 40 (PDMS-1) usage amount is set to 384g, and the solution that use PTBP 137g is dissolved in dichloromethane 2.0L and obtains is as to uncle The dichloromethane solution of butylphenol (PTBP), operates the most equally, manufactures Merlon-polydimethylsiloxane Copolymer (SiPC-3).

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-3) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 6.1 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 47.5, viscous Average molecular weight (Mv) is 17,700.It addition, the amount of unreacted PDMS-1 be below 150ppm, the response rate of PDMS-1 be More than 99.5%.

<manufacturing example 4>Merlon-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-4]

Manufacture in example 3, replace the 2-terminal-modified PDMS of chavicol that repeat number is 40 of dimethylsiloxy units (PDMS-1) the terminal-modified PDMS of the 2-chavicol (PDMS-2) that repeat number is 52 of dimethylsiloxy units is used, Operate the most equally, manufacture Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-4).

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-4) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 6.0 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 47.5, viscous Average molecular weight (Mv) is 177,00.It addition, the amount of unreacted PDMS-2 be below 150ppm, the response rate of PDMS-2 be More than 99.5%.

<manufacturing example 5>Merlon-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-5]

Manufacture in example 1, by the 2-terminal-modified PDMS of chavicol that the repeat number of dimethylsiloxy units is 40 (PDMS-1) usage amount is set to 768g, operates the most equally, manufactures Merlon-Dimethicone Copolyol Thing (SiPC-5).

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-5) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 12 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 46.8, viscous all Molecular weight (Mv) is 17,400.It addition, the response rate that the amount of unreacted PDMS-1 is 200ppm, PDMS-1 be 99.5% with On.

<manufacturing example 6>Merlon-polydimethylsiloxanecopolymer copolymer (A-1) [SiPC-6]

Manufacture in example 1, by the terminal-modified PDMS (PDMS-of acetaminol that the repeat number of dimethylsiloxy units is 40 1) usage amount is set to 256g, operates the most equally, manufactures Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-6)。

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-6) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 4.7 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 49.5, viscous Average molecular weight (Mv) is 18,600.It addition, the amount of unreacted PDMS-1 be below 150ppm, the response rate of PDMS-1 be More than 99.5%.

<manufacturing example 7>Merlon-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-7]

Manufacture in example 2, replace the 2-terminal-modified PDMS of chavicol that repeat number is 40 of dimethylsiloxy units (PDMS-1) 256g and use the 2-terminal-modified PDMS of chavicol that repeat number is 150 of dimethylsiloxy units (PDMS-3) 256g, operates the most equally, manufactures Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-7).

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-7) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 3.9 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 55.9, viscous Average molecular weight (Mv) is 21,400.It addition, the amount of unreacted PDMS-3 be below 150ppm, the response rate of PDMS-3 be More than 99.5%.

<manufacturing example 8>Merlon-polydimethylsiloxanecopolymer copolymer (A-3) [SiPC-8]

Manufacture in example 6, replace the 2-terminal-modified PDMS of chavicol that repeat number is 150 of dimethylsiloxy units (PDMS-3) the terminal-modified PDMS of the 2-chavicol (PDMS-4) that repeat number is 20 of dimethylsiloxy units is used, Operate the most equally, manufacture Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-8).

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-8) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 4.1 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 55.4, viscous Average molecular weight (Mv) is 21,200.It addition, the amount of unreacted PDMS-4 be below 150ppm, the response rate of PDMS-4 be More than 99.5%.

<manufacturing example 9>Merlon-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-9],

Manufacture in example 6, replace the 2-terminal-modified PDMS of chavicol that repeat number is 150 of dimethylsiloxy units (PDMS-3) the terminal-modified PDMS of the 2-chavicol (PDMS-4) that repeat number is 90 of dimethylsiloxy units is used, Operate the most equally, manufacture Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-9).

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-9) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 4.0 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 55.9, viscous Average molecular weight (Mv) is 21,400.It addition, the amount of unreacted PDMS-4 be below 150ppm, the response rate of PDMS-4 be More than 99.5%.

<manufacturing example 10>Merlon-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-10]

Manufacture in example 3, replace the 2-terminal-modified PDMS of chavicol that repeat number is 40 of dimethylsiloxy units (PDMS-1) the terminal-modified PDMS of the 2-chavicol (PDMS-4) that repeat number is 90 of dimethylsiloxy units is used, Operate the most equally, manufacture Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-10).

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-10) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 6.0 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 47.5, viscous Average molecular weight (Mv) is 17,700.The amount of unreacted PDMS-4 is below 150ppm, the response rate of PDMS-4 be 99.5% with On.

<manufacturing example 11>Merlon-polydimethylsiloxanecopolymer copolymer (A-2) [SiPC-11]

(synthesis of the polycarbonate oligomer containing PDMS)

2000 mass ppm are added relative to bisphenol-A to be dissolved in the sodium hydrate aqueous solution of 5.6 mass % Sodium dithionite, dissolving bisphenol-A makes the concentration of BPA be 13.5 mass % wherein, and the sodium hydroxide preparing bisphenol-A is water-soluble Liquid.

With the 9.3 mass % dichloromethane solution 17L/hr of sodium hydrate aqueous solution 40L/hr, PDMS-2 of this bisphenol-A, The flow of phosgene 4.0Kg/hr is passed through internal diameter 6mm, the tube-type reactor of pipe range 30m continuously.Tube-type reactor is with chuck Part, is passed through cooling water in chuck, and the temperature of reactant liquor is maintained at less than 40 DEG C.

The concentration of the polycarbonate oligomer so obtained is 400g/L, and chloro-carbonic acid ester group concentration is 0.75mol/L.Separately Outward, its weight average molecular weight (Mw) is 2,110.

(manufacture of SiPC-11)

The poly-of above-mentioned manufacture is added in the 50L tank reactor possessing baffle plate, slurry type stirring flabellum and cooling chuck Carbonate oligomer solution 15L, dichloromethane 8.9L, p-t-butyl phenol (PTBP) dichloromethane solution [by PTBP 129g The solution being dissolved in dichloromethane 2.0L and obtain], triethylamine 8.8mL, add the sodium hydroxide of BPA the most wherein Aqueous solution [makes bisphenol-A 1231g be dissolved in sodium hydroxide 675g and sodium dithionite 2.4g and is dissolved in water 9.9L and the water that obtains The solution obtained in solution], implement 60 minutes polyreactions.Add the dichloromethane 10L for dilution, stir 10 minutes After, it is separated into the organic facies containing Merlon and the bisphenol-A containing excess and the aqueous phase of sodium hydroxide, and isolates organic Phase.

Being measured by NMR of Merlon-polydimethylsiloxanecopolymer copolymer (SiPC-11) that aforesaid operations obtains is obtained The amount of polydimethylsiloxaneresidue residue be 20 mass %, the viscosity number that measures based on ISO1628-4 (1999) be 49.5, viscous all Molecular weight (Mv) is 18,600.The amount of unreacted PDMS-2 is below 150ppm, the response rate of PDMS-2 is more than 99.5%.

Coordinate according to the use level (unit: mass parts) describing composition described in table 1, use band air ventSingle axle extruding machine, at resin temperature 280 DEG C, obtain granulated pellet.

After being dried 8 hours at 120 DEG C by obtained granulated pellet, use injection machine, at forming temperature 280 DEG C, 80 DEG C of hemostasis of mold temperature shape, obtain test film.Use the test film obtained by granulated pellet or injection moulding Carry out following mensuration.Result is as shown in table 1.

(1) Izod impact strength

According to JIS-K-7110, at-20 DEG C and 23 DEG C, measure band recess cantilever beam impact strength.

(2) formed products outward appearance

At 120 DEG C with drying machine after predrying 5 hours, with following condition by thickness 1.5mm, long 140mm, wide 140mm Formed products carry out 10 injection mouldings, the color appearance on its surface of visualization, be evaluated according to following metewand.

Zero: formed products surface is entirely without the striped observing brown～black

×: formed products surface observation to brown～the striped of black

(injection moulding condition)

Injection machine: Toshiba Machinery Co., Ltd.'s system " IS150E "

Barrel temperature: 300 DEG C

Mold temperature: 80 DEG C

(3) anti-flammability

Testing vertical flammability is carried out according to UL94 method under being equivalent to 1.5mm thickness.

[table 1]

[table 2]

Table 2

Hereinafter the annotation in Tables 1 and 2 is illustrated.

* 1: manufacture the Merlon-polydimethylsiloxanecopolymer copolymer manufactured respectively in example 1～11

* 2: " TARFLON FN1700A " (trade name, Idemitsu Kosen Co., Ltd.'s system, end group have tert-butyl benzene The bisphenol-a polycarbonate of phenol, viscosity number 46.6, viscosity-average molecular weight (Mv)=17,300)

* 3: " TARFLON FN1900A " (trade name, Idemitsu Kosen Co., Ltd.'s system, end group have tert-butyl benzene The bisphenol-a polycarbonate of phenol, viscosity number 51.1, viscosity-average molecular weight (Mv)=19,300)

* 4: " TARFLON FN2200A " (trade name, Idemitsu Kosen Co., Ltd.'s system, end group have tert-butyl benzene The bisphenol-a polycarbonate of phenol, viscosity number 55.6, viscosity-average molecular weight (Mv)=21,300)

* 5: " CR-63 " (Ishihara Sangyo Kaisha, Ltd.'s system, use silica-alumina 1% and dimethyl silscone 0.5% are right Titanium dioxide carries out the material after the process of surface, mean diameter: 0.21 μm)

* 6: " CR-60-2 " (Ishihara Sangyo Kaisha, Ltd.'s system, the polyhydric alcohol titanium oxide being coated with, mean diameter: 0.21 μ m)、

* 7: " PC3 " (Ishihara Sangyo Kaisha, Ltd.'s system, rutile-type, surface oxygen amount: 10 μm ol/g, surface alkali number: 4 μ mol/g)

* 8: " Metablen A-3800 " (trade name, Mitsubishi Rayon Co., Ltd's system)

* 9: " Eftop KFBS " (trade name, composition；Potassium perfluor butane sulfonate, Mitsubishi Materials electronization become Co., Ltd.'s system)

* 10: " IRGAFOS168 " (trade name, three (2,4-di-tert-butyl-phenyl) phosphite ester, Ciba Co., Ltd. System)

* 11: polydimethylsiloxaneresidue residue

As shown in Table 1, the polycarbonate-based resin composition of the present invention can maintain Merlon-polysiloxane Have outside the color of excellence while the excellent characteristic (resistance to impact under such as resistance to impact, particularly low temperature) of copolymer See.It addition, anti-flammability is the most excellent in embodiment 12 and 14.

On the other hand, the comparative example 1 and 3 from table 2 understands, and does not contains the poly-carbon of (A-1) and (A-2) containing (A-3) Acid ester resin compositions, the reduction of the resistance to impact under the reduction of its resistance to impact, particularly low temperature (-20 DEG C) is notable.It addition, Knowable to comparative example 2,4 and 6, do not contain the polycarbonate-based resin composition of (A-1) that averaged repeating numbers n is 25～65, its Even if containing (A-2) that averaged repeating numbers n is 70～350, color appearance is also deteriorated.Understand as shown in comparative example 5, containing (A- 2) and the polycarbonate-based resin composition of (A-3), although the resistance to impact at 23 DEG C can be maintained higher by it, but low Resistance to impact under temperature (-20 DEG C) significantly reduces.Further, understand as shown in comparative example 7, as the titanium oxide of (B) composition When content is too much, in the case of any in 23 DEG C and-20 DEG C, resistance to impact all significantly reduces.

Industrial applicability

The polycarbonate-based resin composition obtained by the present invention can be widely applied to electrical equipment-electronic equipment neck The various field such as territory, automotive field.Particularly can also be as mobile phone, notebook computer, digital camera, videocorder, electronic work The case material of tool etc. utilizes.

Claims

1. a polycarbonate-based resin composition, it contains (A) polycarbonate-based resin 99.9～96 mass parts and (B) oxygen Changing titanium 0.1～4 mass parts, wherein, (A) composition adds up to 100 mass parts with (B) composition,

Described (A) polycarbonate-based resin comprises:

Merlon-poly organo alkyl copolymer (A-1) 5～100 mass %, Merlon-polysiloxane copolymerization Thing (A-2) 0～95 mass % and aromatic copolycarbonate (A-3) 0～95 matter in addition to described (A-1) and (A-2) Amount %,

Described Merlon-poly organo alkyl copolymer (A-1) is that main chain has the repetitive shown in logical formula (I) and leads to The Merlon of the Component units shown in formula (II)-poly organo alkyl copolymer, wherein, the n in logical formula (II) be 25～ 65, and the content of the Component units shown in logical formula (II) is 2～10 mass %,

Described Merlon-poly organo alkyl copolymer (A-2) is that main chain has the repetitive shown in logical formula (I) and leads to The Merlon of the Component units shown in formula (II)-poly organo alkyl copolymer, wherein, the n in logical formula (II) be 70～ 350, and the content of the Component units shown in logical formula (II) is 2～20 mass %,

In the polycarbonate-based resin of (A) composition, from the content of the Component units shown in the logical formula (II) of (A-2) composition It is below 2.5 mass % relative to the total amount of (A-1)～(A-3) composition,

In formula, R¹And R²Separately represent halogen atom, the alkyl of carbon number 1～6 or the alkoxyl of carbon number 1～6, X Represent singly-bound, the alkylidene of carbon number 1～8, the alkylidene radical of carbon number 2～8, the ring alkylidene of carbon number 5～15, carbon The ring alkylidene radical of atomic number 5～15 ,-S-,-SO-,-SO₂-,-O-or-CO-, a and b separately represent 0 ～the integer of 4,

R³～R⁶Separately represent hydrogen atom, halogen atom or the alkyl of carbon number 1～6, the alkoxyl of carbon number 1～6 Or the aryl of carbon number 6～12, Y represents singly-bound, containing aliphatic or aromatic organic residue, and n is averaged repeating numbers.

Polycarbonate-based resin composition the most according to claim 1, wherein, at the Component units shown in logical formula (II) In, Y is the organic residue from chavicol or acetaminol.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein, at the repetitive shown in logical formula (I) In, X is isopropylidene, and a=b=0.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein, at the composition list shown in logical formula (II) In unit, R³～R⁶It is methyl.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein, relative to (A) composition and (B) composition Total 100 mass parts possibly together with (C) containing mixed powder 0.1～1 mass parts of politef.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein,

It is selected from organic sulphur possibly together with 0.01～0.15 mass parts (D) relative to total 100 mass parts of (A) composition and (B) composition At least one in the alkali metal salt of acid and the alkali salt of organic sulfonic acid.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein, in described (A-1), logical formula (II) The content of shown Component units is 3～8 mass %.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein, in described (A-1), logical formula (II) In averaged repeating numbers n be 30～60.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein, in described (A-1), logical formula (II) In averaged repeating numbers n be 30～50.

Polycarbonate-based resin composition the most according to claim 1 and 2, wherein, in described (A-1), formula (II) the averaged repeating numbers n in is 30～45.

11. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the viscosity-average molecular weight of described (A-1) (Mv) it is 16,000～30,000.

12. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the viscosity-average molecular weight of described (A-1) (Mv) it is 16,000～25,000.

13. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the viscosity-average molecular weight of described (A-1) (Mv) it is 17,000～23,000.

14. polycarbonate-based resin compositions according to claim 1 and 2, wherein, in described (A-2), formula (II) content of the Component units shown in is 2～15 mass %.

15. polycarbonate-based resin compositions according to claim 1 and 2, wherein, in described (A-2), formula (II) content of the Component units shown in is 2～10 mass %.

16. polycarbonate-based resin compositions according to claim 1 and 2, wherein, in described (A-2), formula (II) content of the Component units shown in is 3～8 mass %.

17. polycarbonate-based resin compositions according to claim 1 and 2, wherein, in described (A-2), formula (II) the averaged repeating numbers n in is 80～200.

18. polycarbonate-based resin compositions according to claim 1 and 2, wherein, in described (A-2), formula (II) the averaged repeating numbers n in is 80～110.

19. polycarbonate-based resin compositions according to claim 1 and 2, wherein, in described (A-2), formula (II) the averaged repeating numbers n in is 80～100.

20. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the viscosity-average molecular weight of described (A-2) (Mv) it is 16,000～30,000.

21. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the viscosity-average molecular weight of described (A-2) (Mv) it is 16,000～25,000.

22. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the viscosity-average molecular weight of described (A-2) (Mv) it is 17,000～23,000.

23. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the logical formula (II) in described (A-2) Shown Component units is below 2.0 mass % relative to described (A) composition total amount.

24. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described (A-3) is only by described formula (I) Component units shown in is constituted.

25. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described (A) is by (A-1) and (A- 2) constitute,

And comprise (A-1) and (A-2) of 80～5 mass % of 20～95 mass %.

26. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described (A) is by (A-1) and (A- 2) constitute,

And comprise (A-1) and (A-2) of 80～10 mass % of 20～90 mass %.

27. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described (A) is by (A-1) and (A- 3) constitute,

And comprise (A-1) and (A-3) of 80～5 mass % of 20～95 mass %.

28. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described (A) is by (A-1) and (A- 3) constitute,

And comprise (A-1) and (A-3) of 80～10 mass % of 20～90 mass %.

29. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described (A) comprise (A-1)～ (A-3),

And comprise (A-1) of 20～80 mass %, 10～60 (A-2) and (A-3) of 10～50 mass % of mass %.

30. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described (A) comprise (A-1)～ (A-3),

And comprise (A-1) of 25～60 mass %, 10～50 (A-2) and (A-3) of 25～60 mass % of mass %.

31. polycarbonate-based resin compositions according to claim 1 and 2, it contains described (A) polycarbonate-based resin 99.5～97 mass parts and described (B) titanium oxide 0.5～3 mass parts.

32. polycarbonate-based resin compositions according to claim 1 and 2, it contains described (A) polycarbonate-based resin 99.5～98 mass parts and described (B) titanium oxide 0.5～2 mass parts.

33. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described titanium oxide (B) once puts down All particle diameters are 0.05～0.5 μm.

34. polycarbonate-based resin compositions according to claim 1 and 2, wherein, once putting down of described (B) titanium oxide All particle diameters are 0.1～0.4 μm.

35. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described titanium oxide (B) once puts down All particle diameters are 0.15～0.3 μm.

36. polycarbonate-based resin compositions according to claim 1 and 2, wherein, the surface of described titanium oxide (B) by Including aluminum, silicon, magnesium, zirconium, titanium, the hydrous oxide of at least one element of tin element and/or oxide cladding.

37. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described titanium oxide (B) is by the most nitrogenous The polyhydric alcohol of atom, organo-silicon compound, alkanolamine, higher fatty acids carry out surface process.

38. polycarbonate-based resin compositions according to claim 1 and 2, wherein, described titanium oxide (B) is by titanium dioxide Silicon-aluminium oxide 1% and dimethyl silscone 0.5% carry out surface process.

39. polycarbonate-based resin compositions according to claim 5, wherein, relative to described (A) polycarbonate-based tree Fat and total 100 mass parts of (B) titanium oxide, the mixed powder containing politef of (C) containing 0.1～0.6 mass parts.

40. polycarbonate-based resin compositions according to claim 6, wherein, relative to described (A) polycarbonate-based tree Total 100 mass parts of fat and (B) titanium oxide, (D) containing 0.03～0.1 mass parts selected from organic sulfonic acid alkali metal salt and At least one in the alkali salt of organic sulfonic acid.

41. polycarbonate-based resin compositions according to claim 1 and 2, wherein, relative to described (A) Merlon It is total 100 mass parts of resin and (B) titanium oxide, the phosphorus system stabilizer containing 0.1～1 mass parts.

42. 1 kinds of formed products, it comprises the polycarbonate-based resin composition according to any one of Claims 1 to 41.

43. 1 kinds of elec-tric-electronic set spare unit, and it comprises the polycarbonate-based tree according to any one of Claims 1 to 41 Oil/fat composition.

44. 1 kinds of automotive parts, it comprises the polycarbonate-based resin composition according to any one of Claims 1 to 41.